POLYORGANIC FUNCTIONAL GROUPS MODIFIED SILICA, PROCESSES TO MAKE AND USE THEREOF
20190176124 · 2019-06-13
Assignee
Inventors
Cpc classification
B01J20/3219
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3204
PERFORMING OPERATIONS; TRANSPORTING
B01D53/02
PERFORMING OPERATIONS; TRANSPORTING
B01J31/069
PERFORMING OPERATIONS; TRANSPORTING
Y02W10/37
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/265
PERFORMING OPERATIONS; TRANSPORTING
B01J37/0219
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/005
PERFORMING OPERATIONS; TRANSPORTING
B01D2253/25
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3231
PERFORMING OPERATIONS; TRANSPORTING
B01J47/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
C07F7/18
CHEMISTRY; METALLURGY
B01D53/02
PERFORMING OPERATIONS; TRANSPORTING
B01J37/02
PERFORMING OPERATIONS; TRANSPORTING
B01J20/32
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to new compositions of polyorganic functional groups modified silica. The compositions contain a wide range of different functional groups such as mercapto, sulfide, thiourea, amines and amides in the same composition and each of these functional groups are present in an array of numerous different oligomers, configurations and stereochemistry. These functional groups have a strong affinity for metals and particular targets. Combining a high number of these functional groups together in the same composition enhances the overall binding affinity of the functionalised material. Combination with different structural configurations further enhances the capacity to bind to diverse structural variations in the targets found in actual process, product and waste streams. This multitude of binding mechanisms enables very high levels of purification and target removal as well as selectivity to be achieved in product, process and waste streams. The compounds are useful for the purification of products and for the removal of unwanted organic and inorganic compounds from product, process and waste streams, as chromatography medium for the purification and separation of metals, metal complexes and organic and biological compounds, for solid phase extraction, for solid phase synthesis, for metal mediated heterogeneous catalysis, for metal ion abstraction and for the immobilisation of bio-molecules.
Claims
1. Compositions of General Formula I:
[Y].sub.y[A].sub.a[B.sup.1].sub.1b[B.sup.2].sub.2b[C.sup.1].sub.1c[C.sup.2].sub.2c[C.sup.3].sub.3c[C.sup.4].sub.4c[D.sup.1].sub.1d[D.sup.2].sub.2d[D.sup.3].sub.3d[D.sup.4].sub.4d[D.sup.5].sub.5d[D.sup.6].sub.6d[E].sub.e[F].sub.f[G].sub.g[H].sub.h[J].sub.j[K].sub.k[M].sub.m[P].sub.p[U].sub.u[V].sub.v[W].sub.w[X].sub.xGeneral Formula I wherein Y is Si(O.sub.4/2); W is R.sub.zR.sup.1Si(O.sub.q/2); X is (O.sub.3/2)SiC.sub.3H.sub.6SH; A is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.a1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.a2 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SR].sub.a3; B.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SH].sub.b1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.b2 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.b3; B.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SH].sub.b1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.b2 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.b3; C.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.c2; C.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.c2; C.sup.3 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.c2; C.sup.4 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.c2; D.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1[(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.3 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.4 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.5 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.6 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; E is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2NR.sup.3R.sup.4]; F is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2SR].sub.f1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.f2; G is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2SR].sub.g1 [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.g2; H is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.3NZR]; J is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3NZR]; K is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.xR].sub.k1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.k2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.i(CH.sub.2).sub.3NZR].sub.k3; M is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.xR].sub.m1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S ((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.m2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.i(CH.sub.2).sub.3NZR].sub.m3; P is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S).sub.xR].sub.p1 [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.p2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S).sub.i(CH.sub.2).sub.2TR].sub.p3; U is [(O.sub.3/2Si(CH.sub.2).sub.3S(CH.sub.2).sub.3NHC(S)NH.sub.2; V is [O.sub.3/2Si(CH.sub.2).sub.nS[(CH.sub.2).sub.n1S].sub.n2R.sup.9 wherein Z is independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, CO NHR.sup.5, CS NHR.sup.5 and CO OR.sup.5; R.sup.z is independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group and C.sub.1-22-heteroaryl group; T is an optionally substituted C.sub.2-22-alkyl group, C.sub.2-22-cycloalkyl group, C.sub.2-22-aryl group, C.sub.2-22-heteroaryl group and C.sub.2-22-alkylaryl group; R is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, C.sub.1-22-alkylaryl group and an acyl group CO R.sup.2; R.sup.1 is a group which is optionally substituted and selected from a C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.2-22-alkynyl group, aryl group, alkyl amine group, alkyl polyalkyl amine group and a mercaptoalkyl group; R.sup.2 and R.sup.5 are independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group and a C.sub.1-22-aryl group; R.sup.3 and R.sup.4 are either independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.1-22-aryl group, C.sub.1-22-heteroaryl group, C.sub.1-22-alkylaryl group, alkyl amine group, alkyl polyalkyl amine group, a trialkyl ammonium group or both part of a C.sub.3-12-cyclic alkyl or hetero alkyl or aromatic group; R.sup.9 is (CH.sub.2).sub.3N.sup.+(L.sup.1)(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.3, (CH.sub.2).sub.3N.sup.+(L.sup.1)(CH.sub.3).sub.2CH.sub.2CHCH.sub.2 and a compound of General Formula III; n3 is an integer between 0 and 100; L.sup.1 is an anion including but not limited to a halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydride, cyanoborohydride; ##STR00002## n and n1 are integers independently either 2 or 3; n2 is an integer between 0 and 100; i, x and v are independent integers from 1 to 100; q is an integer from 1 to 3, z is an integer from 0 to 2 such that q+z=3; a, a13, 1b, 1b13, 2b, 2b13, 1c, 1c12, 2c, 2c12, 3c, 3c12, 4c, 4c12, 1d, 1d12, 2d, 2d12, 3d, 3d12, 4d, 4d12, 5d, 5d12, 6d, 6d12, e, f, f12, g, g12, h, j, k, k13, m, m13, p, p13, u, x, v, w and y are integers such that the ratio of y:a+(1 and 2)b+(1 to 4)c+(1 to 6)d+e+f+g+h+j+k+m+u+v+w+x is from 0.01 to 10,000; y:a+(1 and 2)b+(1 to 4)c+(1 to 6)d+e+f+g+u+v+w+x is from 0.01 to 10,000; y:f+g+h+j+k+m+u+w+x is from 0.01 to 10,000; y:e+f+g+u+v+w+x is from 0.01 to 10,000; y:f+g+h+j+p+u+w+x is from 0.01 to 10,000; and respectively each of the following ratios a1:a3; a1:a2+a3; 1b2:1b1+1b3; 2b2:2b1+2b3; 1c1:1c2; 2c1:2c2; 3c1:3c2; 4c1:4c2; 1d1:1d2; 2d1:2d2; 3d1:3d2; 4d1:4d2; 5d1:5d2; 6d1:6d2; f1:f2; g1:g2; k1:k3; k1:k2+k3; m1:m3; m1:m2+m3; and p1:p3; p1:p2+p3 vary independently between 0.01 to 100; and in General Formula I component Y and at least one of the following components A, B.sup.1-2, C.sup.1-4, D.sup.1-6, E, H, J, K, M, P, U and V are always present.
2. A composition as claimed in claim 1 wherein for General Formula I [Y].sub.y [A].sub.a [B.sup.1].sub.1b [B.sup.2].sub.2b [C.sup.1].sub.1c[C.sup.2].sub.2c [C.sup.3].sub.3c [C.sup.4].sub.4c [D.sup.1].sub.1d [D.sup.2].sub.2d [D.sup.3].sub.3d [D.sup.4].sub.4d [D.sup.5].sub.5d [D.sup.6].sub.6d [E].sub.e [F].sub.f [G].sub.g [U].sub.u [X].sub.x Y is Si(O.sub.4/2); X is (O.sub.3/2)SiC.sub.3H.sub.6SH; A is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.a1[(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.a2[(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SR].sub.a3; B.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SH].sub.b1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.b2[(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.b3; B.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SH].sub.b1[(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.b2 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.b3; C.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2.sub._Si(O.sub.3/2)].sub.c2; C.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2.sub._CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.c2; C.sup.3 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.c2; C.sup.4 is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SR].sub.c1 [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3Si(O.sub.3/2)].sub.c2; D.sup.1 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.2 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.3 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.4 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.5 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; D.sup.6 is [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SCH.sub.2CH.sub.2CH.sub.2SH].sub.d1 [(O.sub.3/2)Si(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2Si(O.sub.3/2)].sub.d2; E is [(O.sub.3/2)Si(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2NR.sup.3R.sup.4]; F is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2SR].sub.f1 [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.f2; G is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2SR].sub.g1 [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.g2; U is [(O.sub.3/2)Si(CH.sub.2).sub.3S(CH.sub.2).sub.3NHC(S)NH.sub.2; wherein R is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, C.sub.1-22-alkylaryl group and an acyl group CO R.sup.2; R.sup.1 is a group which is optionally substituted and selected from a C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.2-22-alkynyl group, aryl group, alkyl amine group, alkyl polyalkyl amine group and a mercaptoalkyl group; R.sup.2 and R.sup.5 are independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group and a C.sub.1-22-aryl group; R.sup.3 and R.sup.4 are independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.1-22-aryl group, C.sub.1-22-heteroaryl group, C.sub.1-22-alkylaryl group, alkyl amine group, alkyl polyalkyl amine group and a trialky ammonium group; n is an integer from 2 to 3; a, a13, 1b, 1b13, 2b, 2b13, 1c, 1c12, 2c, 2c12, 3c, 3c12, 4c, 4c12, 1d, 1d12, 2d, 2d12, 3d, 3d12, 4d, 4d12, 5d, 5d12, 6d, 6d12, e, f, f12, g, g12, u, x, and y are integers such that the ratio of y:a+(1 to 2)b+(1 to 4)c+(1 to 6)d+e+f+g+h+u+x is from 0.01 to 10,000; y:a+(1 and 2)b+(1 to 4)c+(1 to 6)d+e+f+g+u+x is from 0.01 to 10,000; and respectively each of the following ratios a1:a3; a1:a2+a3; 1b2:1b1+1b3; 2b2:2b1+2b3; 1c1:1c2; 2c1:2c2; 3c1:3c2; 4c1:4c2; 1d1:1d2; 2d1:2d2; 3d1:3d2; 4d1:4d2; 5d1:5d2; 6d1:6d2; f1:f2; g1:g2; vary independently between 0.01 to 100; and in General Formula I component Y and at least one of the following components A, B.sup.1-2, C.sup.1-4, D.sup.1-6, E, and U are always present.
