End-functionalized polymers

Abstract

This invention relates to end-functionalized living polymers or copolymers having a structure represented by the general formula 1 or 2, wherein R.sub.1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. R.sub.2 is a functional end group of a vinyl hetero monomer selected from the group consisting of hydroxy, epoxy, silyl, NH.sub.2, NH(C.sub.1-C.sub.6alkyl), N(C.sub.1-C.sub.6alkyl).sub.2, CHCH.sub.2, CCH, C(CH.sub.3)CH.sub.2, OCHCH.sub.2, (OCH.sub.2CH.sub.2).sub.1-10OH, OR.sub.20, COOR.sub.20, CONHR.sub.20, OCONHR.sub.20, OCOR.sub.20 and NHCOR.sub.20, wherein R.sub.20 is linear or branched C.sub.1-C.sub.20 alkyl or linear or branched C.sub.1-C.sub.20 alkyl substituted with hydroxy, epoxy, silyl, NH.sub.2 or N(C.sub.1-C.sub.6alkyl).sub.2; or R.sub.20 is phenyl, benzyl, CHCH.sub.2, CCH or C(CH.sub.3)CH.sub.2, or R.sub.2 is a residue of an acrylic acid (CH.sub.2CHCOO*), methacrylic acid, (CH.sub.2C(CH.sub.3)COO*) or CH(CH.sub.3)CHCOO* or R.sub.2 is a residue of a dicarboxylic acid HOOCR.sub.cCOO* or C.sub.1-C.sub.6alkyl-OOCR.sub.cCOO* wherein R.sub.c is C.sub.1-C.sub.20 alkylene, C.sub.1-C.sub.20alkenylene or phenylene; or R.sub.2 is a residue derived from the reaction of an isocyanate R.sub.aNCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being R.sub.aNHCOO* or R.sub.aNHCONH* wherein R.sub.a is unsubstituted C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20cycloalkyl or C.sub.1-C.sub.20alkyl substituted with hydroxy, epoxy, silyl, NH.sub.2, NH(C.sub.1-C.sub.6alkyl) or N(C.sub.1-C.sub.6alkyl).sub.2; or R.sub.2 is a residue derived from the reaction of a diisocyanate residue OCNR.sub.bNCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *OOCNHR.sub.bNCO or *HNOCNHR.sub.bNCO or *OOCNHR.sub.bNHCOR.sub.30 wherein R.sub.b is C.sub.1-C.sub.20 alkylene or C.sub.1-C.sub.20cycloalkylene or phenylene and R.sub.30 is a residue of hydroxyethylacrylate (CH.sub.2CHCOO(CH.sub.2).sub.2O*), hydroxyethylmethacrylate (CH.sub.2C(CH.sub.3)COO(CH.sub.2).sub.2O*), hydroxybutylacrylate (CH.sub.2CHCOO(CH.sub.2).sub.4O*) or hydroxybutylmethacrylate (CH.sub.2C(CH.sub.3)COO(CH.sub.2).sub.4O*), A is the hetero atom of the vinyl hetero monomer selected from the group consisting of oxygen, nitrogen, sulfur and silicon; and if R.sub.2 is silyl and M is a direct bond, A is a direct bond; M is a bond or a divalent group linking the heteroatom of the vinyl hetero monomer and the functional end group of the vinyl hetero monomer said M being selected from the group consisting of C.sub.1-50 alkylene, C.sub.1-50 (hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Z.sub.n is a polymer or copolymer segment of random-, gradient- or block-type structure, which is built up from vinylic monomers selected from the group consisting of isoprene, 1,3-butadiene, -C.sub.5-18alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH.sub.2C(R.sub.3)C(R.sub.4)R.sub.5, wherein R.sub.3 is a hydrogen atom or a methyl group, R.sub.4 is oxygen atom or sulfur atom; R.sub.5 is NH.sub.2, hydroxy, unsubstituted C.sub.1-18 alkoxy, C.sub.2-100alkoxy interrupted by at least one N and/or O atom, hydroxy-substituted C.sub.1-18alkoxy, unsubstituted C.sub.1-18alkylamino, di(C.sub.1-18alkyl)amino, hydroxy-substituted C.sub.1-18alkylamino, hydroxy-substituted di(C.sub.1-18alkyl)amino or OCH.sub.2CH.sub.2N(CH.sub.3).sub.2; Y is the chain terminus of the polymer/copolymer Z.sub.n and Y represents the fragment of a polymerization initiator capable of initiating polymerization; Y1 represents a di-, tri- or polyvalent fragment of a di-, tri-, or polyfunctional NMP initiator; m is 2, 3 or 4, preferably 2; n is the number of monomer units Z and is between 10 and 5000. ##STR00001##

