Easily synthesizable, spontaneously water-soluble, essentially voc-free, environmentally friendly (meth)acrylamido-functional siloxanol systems, process for preparation thereof and use

Abstract

The invention relates to a composition and to a process for producing the composition comprising essentially water-soluble (meth)acrylamido-functional siloxanols, and to the use thereof.

Claims

1. A composition, comprising at least one water-soluble acrylamido-functional siloxanol oligomer of formula (V):
(R.sup.1O)[(R.sup.1O).sub.1−a(R.sup.2).sub.aSi(C).sub.1+bO].sub.u[(Y)Si(C).sub.1+bO].sub.u′R.sup.1.(HX)z   (V), obtained by: a) reacting a component A with an acrylic anhydride (B); and optionally b) removing at least a portion of hydrolyzed alcohol, with optional addition of water for removal of the hydrolyzed alcohol, wherein: the component A is at least one aminoalkyl-functionalized silicon compound selected from the group consisting of (i) an aminoalkyl-functional alkoxysilane or a mixture of aminoalkyl-functional alkoxysilanes, each in the presence of water, (ii) a hydrolysis or condensation product of at least one aminoalkyl-functional alkoxysilane, and (iii) a mixture comprising at least one aminoalkyl-functional alkoxysilane and a hydrolysis product, a condensation product, or both, of the at least one aminoalkyl-functional alkoxysilane:, C represents an acrylamido group; Y represents OR.sup.1 or, in crosslinked and/or three-dimensionally crosslinked structures, independently to OR.sup.1 or O.sub.1/2; R.sup.1 represents hydrogen; R.sup.2 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms; HX is an acid, where X is an inorganic or organic acid radical; a is 0 or 1; b is 0 or 1; u is an integer greater than or equal to 2; u′ is greater than or equal to 1; z is greater than or equal to 0; (u +u′) is greater than or equal to 2; and the composition is essentially free of diluents and releases essentially no alcohol during a crosslinking.

2. The composition according to claim 1, wherein: the aminoalkyl-functional alkoxysilane is defined by formula (I):
(R.sup.1O).sub.3−a−b(R.sup.2).sub.aSi(B).sub.1+b  (I); B independently represents a group of formula (II):
—(CH.sub.2).sub.c—[(NH)(CH.sub.2).sub.d].sub.e[(NH)](CH.sub.2).sub.f].sub.gNH.sub.(2−h)R.sup.3.sub.h  (II), R.sup.1 are each independently a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R.sup.2 are each independently a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R.sup.3 are each independently a linear, branched or cyclic alkyl, aryl or alkylaryl group having 1 to 8 carbon atoms, a is 0 or 1, b is 0, 1 or 2, c is 1, 2, 3, 4, 5 or 6, d is 1, 2, 3, 4, 5 or 6, e is 0, 1, 2, 3, 4, 5 or 6, f is 1, 2, 3, 4, 5 or 6, g is 0, 1, 2, 3, 4, 5 and 6, and h is independently 0 or 1, or B is of formula (III):
—(CH.sub.2).sub.j—NH.sub.2−p(CH.sub.2—CH.sub.2—NH.sub.2).sub.p  (III), j is 1, 2 or 3, and p is 0, 1 or 2.

3. The composition according to claim 1, wherein: the acrylic anhydride is of formula (IV):
(CHR.sup.5═CR.sup.4CO).sub.2O  (IV); R.sup.4 are each independently a hydrogen atom or a methyl group; and R.sup.5 are each independently a hydrogen atom or a methyl group.

4. An article, comprising the composition according to claim 1, wherein the article is selected from the group consisting of an adhesion promoter, a dental impression compound, a polymer additive, an adhesive, a sealant, and a fiber composite material.