3. A composition as claimed in claim 2 wherein components Y and at least one of the following components B.sup.1-2, D.sup.1-6, E and U are always present.
4. A composition as claimed in claim 2 wherein components Y and at least one of the following components B.sup.1-2 and E are always present.
5. A composition as claimed in claim 1 wherein for [Y].sub.y [E].sub.e [F].sub.f [G].sub.g [U].sub.u [X].sub.x Y is Si(O.sub.4/2); X is (O.sub.3/2)SiC.sub.3H.sub.6SH; E is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2NR.sup.3R.sup.4]; F is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2SR].sub.f1 [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.f2; G is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2SR].sub.g1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.g2; U is [(O.sub.3/2)Si(CH.sub.2).sub.3S(CH.sub.2).sub.3NHC(S)NH.sub.2; R is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, C.sub.1-22-alkylaryl group and CO CH.sub.3; R.sup.1 is a group which is optionally substituted and selected from a C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.2-22-alkynyl group, aryl group, alkyl amine group, alkyl polyalkyl amine group and a mercaptoalkyl group; R.sup.3 and R.sup.4 are either independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.1-22-aryl group, C.sub.1-22-heteroaryl group, C.sub.1-22-alkylaryl group, alkyl amine group, alkyl polyalkyl amine group or both R.sup.3 and R.sup.4 are part of a C.sub.3-12-cyclic alkyl or hetero alkyl group; n is an integer from 2 to 3; e, f, f12, g, g12, u, w and y are integers such that the ratio of y:e+f+g+u+w is from 0.01 to 1,000; f1:f2 and g1:g2 vary independently between 0.01 to 100 and in General Formula I the components Y and E are always present as well as one of the following components F, G, X and U.
6. A composition as claimed in claim 1 wherein for [Y].sub.y [F].sub.f [G].sub.g [H].sub.h [J].sub.j [K].sub.k [M].sub.m [U].sub.u [X].sub.x Y is Si(O.sub.4/2); X is (O.sub.3/2)SiC.sub.3H.sub.6SH; F is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2SR].sub.n[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.f2; G is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2SR].sub.g1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.g2; H is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.3NZR]; J is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.3NZR]; K is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.xR].sub.k1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.k2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2S).sub.i(CH.sub.2).sub.3NZR].sub.k3; M is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.xR].sub.m1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.m2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.3NZ(CH.sub.2).sub.3SCH.sub.2CH.sub.2CH.sub.2S).sub.3(CH.sub.2).sub.3NZR].sub.m3; U is [(O.sub.3/2)Si(CH.sub.2).sub.3S(CH.sub.2).sub.3NHC(S)NH.sub.2; wherein Z is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, CO NHR.sup.5, CS NHR.sup.5 and CO OR.sup.5; R is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, C.sub.1-22-alkylaryl group and an acyl group CO R.sup.2; R.sup.1 is a group which is optionally substituted and selected from a C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.2-22-alkynyl group, aryl group, alkyl amine group, alkyl polyalkyl amine group and a mercaptoalkyl group; R.sup.5 is independently selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group and a C.sub.1-22-aryl group; n is an integer from 2 to 3; i, u, x and v are independent integers from 1 to 100; f, f12, g, g12, h, j, k, k13, m, m13, w and y are integers such that the ratio of y:f+g+h+j+k+m+u+w is from 0.01 to 1,000; f1:f2; g1:g2; k1:k3; k1:k2+k3; m1:m3 and m1:m2+m3, vary independently between 0.01 to 100; in General Formula I the component Y and at least one of the following components H, J, K, M and U is present.
7. A composition as claimed in claim 6 wherein components Y and one of components F or G is present as well as at least one of H, J, K, M and U is present.
8. A composition as claimed in claim 1 wherein for [Y].sub.y [F].sub.f [G].sub.g [P].sub.p [U].sub.u [X].sub.x Y is Si(O.sub.4/2); X is (O.sub.3/2)SiC.sub.3H.sub.6SH; F is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2SR]n[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.f2; G is [(O.sub.3/2)Si(CH.sub.2)SCH.sub.2CH.sub.2SR].sub.g1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2S(CH.sub.2).sub.nSi(O.sub.3/2)].sub.g2; P is [(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S).sub.xR].sub.p1[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S).sub.v(CH.sub.2).sub.nSi(O.sub.3/2)].sub.p2[(O.sub.3/2)Si(CH.sub.2).sub.nSCH.sub.2CH.sub.2CH.sub.2S((CH.sub.2).sub.2T(CH.sub.2).sub.2SCH.sub.2CH.sub.2CH.sub.2S(CH.sub.2).sub.2TR].sub.3; U is [(O.sub.3/2)Si(CH.sub.2).sub.3S(CH.sub.2).sub.3NHC(S)NH.sub.2; wherein T is an optionally substituted C.sub.2-22-alkyl group, C.sub.2-22-aryl group, C.sub.2-22-heteroaryl group and a C.sub.2-22-alkylaryl group; R is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, C.sub.1-22-alkylaryl group and CO CH.sub.3; R.sup.1 is a group which is optionally substituted and selected from a C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.2-22-alkynyl group, aryl group, alkyl amine group, alkyl polyalkyl amine group and a mercaptoalkyl group; n is an integer from 2 to 3; i, x and v are independent integers from 1 to 100; f, f12, g, g12, p, p13, u, w and y are integers such that the ratio of y:f+g+p+u+w is from 0.01 to 10,000; f1:f2; g1:g2; p1:p3; p1:p2+p3; vary independently between 0.01 to 100; in General Formula I either components Y and P or components Y and U are always present.
9. A composition as claimed in claim 1 wherein either components Y, U, H and K or Y, U, J and M are present.
10. A composition as claimed in claim 1 wherein components Y, X and V or Y, F and V or Y, G and V are present.
11. (canceled)
12. A compound of General Formula II (R.sup.6O).sub.3Si(CH.sub.2).sub.nSQ where n is 2 then Q is (CH.sub.2).sub.2S(CH.sub.2).sub.3SH, (CH.sub.2).sub.3S(CH.sub.2).sub.2SH, (CH.sub.2).sub.3S(CH.sub.2).sub.3SH, (CH.sub.2).sub.4S(CH.sub.2).sub.3SH, (CH.sub.2).sub.3S(CH.sub.2).sub.2S(CH.sub.2).sub.3SH or (CH.sub.2).sub.3S(CH.sub.2).sub.3S(CH.sub.2).sub.3SH and R.sup.6 is selected from a C.sub.1-22-alkyl group or a C.sub.1-22-aryl group and where n is 3 then Q is (CH.sub.2).sub.3Cl, (CH.sub.2).sub.3NR.sup.3R.sup.4, S(CH.sub.2).sub.3S(CH.sub.2).sub.2SH, S(CH.sub.2).sub.3S(CH.sub.2).sub.3SH.
13. A process to make compounds of General Formula II where n is 3 and Q is (CH.sub.2).sub.3Cl, (CH.sub.2).sub.3NR.sup.3R.sup.4, S(CH.sub.2).sub.3S(CH.sub.2).sub.2SH, S(CH.sub.2).sub.3S(CH.sub.2).sub.3SH by the reaction of 3-mercaptopropyl trialkoxy silane with an allyl halide followed by a substitution reaction with a substituted amine or a dimercapto alkane.
14. A compound of General Formula II (R.sup.6O).sub.3Si(CH.sub.2).sub.nSQ where Q is (CH.sub.2).sub.2S(CH.sub.2).sub.3NRZ, ((CH.sub.2).sub.2S(CH.sub.2).sub.3NZ(CH.sub.2).sub.3S(CH.sub.2).sub.2S).sub.xH, (CH.sub.2).sub.3S(CH.sub.2).sub.3NRZ, ((CH.sub.2).sub.3S(CH.sub.2).sub.3NZ(CH.sub.2).sub.3S(CH.sub.2).sub.3S).sub.xH, ((CH.sub.2).sub.2S(CH.sub.2).sub.2T(CH.sub.2).sub.2S(CH.sub.2).sub.2S).sub.xH or ((CH.sub.2).sub.3S(CH.sub.2).sub.2T(CH.sub.2).sub.2S(CH.sub.2).sub.3S).sub.xH wherein Z is selected from a hydrogen, C.sub.1-22-alkyl group, C.sub.2-22-alkenyl group, C.sub.1-22-aryl group, CO NHR.sup.5, CS NHR.sup.5 and CO OR.sup.5; T is an optionally substituted C.sub.2-22-alkyl group, C.sub.2-22-aryl group, C.sub.2-22-heteroaryl group and a C.sub.2-22-alkylaryl group; R is selected from a hydrogen, C.sub.2-22-alkyl group, C.sub.2-22-aryl group, C.sub.2-22-alkylaryl group; R.sup.5 is selected from a hydrogen, C.sub.2-22-alkyl group, C.sub.2-22-aryl group, C.sub.2-22-alkylaryl group; R.sup.6 is selected from a C.sub.1-22-alkyl group or C.sub.1-22-aryl group, n is an integer from 2 to 3 and x is an integer from 1 to 100.
15. A compound of General Formula VI (R.sup.6O).sub.3Si(CH.sub.2).sub.3S[CH.sub.2CH(CH.sub.2M)(CH.sub.2CHCH.sub.2M).sub.n] H where M is a halide, amine, a polyalkyl amine, hydroxyl or a thiourea NH CS NHR.sup.5 and R.sup.5 is selected from a hydrogen, C.sub.1-12-alkyl group, C.sub.2-12-alkenyl group and a C.sub.1-22-aryl group and the integer u is 1 to 40.