Claims

1. A polymer or copolymer of formula 1 or 2: ##STR00044## wherein: R.sub.1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms, R.sub.2 is a functional end group of a vinyl hetero monomer, wherein R.sub.2 is selected from the group consisting of hydroxy, epoxy, NH.sub.2, NH(C.sub.1-C.sub.6alkyl), N(C.sub.1-C.sub.6alkyl).sub.2, CHCH.sub.2, a carbon triple-bonded to another carbon that is bonded to a hydrogen, C(CH.sub.3)CH.sub.2, OCHCH.sub.2, (OCH.sub.2CH).sub.1-10OH, OR.sub.20, COOR.sub.20, CONHR.sub.20, OCONHR.sub.20, OCOR.sub.20, and NHCOR.sub.20, wherein R.sub.20 is linear or branched C.sub.1-C.sub.20 alkyl or linear or branched C.sub.1-C.sub.20 alkyl substituted with hydroxy, silyl, NH.sub.2 or N(C.sub.1-C.sub.6alkyl).sub.2; or R.sub.20 is phenyl, benzyl, CHCH.sub.2, a carbon triple-bonded to another carbon that is bonded to a hydrogen, or C(CH.sub.3)CH.sub.2: A is selected from the group consisting of oxygen, nitrogen, sulfur, and silicon; M is a direct bond or a divalent group selected from the group consisting of C.sub.1-50 alkylene, C.sub.1-50 (hetero)alkylene, arylene, and heteroarylene; X is a nitroxide group: Z.sub.n is a polymer or copolymer segment of random-, gradient-, or block-type structure, consisting of, in polymerized form, at least one vinylic monomer selected from the group consisting of isoprene, 1,3-butadiene, -C.sub.5-18alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethyl acrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene, and a compound of formula CH.sub.2C(R.sub.3)C(R.sub.4)R.sub.5; R.sub.3 is a hydrogen atom or a methyl group; R.sub.4 is oxygen atom or sulfur atom; R.sub.5 is NH.sub.2, hydroxy, unsubstituted C.sub.1-18alkoxy, C.sub.2-100alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C.sub.1-18alkoxy, unsubstituted C.sub.1-18alkylamino, di(C.sub.1-18alkyl) amino, hydroxy-substituted C.sub.1-18alkylamino, hydroxy-substituted di(C.sub.1-18alkyl) amino, or OCH.sub.2CH.sub.2N(CH.sub.3).sub.2; Y is a fragment of an NMP initiator capable of initiating a nitroxide mediated living polymerization (NMP) selected from the group consisting of ##STR00045## CH.sub.2CHCH.sub.2, (C.sub.1-4)alkyl-CR.sub.7C(O)-phenyl, (C.sub.1-4)alkyl-CR.sub.7C(O)(C.sub.1-4)alkoxy, (C.sub.1-4)alkyl-CR.sub.7C(O)(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.7C(O)N-di(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.7C(O)NH(C.sub.1-4)alkyl, and (C.sub.1-4)alkyl-CR.sub.7C(O)NH.sub.2, wherein R.sub.7 is hydrogen or C.sub.1-4 alkyl; Y.sub.1 is a di-, tri-, or poly-valent fragment of a di-, tri-, or polyfunctional NMP initiator; m is 2, 3, or 4; and n is between 10 and 5000.

2. The polymer or copolymer of claim 1, wherein Z.sub.n consists of, in polymerized form, at least one vinylic monomer selected from the group consisting of styrene and a compound of formula CH.sub.2C(R.sub.3)C(R.sub.4)R.sub.5, R.sub.3 is a hydrogen atom or a methyl group; R.sub.4 is oxygen atom; R.sub.5 is NH.sub.2, hydroxy, unsubstituted C.sub.1-18alkoxy, C.sub.2-100alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C.sub.1-18alkoxy, unsubstituted C.sub.1-18alkylamino, di(C.sub.1-18alkyl) amino, hydroxy-substituted C.sub.1-18alkylamino, hydroxy-substituted di(C.sub.1-18alkyl) amino, or OCH.sub.2CH.sub.2N(CH.sub.3).sub.2.