5. The composition according to claim 1, wherein C is selected from the group consisting of
—(CH.sub.2).sub.c—[(NH)(CH.sub.2).sub.d].sub.e[(NH)](CH.sub.2).sub.f].sub.gNH.sub.(1−h)R.sup.3.sub.h—(CO)CR.sup.4═CHR.sup.5,
—(CH.sub.2).sub.j—NH(CH.sub.2—CH.sub.2—NH)—(CO)CR.sup.4═CHR.sup.5, and
—(CH.sub.2).sub.j—NH.sub.2−p(CH.sub.2—CH.sub.2—NH—(CO)CR.sup.4═CHR.sup.5).sub.p, wherein: c 1, 2, 3, 4, 5 or 6; d 1, 2, 3, 4, 5 or 6; e 0, 1, 2, 3, 4, 5 or 6; f 1, 2, 3, 4, 5 or 6; g 0, 1, 2, 3, 4, 5 or 6; h 0 or 1; j 1, 2 or 3; p 0, 1 or 2; R.sup.3 is a linear, branched or cyclic alkyl, aryl or alkylaryl group having 1 to 8 carbon atoms; and R.sup.5 a hydrogen atom or a methyl group.

Description

EXAMPLE 1

(1) A 500 ml stirred apparatus with distillation system was initially charged with 156.00 g of N-(3-(trimethoxysilyl)propyl)ethylenediamine (0.70 mol) and 40.20 g of methanol. 9.52 g of demineralized water (0.53 mol) were added dropwise within 6 minutes while stirring. In the course of this, the bottom temperature rose to 47.8° C. The mixture was stirred at a bottom temperature of 54° C. to 59° C. for a further 2 hours. At a bottom temperature of 23.1° C., 107.9 g of methacrylic anhydride (0.70 mol) were added dropwise within 2 hours. In the course of this, the bottom temperature rose to max. 51.7° C. 0.02 g of 4-hydroxy-tempo was added to the bottoms as an additional stabilizer. Subsequently, 30.21 g of distillate were removed at an absolute pressure of about 200 mbar and a bottom temperature of about 40° C. The methanol content of the distillate was 98.3 area % (GC-TCD determination). The viscosity in the bottoms distinctly increased. For further analysis, 78.1 g of sample were taken from the bottoms. Subsequently, at a bottom temperature of 32.2° C., 99.61 g of water were added within two minutes. In the course of this, the bottom temperature rose to 36.3° C. 45.2 g of methanol/water mixture were distilled off at an absolute pressure of 200 mbar and a bottom temperature of about 49° C. Subsequently, 120.02 g of water were stirred in, and 106.02 g of methanol/water mixture were distilled off at an absolute pressure of 200 mbar to 128 mbar. A clear, slightly viscous, yellowish liquid was obtained as the bottom product. Yield: 227.9 g. As can be seen in Table 1, the product has a solids content of 54.6%.

(2) TABLE-US-00001 TABLE 1 Analysis results for the bottom product from Example 1 Determination Method Result Total N [%] see above 5.2 Solids content [%] 3 g/3 hours/105° C. 54.6 SiO.sub.2 content [%] see above 11.6 pH DIN ISO 4925 7.7 Density [g/cm.sup.3] DIN 51757 1.142 Viscosity [mPa .Math. s] DIN 53015 351 Free methanol [%] see above 0.1 .sup.1H and .sup.13C NMR The singly converted oligomerized target product was found. Amidation has been effected at the primary amine.

EXAMPLE 2

(3) An 8 I stirred apparatus with distillation system was initially charged with 2490.58 g of N-(3-(trimethoxysilyl)propyl)ethylenediamine (11.2 mol) and 640.92 g of methanol. 161.54 g of demineralized water (8.96 mol) were added dropwise within 11 minutes while stirring. In the course of this, the bottom temperature rose to 54.7° C. The mixture was stirred at a bottom temperature of 51° C. to 56° C. for a further 0.8 hour. At a bottom temperature of 36.3° C., a solution of 1727.24 g of methacrylic anhydride (11.2 mol) and 3.40 g of 4-hydroxy-tempo was then metered in within 2.4 hours. In the course of this, the bottom temperature rose to max. 53.6° C. The bottoms remained clear and colourless. Subsequently, 2400.32 g of demineralized water were metered in within 14 minutes. Free methanol was distilled off at an absolute pressure of about 200 mbar to 112 mbar. The bottom temperature during the distillation was 46.0° C. to 52.2° C. The total amount of distillate was 2819.3 g. During the distillation, a total of 3699.72 g of demineralized water were added in four portions. A clear, only slightly yellowish, low-viscosity liquid was obtained as the bottom product. Yield: 8082.3 g. As can be seen in Table 2, the product has a solids content of 40.6%.