16. A process to make compounds of General Formula I by first reacting either or a mixture of HS(CH.sub.2).sub.2SH and HS(CH.sub.2).sub.3SH with allyl amine or diallyl amine or their respective thiourea derivatives or triallyl amine and a radical initiator followed by a reaction with vinyl or allyl trialkoxy silane and a radical initiator and then either grafting onto silica or a sol gel reaction with either sodium silicate or a tetraalkyl orthosilane such as tetraethyl orthosilicate.
17. A process to make compounds of General Formula I by reacting either or a mixture of HS(CH.sub.2).sub.2SH and HS(CH.sub.2).sub.3SH with a dialkenyl organic compound and a radical initiator followed by reaction with vinyl or allyl trialkoxy silane and a radical initiator and then either grafting onto silica or a sol gel reaction with a tetra alkyl orthosilane such as tetraethyl orthosilicate.
18. A process for treating a feed material comprising, contacting a compound as claimed in claim 1 with a feed material: i.) to remove a component or components of the feed material so as to produce a material depleted in the removed component; ii.) to effect a chemical reaction by catalytic transformation of a component of the feed material to produce a desired product; or iii.) to remove an ionic species in the feed material in an ion exchange process.
19. Use of a compound as claimed in claim 1 as a functionalised material for the removal of or reducing the level of an unwanted organic, inorganic or biological compound from a liquid feed material.
20. Use of a compound as claimed in claims claim 1 as a functionalised material for the removal of or reducing the level of precious metals such as platinum, palladium, rhodium, iridium, gold, ruthenium, rhenium or rare earth metals and nickel from reaction mixtures, process, product and waste streams or waste waters or bound or attached to other organic compounds.
21-25. (canceled)
26. Use of a compound as claimed in claim 1 for the separation or purification of organic, biological or inorganic molecules from gaseous, liquid and solid environments.
27-29. (canceled)
Description
EXAMPLE 1
[0077] A solution of 1,2-dimercapto ethane (0.2 mol) and diallyl amine (0.1 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min. Vinyl trimethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.2 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (110 g, 60-200 m, 60 ) and toluene (300 mL). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed with methanol with centrifugation and dried to give a composition of General Formula I where Y, H and K are present and n is 2, Z is hydrogen and R in H is allyl.
EXAMPLE 2
[0078] A solution of 1,2-dimercapto ethane (0.25 mol) and diallyl amine (0.1 mol) was warmed to 120 C. and heated for a total of 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min. Vinyl trimethoxy silane (0.15 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.2 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (120 g, 60-200 m, 60 ) and toluene (300 mL). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, G, H and K are present and n is 2, Z is hydrogen and R in H is allyl.
EXAMPLE 3
[0079] A solution of 1,3-dimercapto propane (2 mol) and diallyl amine (1 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl triethoxy silane (1.4 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (2 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (1.2 kg, 60-200 m, 100-200 ) and toluene (3.6 L). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, J, M and U are present and n is 2, Z is hydrogen and R in J is allyl.
EXAMPLE 4
[0080] A solution of 1,3-dimercapto propane (2.7 mol) and diallyl amine (1 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl triethoxy silane (1.6 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (2.0 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (1.2 kg, 200-500 m, 100-200 ) and toluene (3.6 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, F, J and M are present and n is 2, Z is hydrogen and R in J is allyl.
EXAMPLE 5
[0081] A solution of 1,2-dimercapto ethane (0.6 mol) and diallyl amine (0.4 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min. Vinyl trimethoxy silane (0.8 mol) was added and the solution heated at 120 C. for 6 h with addition of di-tert-butyl peroxide (0.7 mL) every 30 min then cooled to 60 C. and added to a mixture of silica (420 g, 60-200 m, 60 ) and toluene (1.2 L). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol using centrifugation and dried to give a composition of General Formula I where Y, H, K and U are present and n is 2, Z is hydrogen and R in H is allyl.
EXAMPLE 6
[0082] A solution of 1,2-dimercapto ethane (0.6 mol) and diallyl amine (0.4 mol) was waiiiied to 120 C. and heated for 1 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min. Vinyl trimethoxy silane (0.6 mol) was added and the solution heated at 120 C. for 6 h with addition of di-tert-butyl peroxide (0.7 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (420 g, 60-200 m, 60 ) and toluene (1.2 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol using centrifugation and dried to give a composition of General Formula I where Y, G, H and K are present and n is 2, Z is hydrogen and R in H is allyl.
EXAMPLE 7
[0083] A solution of 1,3-dimercapto propane (12 mol) and diallyl amine (10 mol) was warmed to 130 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 20 min. Vinyl triethoxy silane (6 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (10 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (5 kg, 60-200 m, 100 ) and toluene (12 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, F, J and M are present and n is 2, Z is hydrogen and R in J is allyl.
EXAMPLE 8
[0084] A solution of 1,2-dimercapto ethane (0.5 mol) and diallyl amine (0.25 mol) was warmed to 120 C. and heated for a total of 4 h with the addition of di-tert-butyl peroxide (0.8 mL) every 15 min. Allyl trimethoxy silane (0.5 mol) was added and the solution heated at 120 C. for 6 h with addition of di-tert-butyl peroxide (1.5 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (400 g, 60-200 m, 150 ) and toluene (1.2 L). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.1 mol) (formed from reacting allyl thiourea (0.1 mol) and 3-mercaptopropyl trimethoxy silane (0.1 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, G, H, K and U are present and n is 3, Z is hydrogen and R in H is allyl.
EXAMPLE 9
[0085] A solution of 1,3-dimercapto propane (12 mol) and diallyl amine (10 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl triethoxy silane (6 mol) was added and the solution heated at 120 C. for 3 h with the addition of di-tert-butyl peroxide (10 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (6.0 kg, 60-200 m, 60 ) and toluene (14 L). Also added was a solution of N-methyl, N.sup.1 3-(3-(2-triethoxysilyl ethyl sulfyl) propylsulfide) propyl thiourea (1.25 mol) derived from the reaction first between 1,3-dimercapto propane and N-methyl, N.sup.1-allyl thiourea with a radical initiator then secondly the resultant reaction mixture was reacted with vinyl triethoxy silane at 120 C. for 4 h with a radical initiator. The combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (514 L) and dried to give a composition of General Formula I where Y, F, J and M are present and n is 2 and Z is CS NHCH.sub.3 in J and hydrogen in M.
EXAMPLE 10
[0086] A solution of 1,3-dimercapto propane (14 mol) and diallyl amine (10 mol) was warmed to 120 C. and heated for a total of 3 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl triethoxy silane (6 mol) was added and the solution heated at 120 C. for 3 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min then cooled to 60 C. and added to a stirred mixture of silica (6.0 kg, 60-200 m, 60 ) and toluene (14 L). Also added was a solution of N-methyl, N.sup.1 3-(3-(2-triethoxysilyl ethyl sulfyl) propylsulfide) propyl thiourea (1.25 mol) in toluene (100 mL). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol (514 L) and dried to give a composition of General Formula I where Y, F, J, M and U are present and n is 2 and Z is CS NHCH.sub.3 in J and hydrogen in M.
EXAMPLE 11
[0087] A solution of 1,2-dimercapto ethane (12 mol) and diallyl amine (8 mol) was warmed to 120 C. and heated for a total of 1 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl trimethoxy silane (8 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (10 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (6.7 kg, 60-200 m, 60 ) and toluene (17 L). Also added was a solution of N-methyl, N.sup.1 3-(2-(2-trimethoxysilyl ethyl sulfyl) ethylsulfide) propyl thiourea (1 mol) derived from the reaction first between 1,3-dimercapto propane and N-methyl, N.sup.1-allyl thiourea with a radical initiator then the resultant reaction mixture was reacted with vinyl trimethoxy silane at 120 C. for 4 h with a radical initiator. The combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (517 L) and dried to give a composition of General Formula I where Y, G, H and K are present and n is 2 and Z is CS NHCH.sub.3 in H and hydrogen in K.
EXAMPLE 12
[0088] A solution of 1,2-dimercapto ethane (12 mol) and diallyl amine (6 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl trimethoxy silane (8 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (10 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (8 kg, 200-500 m, 100 ) and toluene (24 L). Also added was a mixture of 3-aminopropyl trimethoxy silane (1 mol) and N-methyl, N.sup.1-3-(2-(2-trimethoxysilyl ethyl sulfyl) ethylsulfide) propyl thiourea (1 mol), the latter derived from the reaction first between 1,2-dimercapto ethane and N-methyl, N.sup.1-allyl thiourea with a radical initiator such as AIBN then the resultant reaction mixture was reacted with vinyl trimethoxy silane at 120 C. for 4 h with a radical initator such as di-tert-butyl peroxide. The combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (524 L) and dried to give a composition of General Formula I where Y, H, K and W are present and n is 2, Z is CS NHCH.sub.3 in H and hydrogen in K, R.sup.1 is 3-aminopropyl, the integer z is 0 and q is 3.
EXAMPLE 13
[0089] A solution of 1,2-dimercapto ethane (12 mol) and diallyl amine (6 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl trimethoxy silane (8 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (10 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (8 kg, 200-500 m, 100 ) and toluene (24 L). Also added was a mixture of 3-mercaptopropyl trimethoxy silane (1 mol) and 3-(3-(2-trimethoxysilyl ethyl sulfyl) propylsulfide) propylamine (1 mol), the latter derived from the reaction first between 1,3-dimercapto propane, N-allyl amine and AIBN then the resultant reaction mixture reacted with vinyl trimethoxy silane at 120 C. for 4 h and a radical initiator. The combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (524 L) and dried to give a composition of General Formula I where Y, G, J, K and W are present and n is 2, Z is CS NHCH.sub.3 in J and hydrogen in K, R.sup.1 is 3-mercaptopropyl, the integer z is 0 and q is 3.
EXAMPLE 14
[0090] A solution of 1,2-dimercapto ethane (0.6 mol) and N-diallyl, N.sup.1-methyl thiourea (0.2 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.2 mL) every 20 min. Vinyl trimethoxy silane (0.75 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.2 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (420 g, 60-200 m, 60 ) and toluene (1.2 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, G, H and K are present and n is 2, Z is CS NHCH.sub.3 and R in H is allyl.