3. The polymer or copolymer of claim 2, wherein Z.sub.n consists of, in polymerized form, at least one vinylic monomer selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, and styrene.

4. The polymer or copolymer of claim 1, wherein Z.sub.n consists of, in polymerized form, at least one compound of formula CH.sub.2C(R.sub.3)C(R.sub.4)R.sub.5, wherein: R.sub.3 is a hydrogen atom or a methyl group; R.sub.4 is oxygen atom; and R.sub.5 is NH.sub.2, hydroxy, C.sub.2-100alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C.sub.1-18alkoxy, unsubstituted C.sub.1-18alkylamino, di(C.sub.1-18alkyl) amino, hydroxy-substituted C.sub.1-18alkylamino, hydroxy-substituted di(C.sub.1-18alkyl) amino, or OCH.sub.2CH.sub.2N(CH.sub.3).sub.2.

5. The polymer or copolymer of claim 1, wherein R.sub.2 is selected from the group consisting of hydroxy, OCONHR.sub.20, and OCOR.sub.20, wherein R.sub.20 is linear or branched C.sub.1-C.sub.20 alkyl; a linear or branched C.sub.1-C.sub.20 alkyl substituted with hydroxy, silyl, NH.sub.2, or N(C.sub.1-C.sub.6alkyl).sub.2; a phenyl; a benzyl; CHCH.sub.2; a carbon triple-bonded to another carbon that is bonded to a hydrogen; or C(CH.sub.3)CH.sub.2.

6. The polymer or copolymer of claim 1, wherein Y is a fragment selected from the group consisting of (C.sub.1-4)alkyl-CR.sub.7C(O)-phenyl, (C.sub.1-4)alkyl-CR.sub.7C(O)(C.sub.1-4)alkoxy, (C.sub.1-4)alkyl-CR.sub.7C(O)(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.7C(O)N-di(C.sub.1-4)alkyl, (C.sub.1-4)alkyl-CR.sub.7C(O)NH(C.sub.1-4)alkyl, and (C.sub.1-4)alkyl-CR.sub.7C(O)NH.sub.2, wherein R.sub.7 is hydrogen or C.sub.1-4 alkyl.

7. The polymer or copolymer of claim 1, wherein a number average molecular weight of the polymer or copolymer is between 1000 and 200,000 g/mol and a polydispersity of the polymer or copolymer is between 1.0 and 2.5.

8. The polymer or copolymer of claim 7, wherein the polydispersity is between 1.0 and 1.5.

9. A process of preparing the polymer or copolymer of claim 1, comprising: adding a functional vinyl hetero monomer to a living radical polymerization system, thereby obtaining a polymer or copolymer.

10. The process of claim 9, wherein the living radical polymerization system is of formula 5 or 6: ##STR00046##

11. The process of claim 9, wherein R.sub.2 is OH, and the adding comprises adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer.

12. The process of claim 9, wherein R.sub.2 is NH.sub.2, NH(C.sub.1-C.sub.6alkyl) or N(C.sub.1-C.sub.6alkyl).sub.2 and the adding comprises adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

13. The process of claim 9, wherein R.sub.2 is OCHCH.sub.2 and the adding comprises adding a divinyl ether to the living polymerization system, thereby obtaining an alkenyl-terminated polymer or copolymer.

14. The process of claim 13, wherein the divinyl ether is 1,4-butanediol divinyl either.

15. The process of claim 9, further comprising: reacting the polymer or copolymer obtained in the adding with a compound selected from the group consisting of (meth)acryloyl chloride, (meth)acrylic anhydride, C.sub.1-C.sub.4-alkyl (meth)acrylate, and 3-isopropenyl-,-dimethylbenzyl isocyanate, thereby obtaining an alkenyl terminated polymer or copolymer, wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

16. The process of claim 9, further comprising: reacting the polymer or copolymer obtained in the adding with a cyclic anhydride compound, thereby obtaining a carboxylic acid terminated polymer or copolymer, wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

17. The process of claim 9, further comprising: reacting the polymer or copolymer obtained in the adding with a compound having a silyl group and a functional group capable of reacting with a hydroxyl or amino group, thereby obtaining a silyl terminated polymer or copolymer, wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

18. The process of claim 13, further comprising: reacting the alkenyl-terminated polymer or copolymer with a hydrosilyl compound, thereby obtaining a silyl terminated polymer or copolymer.