(4) TABLE-US-00002 TABLE 2 Analysis results for the bottom product from Example 2 Determination Method Result Total N [%] see above 4.1 Solids content [%] 3 g/3 hours/105° C. 40.6 SiO.sub.2 content [%] see above 8.3 pH DIN ISO 4925 7.1 Density [g/cm.sup.3] DIN 51757 1.097 Viscosity [mPa .Math. s] DIN 53015 20 Free methanol [%] see above 1.4 .sup.1H and .sup.13C NMR The singly converted oligomerized target product was found. Amidation has been effected at the primary amine.

COMPARATIVE EXAMPLE 1 (comparative example for WO 00/75148 A1)

(5) A 1 I stirred apparatus with distillation system was initially charged with 398.07 g of aminopropyltriethoxysilane (1.8 mol), and 1.99 g of dibutyltin oxide, 0.037 g of ionol and 0.18 g of 4,4′-thiobis(6-tert-butyl-m-cresol) were stirred in. Subsequently, within 2 hours, a mixture of 360.35 g of methyl methacrylate (3.60 mol) and 5.41 g of dipropylamine was metered in at a bottom temperature of 152.8° C. to 165.5° C. After a reaction time of 0.3 hour, at a top temperature of 76.5° C. to 80.4° C., a mixture of methanol, ethanol, methyl methacrylate and ethyl methacrylate was removed. After a distillation time of 2.5 hours, at an absolute pressure of 316 mbar to <1 mbar and a bottom temperature of 157.2° C., residual amounts of low boilers were removed from the bottom product. A total of 287.8 g of distillate was removed. 461.35 g of pale yellowish and low-viscosity liquid were obtained as the bottom product. In accordance with the disclosure of WO 00/75148 A1, the crude methacrylic product is distilled under high vacuum. For the purposes of determining the solubility, it was entirely sufficient to use the crude product that still contains dibutyltin oxide. For later use, a rectification disclosed by WO 00/75148 A1 would be necessary.

(6) TABLE-US-00003 TABLE 3 Analysis results from Comparative Example 1 Determination Method Result Total N [%] see above 5.0 SiO.sub.2 content [%] see above 22.0 Free methanol [%] see above 0.1 pH DIN ISO 4925 9.7 Viscosity [mPa .Math. s] DIN 53015 50.1
Solubility Characteristics:

(7) Table 4 shows the solubility characteristics as a function of the aminosilane used in the reaction with methacrylic anhydride. Bottom products from Example 1 and Example 2 show good solubility (dissolve spontaneously within a few seconds and lead to clear mixtures) even in the case of direct dissolution in demineralized water (without addition of acetic acid). The bottom product from Example 2 shows good solubility characteristics even at distinctly increased concentrations. In comparison, the product from Comparative Example 1, and also the commercially available Y-5997 (Momentive Performance Materials, mixture of 2-methacrylamidoalkoxypropylsilane having ethoxy and methoxy groups as alkoxy groups), does not dissolve in demineralized water (Table 6). Only at low pH values does this product show solubility after vigorous stirring for 10 minutes (Table 7).

(8) TABLE-US-00004 TABLE 4 Overview of the solubility tests of the bottom products (3.0% bottom product in demineralized water) pH Turbidity [FNU] Bottom product (hydro- after after after from Example lysate) 1 min. 1 h 24 h 1 (reactant: 7.3 clear clear clear N-(3-(tri- (0.3 FNU) (0.5 FNU) - methoxysilyl)propyl)- after storage ethylenediamine at RT for 6 d 1 4.1.sup.1) clear clear clear (0.3 FNU) (1.0 FNU) - after storage at RT for 7 d 2 (reactant: 5.4.sup.1) clear clear clear N-(3-(tri- (1.1 FNU) (0.9 FNU) methoxysilyl)propyl) ethylene-diamine .sup.1)The pH of the hydrolysate was adjusted by addition of acetic acid.