EXAMPLE 15
[0091] A solution of 1,3-dimercapto propane (1 mol) and N-diallyl, N.sup.1-methyl thiourea (0.2 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (1 mL) every 25 min. Vinyl trimethoxy silane (1.2 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min then cooled to 60 C. and added to a stirred mixture of silica (800 g, 200-500 m, 160 ) and toluene (2.5 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, J and M are present and n is 2, Z is CS NHCH.sub.3 and R in J is allyl.
EXAMPLE 16
[0092] A solution of 1,2-dimercapto ethane (0.6 mol) and N-diallyl, N.sup.1-methyl thiourea (0.4 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.3 mL) every 15 min. Vinyl trimethoxy silane (0.55 mol) was added and the solution heated at 120 C. for 3 h with the addition of di-tert-butyl peroxide (0.5 mL) every 30 min then cooled to 60 C. and added along with vinyl trimethoxy silane (0.2 mol) to a stirred mixture of silica (500 g, 60-200 m, 100 ) and toluene (1.4 L). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, G, H, K and W are present and n is 2, Z is CS NHCH.sub.3, R is allyl in H, R.sup.1 is vinyl, the integer z is 0 and q is 3.
EXAMPLE 17
[0093] A solution of 1,3-dimercapto propane (1 mol) and N-diallyl, N.sup.1-methyl thiourea (0.5 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (2 mL) every 15 min. Vinyl trimethoxy silane (1.1 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (2 mL) every 20 min then cooled to 60 C. and added along with dimethyl dimethoxy silane (0.1 mol) to a stirred mixture of silica (800 g, 200-500 m, 160 ) and toluene (2.4 L). The mixture was stirred and refluxed for 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, F, J, M and W are present and n is 2, Z is CS NHCH.sub.3, R is allyl in J, R and R.sup.1 in W are methyl, the integer z is 1 and q is 2.
EXAMPLE 18
[0094] A solution of 1,3-dimercapto propane (1 mol) and N-diallyl, N.sup.1-methyl thiourea (0.5 mol) was warmed to 120 C. and heated for a total of 4 h with the addition of di-tert-butyl peroxide (2 mL) every 15 min. Vinyl trimethoxy silane (1.1 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (2 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (750 g, 200-500 m, 160 ) and xylene (2.4 L). The mixture was stirred and heated at 120 C. for 1 h then trimethyl methoxy silane (0.05 mol) added and the heating continued for another 4 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, J, M and W are present and n is 2, Z is CS NHCH.sub.3, R is allyl in J, R and R.sup.1 in W are methyl, the integer z is 2 and q is 1.
EXAMPLE 19
[0095] A solution of 1,2-dimercapto ethane (12 mol) and diallyl amine (6 mol) was warmed to 120 C. and heated for 1 h with the addition of di-tert-butyl peroxide (10 mL) every 15 min. Vinyl trimethoxy silane (8 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (7 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (8 kg, 200-500 m, 100 ) and xylene (24 L). The mixture was stirred and heated at 120 C. for 1 h then the mixture from the reaction between 1,3-dimercapto propane (0.7 mol) and vinyl trimethoxy silane (1 mol) with a radical initiator; and 2-trimethoxysilyl ethyl sulfyl hexane (1 mol) derived fiom the radical reaction between 1-mercapto hexane and vinyl trimethoxy silane at 120 C. for 4 h with AIBN, was added. The combined mixture was stirred and heated for a total of 6 h. On cooling the solid was filtered, washed well with methanol (524 L) and dried to give a composition of General Formula I where Y, F, G, H, K and W are present and n is 2, Z is hydrogen, R is allyl in H, R.sup.1 is hexylsulfylethyl, the integer z is 0 and q is 3.
EXAMPLE 20
[0096] A solution of 1,2-dimercapto ethane (1.2 mol), 1,3-dimercapto propane (0.6 mol) and vinyl trimethoxy silane (2.1 mol) was heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.8 mL) every 30 min. N-allyl, N.sup.i-methyl thiourea (0.5 mol) was added and the solution heated at 120 C. for 2 h with the addition of di-tert-butyl peroxide (2.0 mL) every 20 min. The resultant solution was added to a stifled mixture of silica (1.8 kg, 200-500 m, 100-200 ) and toluene (5.5 L) and the combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (56 L) and dried to give a composition of General Formula I where Y, F, G, H and J are present and n is 2, Z is CS NHCH.sub.3 and R is allyl in H and J.
EXAMPLE 21
[0097] A solution of 1,2-dimercapto ethane (1.2 mol), 1,3-dimercapto propane (0.6 mol) and vinyl trimethoxy silane (2.1 mol) was heated at 120 C. for 5 h with the addition of di-tert-butyl peroxide (1.6 mL) every 30 min. N-allyl, thiourea (1.8 mol) was added and the solution heated at 120 C. for 2 h with the addition of di-tert-butyl peroxide (1.6 mL) every 15 min. The resultant solution was added to a stirred mixture of silica (1.8 kg, 200-500 m, 100-200 ) and xylene (5.6 L) then the combined mixture was stirred and heated at 120 C. for a total of 6 h. On cooling the solid was filtered, washed well with methanol (56 L) and dried to give a composition of General Formula I where Y, F, G, H and J are present and n is 2, Z is CS NH.sub.2 and R is allyl in H and J.
EXAMPLE 22
[0098] A solution of 1,2-dimercapto ethane (0.2 mol) and N-allyl, thiourea (0.15 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.3 mL) every 20 min. Vinyl trimethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 5 h with the addition of di-tert-butyl peroxide (0.3 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (120 g, 60-200 m, 100-200 ) and toluene (360 mL). The mixture was stirred and refluxed for 1 h then 3-mercaptopropyl trimethoxysilane (0.04 mol) was added and the mixture stirred and refluxed for a further 4 h. On cooling the solid was filtered, washed well with methanol (4400 mL) and dried to give a composition of General Formula I where Y, G, H and X are present, Z is CS NH.sub.2 and n is 2.
EXAMPLE 23
[0099] A solution of 1,2-dimercapto ethane (0.2 mol) and N-allyl M-methyl thiourea (0.22 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.6 mL) every 15 min. Vinyl trimethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 5 h with the addition of di-tert-butyl peroxide (0.3 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (120 g, 60-200 m, 100-200 ) and toluene (370 mL). The mixture was stirred and refluxed for 1 h then 3-mercaptopropyl trimethoxysilane (0.04 mol) added and the mixture refluxed with stirring for a further 4 h. On cooling the solid was filtered, washed well with methanol (4400 mL) and dried to give a composition of General Formula I where Y, H and X are present and Z is CS NHCH.sub.3 and n is 2.
EXAMPLE 24
[0100] A solution of 1,3-dimercapto propane (0.4 mol) and N-allyl, N.sup.1-methyl thiourea (0.25 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (1.0 mL) every 15 min. Vinyl trimethoxy silane (0.3 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.8 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (220 g, 200-500 m, 100-200 ) and xylene (660 mL). The mixture was stirred and heated at 120 C. for a total of 5 h. On cooling the solid was filtered, washed well with methanol (4700 mL) and dried to give a composition of General Formula I where Y, F and J are present and Z is CS NHCH.sub.3 and n is 2.
EXAMPLE 25
[0101] A solution of 1,3-dimercapto propane (0.4 mol) and N-allyl, N.sup.1-methyl thiourea (0.45 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (1.0 mL) every 15 min. Vinyl trimethoxy silane (0.3 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.8 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (220 g, 200-500 rim, 100-200 ) and toluene (660 mL). The mixture was stirred and refluxed for a total of 5 h. On cooling the solid was filtered, washed well with methanol (4700 mL) and centrifugation then dried to give a composition of General Fmmula I where Y and J are present and Z is CS NHCH.sub.3 and n is 2.
EXAMPLE 26
[0102] A solution of 1,3-dimercapto propane (0.2 mol), 1,2-dimercapto ethane (0.2 mol) and N-allyl, N.sup.1-methyl thiourea (0.5 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min. Vinyl trimethoxy silane (0.3 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.5 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (280 g, 200-500 m, 100-200 ) and toluene (860 mL). The mixture was stirred and refluxed for 1 h then 3-mercaptopropyl trimethoxysilane (0.04 mol) added and the mixture refluxed with stirring for a further 4 h. On cooling the solid was filtered, washed well with methanol (4800 mL) and dried to give a composition of General Formula I where Y, X, H and J are present and Z is CS NHCH.sub.3 and n is 2.
EXAMPLE 27
[0103] A solution of 1,3-dimercapto propane (0.3 mol) and 1,5-hexadiene (0.22 mol) was warmed to 120 C. and heated for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 15 min. Vinyl trimethoxy silane (0.2 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.6 mL) every 15 min then cooled to 60 C. and added to a stirred mixture of silica (160 g, 200-500 100-200 ) and toluene (500 mL). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3 H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol (4600 mL) and dried to give a composition of General Formula I where Y, F, P and U are present, R in F is hydrogen and n is 2.
EXAMPLE 28
[0104] A solution of 1,3-dimercapto propane (0.3 mol) and 1,5-hexadiene (0.32 mol) was warmed to 120 C. and heated for a total of 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 20 min. Vinyl trimethoxy silane (0.15 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.4 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (160 g, 60-200 m, 100-200 ) and toluene (500 mL). The mixture was stirred and refluxed for 1 h then 3-mercaptopropyl trimethoxysilane (0.02 mol) added and the mixture refluxed with stirring for a further 4 h. On cooling the solid was filtered, washed well with (4600 mL) and dried to give a composition of General Formula I where Y, P and X are present and n is 2.
EXAMPLE 29
[0105] A solution of 1,2-dimercaptoethane(0.2 mol) and allyl thiourea (0.15 mol) was warmed to 120 C. and heated for a total of 4 h with the addition of di-tert-butyl peroxide (0.3 mL) every 20 min. Vinyl triethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.2 mL) every 30 min then cooled to 60 C. and added to a stirred mixture of silica (120 g, 60-200 m, 100-200 ) and xylene (360 mL). The mixture was stirred and heated at 120 C. for 5 h. On cooling the solid was filtered, washed well with methanol (4400 mL) and dried to give a composition of General Formula I where Y, G and U are present and n is 2.
EXAMPLE 30
[0106] A solution of 1,3-dimercapto propane (0.2 mol) and allyl thiourea (0.25 mol) was warmed to 120 C. and heated for a total of 4 h with the addition of di-tert-butyl peroxide (0.3 mL) every 15 min Vinyl triethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.2 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (120 g, 60-200 m, 100-200 ) and toluene (360 mL). The mixture was stirred and refluxed for 1 h then 3-mercaptopropyl trimethoxysilane (0.04 mol) added and the mixture refluxed with stirring for a further 4 h. On cooling the solid was filtered, washed well with methanol (4400 mL) and dried to give a composition of General Formula I where Y, U and X are present and n is 2.
EXAMPLE 31
[0107] Under nitrogen gas sodium ethoxide (0.1 mol) was added to a solution of 1,2-dimercapto ethane (0.1 mol) in ethanol (50 mL) and after stirring for 15 min, 1-chloro, 3-thioacetyl propane(0.11 mol) was added and the mixture refluxed for 2 h. Vinyl trimethoxy silane (0.11 mol) was added and the mixture refluxed for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 30 min. Morpholine (0.1 mol) was added and the mixture refluxed for a further 1 h. On cooling the sodium chloride was filtered off and the solution added to a stirred mixture of silica (80 g, 150-300m, 100 ) and xylene (240 mL) and the combined mixture was stirred and heated at 120 C. for a total of 6 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered off, washed well with methanol (5240 mL) and dried to give a composition of General Formula I where Y, A and G are present and n is 2 and R is hydrogen.
EXAMPLE 32
[0108] Under nitrogen gas sodium ethoxide (0.1 mol) was added to a solution of 1,2-dimercapto ethane (0.1 mol) in ethanol (50 mL) and after stirring for 15 min, 1-chloro, 3-thioacetyl propane (0.11 mol) was added and the mixture refluxed for 2 h. Vinyl trimethoxy silane (0.11 mol) was added and the mixture refluxed for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 30 min. Morpholine (0.1 mol) was added and the mixture refluxed for a further 1 h. On cooling the sodium chloride was filtered off and the solution added to a stirred mixture of silica (100 g, 37-74 m, 62 ) and xylene (250 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.03 mol) was added and heating and stirring was continued for another 7 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5240 mL) and dried to give a composition of General Formula I where Y, X, A and G are present and n is 2 and R is hydrogen.
EXAMPLE 33
[0109] Under nitrogen gas sodium ethoxide (0.1 mol) was added to a solution of 1,2-dimercapto ethane (0.14 mol) in ethanol (50 mL) and after stiffing for 15 min, 1-chloro, 3-thioacetyl propane (0.11 mol) was added and the mixture refluxed for 2 h. Vinyl trimethoxy silane (0.15 mol) was added and the mixture refluxed for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 30 min. Morpholine (0.1 mol) was added and the mixture refluxed for a further 1 h. On cooling the sodium chloride was filtered off then the solution added to a stirred mixture of silica (130 g, 37-74 m, 63 ) and xylene (320 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.03 mol) was added and heating and stirring was continued for another 7 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5400 mL) and dried to give a composition of General Formula I where Y, X, A and G are present and n is 2 and R is hydrogen.
EXAMPLE 34
[0110] Under nitrogen gas sodium ethoxide (0.1 mol) was added to a solution of 1,2-dimercapto ethane (0.14 mol) in ethanol (50 mL) and after stirring for 15 min, 1-chloro, 3-thioacetyl propane (0.11 mol) was added and the mixture refluxed for 2 h. Morpholine (0.1 mol) was added and the mixture refluxed for 1 h then vinyl trimethoxy silane (0.15 mol) was added and the mixture refluxed for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 30 min. On cooling the sodium chloride was filtered off then the solution added to a stirred mixture of silica (140 g, 40-70 m, 60 ) and xylene (360 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.04 mol) was added and heating and stirring was continued for another 8 h. On cooling, water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5340 mL) and dried to give a composition of General Formula I where Y, X, A and G are present and n is 2 and R is hydrogen.
EXAMPLE 35
[0111] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 2-mercapto 1-(0.16 mol) in methanol (50 mL) was added and the resultant solution refluxed for 2 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (100 g, 40-70 m, 60 ) and xylene (240 mL) then the combined mixture was stirred and heated at 120 C. for 6 h during which methanol was removed using Dean and Stark apparatus. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y and B.sup.1 (1b.sub.2 and 1b.sub.3) are present.
EXAMPLE 36
[0112] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed and a solution of 2-mercapto 1-sodium sulfide ethane (0.10 mol) in methanol (50 mL) added and the resultant solution refluxed for 2 h. Sodium sulfide (0.06 mol) was added and the mixture refluxed for a further 1 h then cooled. The solid was filtered off and the solution added to a stirred mixture of silica (100 g, 40-70 m, 60 ) and xylene (250 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which the methanol was removed using Dean and Stark apparatus. N-3-(3-trimethoxysilylpropylsulfyl)propylthiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.1mol) (formed from reacting allyl thiourea (0.1 mol) and 3-mercaptopropyl trimethoxy silane (0.1 mol) for 2 h at 125 C.) was added and the mixture heated and stirred for a further 4 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, U and B.sup.1 (1b.sub.2 and 1b.sub.3 are present.)
EXAMPLE 37
[0113] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 2-mercapto 1-sodium sulfide ethane (0.10 mol) in methanol (50 mL) added and the resultant solution refluxed for 2 h. Sodium sulfide (0.06 mol) was added and the mixture refluxed for a further 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (110 g, 40-70 m, 60 ) and xylene (300 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.04 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, X and B.sup.1 (1b.sub.2 and 1b.sub.3) are present.
EXAMPLE 38
[0114] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 3-mercapto 1-sodium sulfide propane (0.16 mol) in methanol (50 mL) was added and the resultant solution refluxed for 2 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (100 g, 40-70 m, 60 ) and xylene (240 mL) then the combined mixture was stirred and heated at 120 C. for 6 h during which methanol was removed using Dean and Stark apparatus. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y and B.sup.2 (2b.sub.2 and 2b.sub.3) are present.
EXAMPLE 39
[0115] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 3-mercapto 1-sodium sulfide propane (0.10 mol) in methanol (50 mL) was added and the resultant solution refluxed for 2 h. Sodium sulfide (0.06 mol) was added and the mixture refluxed for a further 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (150 g, 40-70 m, 60 ) and xylene (380 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) along with a solution from the reaction between 1,2-dimercapto ethane (0.02 mol), 1,3-dimercapto propane (0.02 mol) and vinyl trimethoxy silane (0.05 mol) heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 30 min, was added and heating and stirring was continued for another 7 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5380 mL) and dried to give a composition of General Formula I where Y, X, B.sup.2 (2b.sub.2 and 2b.sub.3), F, and G are present.
EXAMPLE 40
[0116] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 3-mercapto 1-sodium sulfide propane (0.06 mol) in methanol (50 mL) was added and the resultant solution refluxed for 2 h then sodium sulfide (0.1 mol) added and the mixture refluxed for a further 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (120 g, 150-300 m, 100 ) and xylene (320 mL) and the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5320 mL) and dried to give a composition of General Formula I where Y, X and B.sup.2 (2b.sub.2 and 2b.sub.3) are present.
EXAMPLE 41
[0117] Sodium methoxide (0.2 mol) was added to a stirred solution of 1,2-dimercapto ethane (0.2 mol) in methanol (50 mL) under an atmosphere of nitrogen. After 15 min, 1,2-dichloroethane (0.1 mol) was added and the resultant mixture refluxed for 2 h.
[0118] Vinyl trimethoxy silane (0.14 mol) was added and the mixture refluxed for a further 2 h with the addition of AIBN (0.05 g) every 15 min. The mixture was filtered and the solid washed with xylene (100 mL). The combined filtrates were added to a stirred mixture of silica (90 g, 40-70 m, 60 ) and xylene (180 mL) then the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) was added and heating and stirring was continued for another 6 h. On cooling water (100 mL) was added and after 1 h stirring the solid was filtered, washed well with methanol (5240 mL) and dried to give a composition of General Formula I where Y, X, C.sup.1 (1c.sub.1 and 1c.sub.2) and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 42
[0119] Under nitrogen gas sodium methoxide (0.2 mol) was added to a stirred solution of 1,2-dimercapto ethane (0.2 mol) in methanol (50 mL) under an atmosphere of nitrogen. After 15 min, 1,2-dichloroethane (0.1 mol) was added and the resultant mixture refluxed for 2 h. Vinyl trimethoxy silane (0.14 mol) was added and the mixture refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min. The mixture was filtered and the solid washed with xylene (100 mL). The combined filtrates were added to a stirred mixture of silica (80 g, 40-70 m, 60 ) and xylene (150 mL) then the combined mixture stirred and heated at 120 C. for 6 h during which methanol was removed. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5240 mL) and dried to give a composition of General Formula I where Y, C.sup.1 (1c.sub.1 and 1c.sub.2) and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 43
[0120] Sodium methoxide (0.2 mol) was added to a stirred solution of 1,2-dimercapto ethane (0.2 mol) in methanol (50 mL) under an atmosphere of nitrogen. After 15 min, 1,2-dichloroethane (0.1 mol) was added and the resultant mixture refluxed for 2 h. Vinyl trimethoxy silane (0.14 mol) was added and the mixture refluxed for a further 2 h with the addition of AIBN (0.05 g) every 15 min. The mixture was filtered and the solid washed with xylene (100 mL). The combined filtrates were added to a stirred mixture of silica (180 g, 40-70 m, 60 ) and xylene (420 mL) then the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) along with a solution from the reaction between 1,2-dimercapto ethane (0.02 mol), 1,3-dimercapto propane (0.02 mol) and vinyl trimethoxy silane (0.05 mol) heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 30 min, was added and heating and stirring continued for another 8 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5480 mL) and dried to give a composition of General Formula I where Y, X, C.sup.1 (1c.sub.1 and 1c.sub.2), F and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 44
[0121] Sodium methoxide (0.2 mol) was added to a stirred solution of 1,3-dimercapto propane (0.2 mol) in methanol (50 mL) under an atmosphere of nitrogen. After 15 min, 1,2-dichloroethane (0.1 mol) was added and the resultant mixture refluxed for 2 h. Vinyl trimethoxy silane (0.14 mol) was added and the mixture refluxed for a further 2 h with the addition of AIBN (0.05 g) every 15 min. The mixture was filtered and the solid washed with xylene (100 mL). The combined filtrates were added to a stirred mixture of silica (90 g, 40-70 m, 60 ) and xylene (160 mL) then the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) was added and heating and stirring was continued for another 7 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5240 mL) and dried to give a composition of General Formula I where Y, X, C.sup.2 (2ci and 2c.sub.2) and F are present.