(9) TABLE-US-00005 TABLE 5 Overview of the solubility tests on the bottom product from Example 2 Hydrolysate w(bottom product) w(H.sub.2O) Turbidity [FNU] [%] [%] pH 1 min. 24 h 6 94 6.8 0.7 (clear) 0.6 (clear) 12 88 6.7 0.9 (clear) 0.9 (clear) * w = weight

(10) TABLE-US-00006 TABLE 6 Solubility of 3% of the product from Comparative Example 1 and Y-5997 in demineralized water pH Turbidity [FNU] (hydro- after after after Product lysate) 10 min. 1 h 24 h Y-5997 9.1 not turbid/ turbid/ dissolved precipitates precipitates From not not turbid/ turbid/ Example 3 determined dissolved precipitates precipitates

(11) TABLE-US-00007 TABLE 7 Solubility of 3% Y-5997 in demineralized water. The pH of the hydrolysate was adjusted by addition of acetic acid. pH Turbidity [FNU] (hydro- after after after after lysate) 1 min. 10 min. 1 h 24 h 4.1 turbid clear clear clear (0.3 TE/F) (1.7 FNU) - after storage at RT for 7 d
VOC Release as a Function of Active Ingredient Concentration:

(12) As is apparent in Table 8, Y-5997 has a maximum VOC release of 18% at a 40% active ingredient concentration. The methacrylamidopropylsiloxanol from Example 2 releases only max. 1.4% VOC at the same active ingredient concentration.

(13) TABLE-US-00008 TABLE 8 comparison of maximum VOC release as a function of active ingredient concentration VOC [w/w %] Active ingredient Methacrylamido- concentration propylsiloxane [w/w %] Y-5997 from Example 2 40 18 1.4 20 9.0 0.7 3 1.35 0.11 * w = weight

(14) TABLE-US-00009 TABLE 9 Calculation of maximum VOC release Methacrylamido- propylsiloxane Determination Method Unit from Example 2 Y-5997 Methanol after see above w/w % 1.4 34 hydrolysis Ethanol after see above w/w % <0.1 11 hydrolysis VOC Sum total of w/w % 1.4 45 methanol/ethanol after hydrolysis * w = weight
Solubility and Maximum VOC Release as a Function of Active Ingredient Concentration:

(15) As apparent in Table 10, Y-5997 shows poor solubility at relatively high active ingredient concentrations in water/acetic acid. The addition of acetic acid helps to dissolve the Y-5997 at low active ingredient concentrations in water. For this purpose, however, the hydrolysate has to be stirred vigorously for 8 minutes. The methacrylamidopropylsiloxanol from Example 2 shows spontaneous solubility even at a high active ingredient concentration. Addition of acetic acid is unnecessary (see Table 11).

(16) TABLE-US-00010 TABLE 10 Solubility and maximum VOC release from Y-5997 as a function of active ingredient concentration Active ingredient concentration VOC [w/w %] [w/w %] Dissolution characteristics 40 18 Product is insoluble in demineralized water. However, the hydrolysate still remains distinctly turbid in 1.50% acetic acid. 20 9.0 Product is insoluble in demineralized water. However, the hydrolysate still remains distinctly turbid in 1.50% acetic acid. 3 1.35 A clear hydrolysate is obtained in 1.50% acetic acid after vigorous stirring for 8 min. * w = weight

(17) TABLE-US-00011 TABLE 11 Solubility and maximum VOC release from methacrylamidopropylsiloxanol (Example 2) as a function of active ingredient concentration: Active ingredient concentration VOC [w/w %] [w/w %] Dissolution characteristics 40 1.40 Product was not diluted 20 0.70 Dissolves spontaneously in water: clear liquid, unchanged after 4 d 8 0.28 Dissolves spontaneously in water: clear liquid, unchanged after 4 d 3 0.11 Dissolves spontaneously in water: clear liquid, unchanged after 4 d * w = “weight”