EXAMPLE 45
[0122] Sodium methoxide (0.2 mol) was added to a stirred solution of 1,3-dimercapto propane (0.2 mol) in methanol (50 mL) under an atmosphere of nitrogen. After 15 min, 1,2-dichloroethane (0.1 mol) was added and the resultant mixture refluxed for 2 h. Vinyl trimethoxy silane (0.14 mol) was added and the mixture refluxed for a further 4 h with the addition of AIBN (0.05 g) every 15 min. The mixture was filtered and the solid washed with xylene (100 mL). The combined filtrates were added to a stirred mixture of silica (180 g, 40-70 m, 60 ) and xylene (480 mL) then the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) was added along with a solution from the reaction between 1,2-dimercapto ethane (0.02 mol), 1,3-dimercapto propane (0.02 mol) and vinyl trimethoxy silane (0.05 mol) heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 30 min and heating and stiffing was continued for another 7 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5480 mL) and dried to give a composition of General Formula I where Y, X, C.sup.2 (2c.sub.1 and 2c.sub.2), F and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 46
[0123] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure then a solution of 2-mercapto 1-sodium sulfide ethane (0.16 mol) in methanol (50 mL) added. The resultant solution was refluxed for 2 h then sodium methoxide (0.16 mol) added. After 15 min, 1-chloro, 3-thioacetyl propane (0.16 mol) was added and the mixture refluxed for 2 h. Morpholine (0.16 mol) was added and the mixture refluxed for 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (120 g, 150-300 m, 100 ) and xylene (320 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5360 mL) and dried to give a composition of General Formula I where Y, X and C.sup.3 (3c.sub.1 and 3c.sub.2) are present.
EXAMPLE 47
[0124] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and a solution of 3-mercapto 1-sodium sulfide propane (0.16 mol) in methanol (50 mL) added. The resultant solution was refluxed for 2 h then sodium methoxide (0.16 mol) added. After 15 min, 1-chloro, 3-thioacetyl propane (0.16 mol) was added and the mixture refluxed for 2 h. Morpholine (0.16 mol) was added and the mixture refluxed for 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (100 g, 150-300 m, 100 ) and xylene (240 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. Heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y and C.sup.4 (4c.sub.1 and 4c.sub.2) are present.
EXAMPLE 48
[0125] Under nitrogen gas a solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure then a solution of 3-mercapto 1-sodium sulfide propane (0.16 mol) in methanol (50 mL) was added and the resultant solution refluxed for 2 h. Sodium methoxide (0.16 mol) was added followed by 1-chloro, 3-thioacetyl propane (0.16 mol) 15 min later and the mixture refluxed for 2 h. Morpholine (0.16 mol) was added and the mixture refluxed for 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of silica (200 g, 150-300 m, 100 ) and xylene (540 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.06 mol) along with a solution from the reaction between 1,2-dimercapto ethane (0.02 mol), 1,3-dimercapto propane (0.02 mol) and vinyl trirnethoxy silane (0.05 mol) heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 30 min, was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5500 mL) and dried to give a composition of General Formula I where Y, X, C.sup.4 (4c.sub.1 and 4c.sub.2) F and G are present.
EXAMPLE 49
[0126] Under nitrogen gas a solution of 1,2-dimercapto ethane (0.16 mol) and vinyl trirnethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.1 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.1 g) every 15 min. The excess allyl chloride was removed under reduced pressure. A solution of sodium sulfide (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (130 g, 37-74 m, 63 ) and xylene (320 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y and D.sup.1 (1d.sub.1 and 1d.sub.2) are present.
EXAMPLE 50
[0127] Under nitrogen gas a solution of 1,2-dimercapto ethane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure. A solution of sodium sulfide (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (140 g, 37-74 m, 165 ) and xylene (340 mL) then the mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.02 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, D.sup.1 (1d.sub.1 and 1d.sub.2), G (g.sub.1 and g.sub.2) and X are present.
EXAMPLE 51
[0128] Under nitrogen gas a solution of 1,3-dimercapto propane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed under reduced pressure. A solution of sodium sulfide (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stiffed mixture of silica (130 g, 150-300 m, 60 ) and xylene (320 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5350 mL) and dried to give a composition of General Formula I where Y, D.sup.2 (2d.sub.1 and 2d.sub.2) and F are present.
EXAMPLE 52
[0129] Under nitrogen gas a solution of 1,3-dimercapto propane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed under reduced pressure. A solution of sodium sulfide (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled and then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (160 g, 150-300 m, 60 ) and xylene (440 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.02 mol) was added along with a solution from the reaction between 1,2-dimercapto ethane (0.02 mol), 1,3-dimercapto propane (0.02 mol) and vinyl trimethoxy silane (0.05 mol) heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 30 min and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5360 mL) and dried to give a composition of General Formula I where Y, X, D.sup.2 (2d.sub.1 and 2d.sub.2), F and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 53
[0130] A solution of 1,2-dimercapto ethane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.04 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed. A solution of 2-mercapto 1-sodium sulfide ethane (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (130 g, 150-300 m, 100 ) and xylene (240 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, D.sup.3 (3d.sub.1 and 3d.sub.2) and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 54
[0131] A solution of 1,2-dimercapto ethane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed under reduced pressure. A solution of 3-mercapto 1-sodium sulfide propane (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stifled mixture of silica (130 g, 150-300 m, 100 ) and xylene (340 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed. Heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5320 mL) and dried to give a composition of General Formula I where Y, D.sup.4 (4d.sub.1 and 4d.sub.2) and G (g.sub.1 and g.sub.2) are present.
EXAMPLE 55
[0132] A solution of 1,3-dimercapto propane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0.2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed under reduced pressure. A solution of 2-mercapto 1-sodium sulfide ethane (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (130 g, 150-300 m, 60 ) and xylene (340 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5320 mL) and dried to give a composition of General Formula I where Y, D.sup.5 (5d.sub.1 and 5d.sub.2) and F are present.
EXAMPLE 56
[0133] A solution of 1,3-dimercapto propane (0.16 mol) and vinyl trimethoxy silane (0.19 mol) was heated at 120 C. for 1 h with the addition of di-tert-butyl peroxide (0. 2 mL) every 15 min then cooled. Allyl chloride (0.25 mol) was added and the solution refluxed for 2 h with the addition of AIBN (0.05 g) every 15 min then the excess allyl chloride was removed under reduced pressure. A solution of 3-mercapto 1-sodium sulfide propane (0.12 mol) in methanol (80 mL) was added and the mixture refluxed for 2 h under an atmosphere of nitrogen, cooled then filtered. The solid was washed with xylene (100 mL) and the combined filtrates added to a stirred mixture of silica (140 g, 150-300 m, 60 ) and xylene (360 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed. 3-Mercaptopropyl trimethoxysilane (0.02 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after 1 h stirring the solid was filtered, washed well with methanol (5350 mL) and dried to give a composition of General Formula I where Y, F, D.sup.6 (6d.sub.1 and 6d2) and X are present.
EXAMPLE 57
[0134] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure and diethylene triamine (0.20 mol) added. The resultant solution was refluxed for 2 h then methanol (100 mL) added and the solution refluxed for a further 1 h. The solution was added to a stiffed mixture of silica (125 g, 150-300 m, 60 ) and xylene (320 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stiffing was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5330 mL) and dried to give a composition of General Formula I where Y, X and E are present.
EXAMPLE 58
[0135] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure and tetraethylene pentaamine (0.23 mol) added. The resultant solution was refluxed for 2 h then methanol (100 mL) added and the solution refluxed for a further 1 h. The solution was then added to a stirred mixture of silica (125 g, 150-300 m, 60 ) and xylene (320 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stifling was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, X and E are present.
EXAMPLE 59
[0136] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure and piperazine (0.23 mol) added. After refluxing for 2 h reflux, methanol (100 mL) was added and the solution refluxed for a further 1 h. The solution was added to a stirred mixture of silica (125 g, 150-300 m, 60 ) and xylene (320 mL) and the combined mixture stifled and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stirring was continued for 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, X and E are present.
EXAMPLE 61
[0137] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure and tributylamine (0.23 mol) added. The resultant solution was refluxed for 2 h then methanol (100 mL) added and the solution refluxed for a further 1 h. The solution was added to a stirred mixture of silica (125 g, 150-300 m, 60 ) and xylene (320 mL) and the combined mixture stirred and heated at 120 C. for 1 h during which methanol was removed. 3-Mercaptopropyl trimethoxysilane (0.05 mol) was added and heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, X and E are present.
EXAMPLE 62
[0138] A solution of 1,3-dimercapto propane (12 mol) and diallyl amine (10 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (10 mL) every 20 min. Vinyl triethoxy silane (6 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (10 mL) every 30 min then the solution was added to a stirred mixture of silica (8.0 kg, 60-200 m, 60 ) and toluene (20 L). Also added after 1 h was a solution from the reaction between 1,3-dimercapto propane (1.5 mol) and vinyl triethoxy silane (2 mol) at 120 C. for 4 h. The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol (520 L) and centrifugation and dried to give a composition of General Formula I where Y, F, J, M and U are present and Z is hydrogen and n is 2.
EXAMPLE 63
[0139] A solution of 1,2-dimercapto ethane (0.2 mol) and diallyl amine (0.1 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.1 mL) every 20 min. Vinyl trimethoxy silane (0.14 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (0.1 mL) every 25 min then cooled to room temperature. The solution was added to a stirred mixture of tetraethyl orthosilicate (125 g, 0.6 mol) dissolved in methanol (400 mL) and 1 M HCl (72 mL). The mixture was then warmed at 80 C. until the methanol had evaporated and a glass had fowled. The glass was milled then stirred in refluxing methanol and filtered. The material was dried to give a compound of General Formula I, where Y, G, H and K are present.
EXAMPLE 64
[0140] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stifling for 2 h with the addition of AIBN (0.05 g) every 15 min. Excess allyl chloride was removed under reduced pressure then a solution of 3-mercapto 1-sodium sulfide propane (0.06 mol) in methanol (50 mL) added and the resultant solution refluxed for 2 h. Sodium sulfide (0.1 mol) was added and the mixture refluxed for a further 1 h then cooled. The sodium chloride was filtered off and the solution added to a stirred mixture of tetraethyl orthosilicate (1.6 mol) dissolved in methanol (1.3 L) and 1 M HCl (200 mL). The mixture was then warmed at 80 C. until the methanol had evaporated and a glass had formed. The glass was milled, stirred in first refluxing water then methanol and filtered. The material was then dried to give a compound of General Formula I where Y and B.sup.2 (2b.sub.1 and 2b.sub.2) are present.
EXAMPLE 65
[0141] Under nitrogen gas a solution of 1,3-dimercapto propane (6 mol), 1,2-dimercapto ethane (6 mol) and diallyl amine (6 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (7 mL) every 15 min. Vinyl triethoxy silane (8 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (7 mL) every 20 min. The solution was then added to a stirred mixture of silica (8.0 kg, 60-200 m, 60 ) and toluene (20 L). Also added was a filtered solution from the following reaction sequence, sodium ethoxide (0.5 mol) with 1,2-dimercapto ethane (0.5 mol) in ethanol (200 mL) and after 15 min of stirring 1-chloro, 3-thioacetyl propane (0.55 mol) was added and the mixture refluxed for 2 h; vinyl trimethoxy silane (0.55 mol) was added then the mixture refluxed for 4 h with the addition of di-tert-butyl peroxide (0.4 mL) every 30 min. Morpholine (0.5 mol) was added and the mixture refluxed for a further 1 h. The filtered solution from the reaction sequence of a solution of 3-mercaptopropyl trimethoxysilane (0.6 mol) refluxed with allyl chloride (1.2 mol) for 2 h with the addition of AIBN (0.5 g) every 15 min was then added; the excess allyl chloride was removed under reduced pressure and a solution of 2-mercapto, 1-sodium sulfide ethane (0.30 mol) in methanol (100 mL) added and the resultant solution refluxed for 2 h then sodium sulfide (0.3 mol) added and the mixture refluxed for a further 1 h then cooled. The combined mixture was stirred and refluxed for 6 h. On cooling water (21 L) was added and the mixture stirred for 1 h then the solid filtered, washed with methanol (520 L) and water (220 L). The material was dried to give a composition of General Formula I where Y, A, B.sup.2 (2b.sub.1 and 2b.sub.2), G (g.sub.1 and g.sub.2), H, J, K and M are present and n is 2 and Z is hydrogen.
EXAMPLE 66
[0142] A solution of 1,3-dimercapto propane (3 mol), 1,2-dimercapto ethane (8 mol) and diallyl amine (5 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert butyl peroxide (2 mL) every 20 min. Vinyl triethoxy silane (8 mol) was added and the solution heated at 120 C. for 6 h with the addition of di-tert-butyl peroxide (10 mL) every 20 min. Then a filtered solution from the reaction sequence as follows, sodium ethoxide (0.5 mol) with 1,2-dimercapto ethane (0.5 mol) in ethanol (200 mL) and after 15 min of stirring 1-chloro, 3-thioacetyl propane (0.55 mol) was added and the mixture refluxed for 2 h; and 3-diethylene triamine 1-(3-trimethoxysilylpropyl sulfyl) propane (0.5 mol) was added to a stirred mixture of silica (8.0 kg, 60-200 m, 60 ) and toluene (20 L). Also added was a filtered solution from the following reaction sequence, 3-mercaptopropyl trimethoxysilane (0.5 mol) and allyl chloride (0.8 mol) refluxed with stirring for 2 h with the addition of AIBN (0.1 g) every 15 min; the excess allyl chloride was removed under reduced pressure and a solution of 2-mercapto 1-sodium sulfide ethane (0.40 mol) in methanol (100 mL) added and the resultant solution refluxed for 2 h then sodium sulfide (0.1 mol) was added and the mixture refluxed for a further 1 h then cooled. On cooling the reaction mixture was stirred with de-ionised water (10 L) and the solid was filtered, washed well with methanol (520 L) and de-ionised water (20 L) and dried to give a composition of General Formula I where Y, A, B.sup.2 (2b.sub.1 and 2b.sub.2), E, F, G (g.sub.1 and g.sub.2), H, J, K and M are present and Z is hydrogen and n is 2.
EXAMPLE 67
[0143] A solution of 1,3-dimercapto propane (1.2 mol) and N-methyl, N.sup.1-diallyl thiourea (1 mol) was warmed to 120 C. and heated for 2 h with the addition of di-tert-butyl peroxide (0.8 mL) every 20 min. Vinyl trimethoxy silane (0.8 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.1 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (500 g, 300-500 m, 100-200 ) and toluene (1.4 L). The combined mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol (52 L) and dried to give a composition of General Formula I where Y, J and M are present, n is 2 and Z is CS NHCH.sub.3.
EXAMPLE 68
[0144] A solution of 1,3-dimercapto propane (0.6 mol) and triallyl amine (0.4 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-tert-butyl peroxide (0.5 mL) every 15 min. Vinyl trimethoxy silane (0.5 mol) was added and the solution heated at 120 C. for 4 h with the addition of di-tert-butyl peroxide (0.2 mL) every 20 min then cooled to 60 C. and added to a stirred mixture of silica (400 g, 200-500 m, 100-200 ) and toluene (1.2 L). The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.2 mol) (formed from reacting allyl thiourea (0.2 mol) and 3-mercaptopropyl trimethoxy silane (0.2 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling the solid was filtered, washed well with methanol (51.5 L) and dried to give a composition of General Formula I where Y, J, M and U are present, n is 2 and Z and R are allyl.
EXAMPLE 69
[0145] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure and the solution added to a stirred mixture of silica (100 g, 150-300 m, 100 ) and xylene (280 mL) then the combined mixture was stirred and heated at 120 C. for 6 h. On cooling the solid was filtered, washed well with methanol (2300 mL) and dried to give a composition of General Formula I where Y and E are present.
EXAMPLE 70
[0146] A solution of 3-mercaptopropyl trimethoxy silane (0.24 mol) and N-diallyl, N.sup.1-methyl thiourea (0.12 mol) was warmed to 120 C. and heated for a total of 2 h with the addition of di-teat-butyl peroxide (0.3 mL) every 15 min then added to a stirred mixture of silica (100 g, 60-200 m, 100 ) and toluene (260 mL). The mixture was stirred and refluxed for a total of 6 h. On cooling the solid was filtered, washed well with methanol and dried to give a composition of General Formula I where Y, X and M are present and Z is methyl.
EXAMPLE 71
[0147] A mixture of 3-mercaptopropyl silica (20 g, 60-200 m, 100 , 1.2 mmol/g), diallyl dimethyl ammonium chloride (0.12 mol, 60% in water) and de-ionised water (60 mL) was heated at 110 C. for 20 h with the addition of tert-butyl hydrogen peroxide (0.1 mL) every 15 min. On cooling to 50 C. de-ionised water was added and the solution stirred for 10 min then filtered. The solid was stirred and filtered in de-ionised water (5100 mL) then in methanol (100 mL) and dried to give to give a composition of General Formula I where Y, X and V are present and n is 3, n2 is zero; R.sup.9 is a mixture of (CH.sub.2)N.sup.+(Cl.sup.)(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.3, (CH.sub.2).sub.3N.sup.+(Cl.sup.)(CH.sub.3).sub.2CH.sub.2CH.sub.2CHCH.sub.2 where L.sup.1 is chloride and a compound of General Formula III; n3 is an integer between 1 and 100.
EXAMPLE 72
[0148] A solution of 3-mercaptopropyl trimethoxysilane (0.04 mol), diallyl dimethyl ammonium chloride (0.072 mol, 60% in water) and ethanol (30 mL) was heated at reflux for 2 h with the addition of tert-butyl hydrogen peroxide (0.1 mL) every 15 min. The solution was then added to a stirred mixture of silica (20 g, 40-60 m, 60 ) and ethanol (30 mL) then refluxed for 6 h. On cooling the solid was filtered, washed well with de-ionised water (5100 mL) followed by methanol (100 mL) and dried to give a composition of General Formula I where Y, X and V are present and n is 2, n1 is 2; n2 is one; R.sup.9 is a mixture of (CH.sub.2).sub.3N.sup.+(Cl.sub.)(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.3, (CH.sub.2).sub.3N.sup.+(Cl.sup.)(CH.sub.3).sub.2CH.sub.2CHCH.sub.2 L.sup.1 is chloride; and a compound of General Formula III; n3 is an integer between 1 and 20.
EXAMPLE 73
[0149] A solution of 1,2-dimercapto ethane (0.10 mol) and vinyl trimethoxy silane (0.12 mol) was heated at 110 C. for 1 h with the addition of di-tert-butyl peroxide (0.3 mL) every 30 min. Diallyl dimethyl ammonium chloride (0.24 mol, 60% in water) and ethanol (60 mL) were added and the resultant solution heated for 2 h with the addition of tert-butyl hydrogen peroxide (0.05 mL) every 15 min. The solution was then added to a stirred mixture silica (100 g, 150-300 p.m, 100 ) and ethanol (200 mL) and refluxed for 6 h. On cooling the solid was filtered, washed well with de-ionised water (5300 mL) followed by methanol (300 mL) and dried to give a composition of General Formula I where Y, G and V are present and n is 3, n2 is zero; L.sup.1 is chloride; n3 is an integer between 1 and 50, R.sup.9 is a mixture of a compound of General Formula III and (CH.sub.2).sub.3N.sup.+(Cl.sup.)(CH.sub.3).sub.2CH.sub.2CH.sub.2CH.sub.3, (CH.sub.2).sub.3N.sup.+(Cl.sup.)(CH.sub.3).sub.2CH.sub.2CHCH.sub.2.