EXAMPLE 3

(18) A 1 I stirred apparatus with distillation system was initially charged with 251.08 g of Dynasylan® TRIAMO (4,7,10-triazadecyltrimethoxysilane, 1.0 mol) and 80.00 g of methanol. 14.42 g of demineralized water (0.8 mol) were added dropwise within 2 minutes while stirring. In the course of this, the bottom temperature rose from 36.8° C. to 41.5° C. The mixture was stirred at a bottom temperature of 63-65° C. for a further 1 hour. Subsequently, the bottoms were cooled to 26.5° C., and 215.84 g of methacrylic anhydride (1.0 mol) were metered in within 1.5 hours. In the course of this, the bottom temperature rose to max. 56.0° C. 0.42 g of 4-hydroxy-tempo was added to the bottoms as an additional stabilizer (prior to the addition of methacrylic anhydride). A bottoms sample (35.0 g) was taken for analytical studies. 300.34 g of demineralized water were metered into the bottoms within 3 minutes. 430.5 g of distillate (methanol/water mixture) were removed at an absolute pressure of about 180 mbar and a bottom temperature of about 42° C. During the distillation, a total of 451.18 g of demineralized water were stirred into the bottoms. At the end of the distillation, the bottom temperature was 52° C. at an absolute pressure of 100 mbar. A clear, pale yellowish liquid was obtained as the bottom product.

(19) Yield: 818.7 g

(20) As can be seen from Table 12, the product has a solids content of 39.1%. It dissolves spontaneously in water (see Table 13).

(21) TABLE-US-00012 TABLE 12 Analysis results for Example 3 Determination Method Result Total N [%] see above 4.2 Solids content [%] 3 g/8 hours/125° C. 39.1 SiO2 content [%] AN-SAA 1171 6.7 pH DIN ISO 4925 6.1 Density [g/cm.sup.3] DIN 51757 1.106 Viscosity [mPa .Math. s] DIN 53015 180 Free methanol [%] Based on SAA0272 0.2 1H and 13C NMR Conversion level of the amidation: about 80 mol %; target product present as oligomer

(22) TABLE-US-00013 TABLE 13 Overview of the solubility tests for Example 3 Hydrolysate w(bottom product) w(H2O) Turbidity [FNU] [%] [%] pH 1 min. 24 h 6 94 6.8 2.9 (clear) 1.6 (clear) 12 88 6.7 3.1 (clear) 2.7 (clear) Hydrolysate w(bottom product) w(0.5% acetic acid) Turbidity [FNU] [%] [%] pH 1 min. 24 h 6 94 5.1 1.7 (clear) 1.7 (clear) 12 88 4.2 1.7 (clear) 2.6 (clear)

EXAMPLE 4

(23) A 1 I stirred apparatus with distillation system was initially charged with 332.07 g of 3-aminopropyltriethoxysilane (1.50 mol) and 81.04 g of ethanol. 21.6 g of demineralized water (1.2 mol) were added dropwise within 3 minutes while stirring. In the course of this, the bottom temperature rose from 32.3° C. to 33.5° C. The mixture was stirred at a bottom temperature of about 60° C. for a further 1 hour. Subsequently, the bottoms were cooled to 28.9° C., and 77.1 g of methacrylic anhydride (0.5 mol) were metered in within 36 minutes. In the course of this, the bottom temperature rose to max. 54° C. 0.42 g of 4-hydroxy-tempo was added to the bottoms as an additional stabilizer (prior to the addition of methacrylic anhydride). 300.11 g of demineralized water were metered into the bottoms within 3 minutes. For analytical studies, a bottoms sample (56.3 g) was taken. By adding 27.30 g of glacial acetic acid, a pH of about 7.9 was obtained. 390.9 g of distillate (ethanol/water mixture) were removed at an absolute pressure of about 146 mbar and a bottom temperature of about 40° C. During the distillation, a total of 50 g of demineralized water and 121.6 g of glacial acetic acid were stirred into the bottoms. At the end of the distillation, the bottom temperature was 50° C. at an absolute pressure of 170 mbar. The bottom product obtained was a slightly turbid, yellowish liquid, which was filtered through a pressure filter.

(24) Yield; 531.6 g of yellowish, slightly turbid liquid.

(25) The product dissolves spontaneously in water.

(26) TABLE-US-00014 TABLE 14 Analysis result for Example 4 Determination Method Result Total N [%] see above 3.4 Solids content [%] 3 g/19 hours/125° C. 42.4 SiO2 content [%] AN-SAA 1171 14.7 pH DIN ISO 4925 4.4 Density [g/cm.sup.3] DIN 51757 1.145 Viscosity [mPa .Math. s] DIN 53015 76 Ethanol after hydrolysis [%] Based on SAA0272 1.6 1H and 13C NMR Conversion level of the amidation: >90 mol %, target product present as oligomer