EXAMPLE 74
[0150] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure then diethylene triamine (0.20 mol) added. After heating at 100 C. for 2 h methanol (100 mL) was added and the solution refluxed for a further 1 h. The solution was added to a stirred mixture of silica (100 g, 150-300 m, 60 ) and xylene (250 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. Heating and stirring was continued for another 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y and E are present.
EXAMPLE 75
[0151] A solution of 3-mercaptopropyl trimethoxysilane (0.16 mol) and allyl chloride (0.32 mol) was refluxed with stirring for 2 h with the addition of AIBN (0.05 g) every 15 min. The excess allyl chloride was removed under reduced pressure then tetraethylene pentaamine (0.23 mol) added. After a 2 h reflux methanol (100 mL) was added and the solution refluxed for a further 1 h. The solution was added to a stirred mixture of silica (100 g, 150-300 m, 60 ) and xylene (240 mL) then the combined mixture was stirred and heated at 120 C. for 1 h during which methanol was removed using Dean and Stark apparatus. The mixture was stirred and refluxed for 1 h and then N-3-(3-trimethoxysilylpropylsulfyl)propyl thiourea (CH.sub.3O).sub.3SiC.sub.3H.sub.6SC.sub.3H.sub.6NHC(S)NH.sub.2 (0.05 mol) (formed from reacting allyl thiourea (0.05 mol) and 3-mercaptopropyl trimethoxy silane (0.05 mol) for 2 h at 125 C.) was added and the mixture stirred and refluxed for a further 5 h. On cooling water (100 mL) was added and after stirring for 1 h the solid was filtered, washed well with methanol (5300 mL) and dried to give a composition of General Formula I where Y, E and U are present.
EXAMPLE 76
[0152] The product from Example 16 (0.05 g) was added to a sample (6 mL) of a product stream containing 205 ppm of iridium originating from the use of iridium trichloride. The mixture was filtered after agitating for 1 h at 30 C. Analysis of the filtrate showed the iridium had been removed. Examples 5-12, 19, 32-38, 40-48, 57-59 and 64-68 were equally effective in this test.
EXAMPLE 77
[0153] The product from Example 67 (0.03 g) was added to a sample (10 mL) of a product stream containing 55 ppm of iridium originating from the use of the catalyst chlorocarbonylbis(triphenylphosphine) iridium(I). The mixture was filtered after agitating for 6 h at 60 C. Analysis of the filtrate showed the iridium had been removed. Examples 14-18, 20-26 and 31-46 were equally effective in this test.
EXAMPLE 78
[0154] The product from Example 35 (0.03 g) was added to a sample (3 mL) of a process stream containing 150 ppm of rhodium originating from the use of the catalyst chlorotris(triphenylphosphine) rhodium(I) (Wilkinson's catalyst). The mixture was filtered after agitating for 1 h at room temperature. Analysis of the filtrate showed the rhodium had been removed. Examples 9-13, 16-18, 33-56, and 64-70 were equally effective in this test.
EXAMPLE 79
[0155] The product from Example 40 (0.03 g) was added to a sample (3 mL) of a process stream containing 150 ppm of rhodium originating from the use of the catalyst acetylacetonatodicarbonyl rhodium(I). The mixture was filtered after agitating for 1 h at room temperature. Analysis of the filtrate showed the rhodium had been removed. Examples 14-18, 35-38, 40-51 and 64-68 were equally effective in this test.
EXAMPLE 80
[0156] The product from Example 3 (0.01 g) was added to a sample (3 mL) of a product stream containing 60 ppm of palladium originating from the use of palladium acetate as the catalyst. The mixture was filtered after agitating for 30 min at 30 C. Analysis of the filtrate showed the palladium had been completely removed. Examples 1, 4-26, 39-41, 49-61 and 64-66 were equally effective in this test.
EXAMPLE 81
[0157] The product from Example 16 (0.03 g) was added to a sample (3 mL) of a product stream containing 120 ppm of palladium originating from the use of the catalyst tetrakis(triphenylphosphine) palladium(0). The mixture was filtered after agitating for 2 h at 30 C. Analysis of the filtrate showed the palladium had been removed. Examples 14-15, 20-26, 31-37, 39-47 and 64-70 were equally effective in this test.
EXAMPLE 82
[0158] The product from Example 15 (0.03 g) was added to a sample (2 mL) of a product stream containing 200 ppm of palladium originating from the use of the catalyst tris(dibenzylideneacetone) dipalladium(0). The mixture was filtered after agitating for 1 h at 30 C. Analysis of the filtrate showed the palladium had been removed. Examples 16-18, 20-26, 35-40, 43-46 and 65-69 were equally effective in this test.
EXAMPLE 83
[0159] The product from Example 23 (0.04 g) was added to a sample (15 mL) of a process stream containing 50 ppm of platinum originating from the use of the catalyst chloroplatinic acid. The mixture was filtered after agitating for 6 h at 30 C. Analysis of the filtrate showed the platinum had been removed. Examples 1-3, 9-13, 20-26, 32-38, 48, 52, 57-59, 65-67 and 71-75 were equally effective in this test.
EXAMPLE 84
[0160] The product from Example 38 (0.04 g) was added to a sample (20 mL) of a product stream containing 5 ppm of platinum originating from the use of the catalyst chloroplatinic acid. The mixture was filtered after agitating for 6 h at 50 C. Analysis of the filtrate showed the platinum had been removed. Examples 1-3, 9-13, 20-26, 32-37, 48, 52, 57-59, 65-67 and 71-75 were equally effective in this test.
EXAMPLE 85
[0161] A silane waste process stream (20 L) containing 40 ppm of platinum was passed down, at 50 C., a column containing the product (100 g) from Example 38. Analysis of the treated stream showed the residual platinum content was less than 1 ppm. Examples 23 and 66 were equally effective in this test.
EXAMPLE 86
[0162] A hydroformylation waste process stream (5 L) containing 300 ppm of rhodium was passed down, at 80 C., a column containing the product (100 g) from Example 14. Analysis of the treated stream showed the residual rhodium content was less than 1 ppm. Examples 35 and 42 were equally effective in this test.
EXAMPLE 87
[0163] The product from Example 15 (0.04 g) was added to a sample (4 mL) of a process stream containing 50 ppm of ruthenium originating from the use of a Grubbs' catalyst, bis(tricyclohexylphosphine) benzyledine ruthenium(IV) dichloride. The mixture was filtered after agitating for 6 h at 30 C. Analysis of the filtrate showed the ruthenium had been removed. Examples 23, 34 and 65 were equally effective in this test.
EXAMPLE 88
[0164] The product from Example 14 (0.01 g) was added to a sample (5 mL) of a product stream containing 5 ppm of ruthenium originating from the use of the Grubbs' catalyst above in Example 87. The mixture was filtered after agitating for 6 h at 60 C. Analysis of the filtrate showed all ruthenium had been removed. Examples 21-26, 33-35, 39, 43-45, 57, 65 and 66 were equally effective in this test.
EXAMPLE 89
[0165] 30 L of a solution containing 10,000 ppm of combined zinc and iron, 4 ppm each of platinum and palladium, 3 ppm of ruthenium and 1.5 ppm of rhodium was passed through a fixed bed of the product from Example 37 (100 g) at a flow rate of 0.3 L/h. The reduction in metal content of the treated solution was platinum 99%; palladium 99%, ruthenium 60% and rhodium 70%.
EXAMPLE 90
[0166] The product from Example 57 (0.2 g) was added to a sample from a process stream (40 mL) containing 60 ppm of copper originating from the use of a copper(I) catalyst. The mixture was agitated gently at room temperature for 2 h then filtered. Analysis of the filtrate showed the copper had been removed. Examples 1-8, 20-26, 31-39 and 58-61 were also effective in this test.
EXAMPLE 91
[0167] A process stream containing 2-chloro-N,N-diethylacetamide (19 mg) was treated with the product from Example 21 (2 molar equivalents) by heating with stirring for 15 h at 50 C. The solid was filtered and analysis of the stream indicated the complete removal of 2-chloro-N,N-diethylacetamide.
EXAMPLE 92
[0168] A solution of palladium acetate (0.48 g) in dichloromethane (30 mL) was added to the product from Example 35 (2.0 g) and the mixture left to agitate overnight at 20 C. The yellow solid was filtered, washed well with dichloromethane then dried.
EXAMPLE 93
[0169] A mixture of the palladium catalyst formed in Example 92 (50 mg), 4-bromotoluene (1.6 mmol), phenyl boronic acid (1.6 mmol) and potassium carbonate (2.4 mmol) in xylene (10 mL) was stirred at 110 C. for 1 h. The mixture was filtered and the solid washed well with ether. The combined organic extracts were washed with water, dried then concentrated to give 4-methyl biphenyl in 99% yield.
EXAMPLE 94
[0170] A solution of 2-chloroacetophenone (100 mg) in anhydrous ether (5 mL) was treated with the product from Example 21 (2 molar equivalents) by heating the mixture at 30 C. with stirring for 1.5 h. The mixture was filtered and the organic solvent concentrated and analysis of the residue indicated less than 1% residual alkyl chloride.
EXAMPLE 95
[0171] A solution of 2-chloromethyl pyridine (100 mg) in anhydrous toluene (10 mL) was treated with the product from Example 17 (2 molar equivalents) by heating at 60 C. with stining for 2 h. The mixture was filtered then the organic solvent concentrated and the residue analysis indicating less than 1% residual alkyl chloride.
EXAMPLE 96
[0172] The product from Example 57 (0.03 g) was added to a sample (3 mL) of a waste stream containing 25 ppm of felTous and ferric ions. The mixture was filtered after agitating for 6 h at 30 C. Analysis of the filtrate showed the iron had been removed. Examples 1-13 and 58-60 were equally effective in this test.