19. The process of claim 9, wherein R.sub.2 is silyl, and the adding comprises adding a vinyl silane to the living polymerization system, thereby obtaining a silyl-terminated polymer or copolymer.

20. The process of claim 11, further comprising: reacting the hydroxy-terminated polymer or copolymer with epichlorohydrin, thereby obtaining an epoxy terminated polymer or copolymer.

21. The process of claim 9, further comprising: reacting the polymer or copolymer obtained in the adding with diisocyanate monomer, thereby obtaining an isocyanate-terminated polymer or copolymer, wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

22. A process of producing a resin, adhesive, sealant, binder, crosslinker, ink, plastic, coating, foam, epoxy, or any combination thereof, the process comprising: producing the resin, adhesive, sealant, binder, crosslinker, ink, plastic, coating, foam, epoxy, or a combination thereof with the polymer or copolymer of claim 1 as a building block.

Description

EXAMPLES

Experimental

(1) Gel Permeation Chromatography (GPC):

(2) The eluent is THF at a flow rate of 1.0 mL/min. The calibration curve is based on polystyrene standards.

(3) Solid Content:

(4) Solid content is tested using Halogen HB43 apparatus at 200 C. for 10 min.

(5) Determining of Functionality:

(6) .sup.1H NMR spectroscopy is performed in 5 mm diameter tubes in CDCl.sub.3 at 25 C. using a Bruker Avance 500 (500 MHz) spectrometer. The chemical shift scale is calibrated on the basis of the solvent peak (=7.26 ppm). In order to determine the OH functionality, two drops of trifluoroacetic anhydride are added into the tubes and the signal of the now downfield shifted CF.sub.3COOCH.sub.2 protons are integrated.

(7) Intermediate 1: Living Controlled Polybutylacrylate: PnBA30-NOR

(8) The mixture of 76.8 g n-butylacrylate (nBA, 0.6 mol), and 3.2 g of NOR regulator I (0.01 mol) (prepared as described in WO 2008/003602) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until the solid content (SC) of 51%. Residual nBA monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish free-flowing living controlled poly(nBA) is obtained (SC of 98%). GPC: Mn=3550 g/mol, PD=1.19.

(9) ##STR00029##

(10) NOR Regulator I

(11) Intermediate 2: Living Controlled Poly(nBA): NOR-PnBA30-NOR

(12) The mixture of 76.8 g nBA (0.6 mol), and 6.2 g of NOR regulator II (0.01 mol) (prepared as described below) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until the SC of 51%. Residual n-BA monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish free-flowing living controlled poly(nBA) is obtained (SC of 98%). GPC: Mn=3650 g/mol, PD=1.21.

(13) NOR Regulator II:

(14) ##STR00030##

(15) Preparation of the NOR Regulator II

(16) To the solution of 6.37 g (0.03 mol) 2,6-diethyl-2,3,6-trimethylpiperidin-4-on-N-oxyl (prepared according to WO 2004/085397) in 40 mL ethanol are added 5.2 g (0.03 mol) N,N,N,N,N-pentamethyltriethylene diamine, 1.19 g (0.012 mol) CuCl and 0.19 g (0.003 mol) Cu. To the stirred mixture is then during 5 minutes added the solution of 5 g (0.014 mol) N,N-2-bromoiso-butyroyl-1,2-diaminoethane (prepared according to Kruger, H. J.; Peng, G.; Holm, R. H. Inorganic Chemistry (1991), 30(4), 734-42) in 70 mL ethanol. The mixture is then stirred 40 h at room temperature and evaporated on a rotary evaporator. The residue is treated with 100 mL ethyl acetate and filtrated. The filtrate is successively washed with 200 mL water, 200 mL 2% EDTA solution, dried over Na.sub.2SO.sub.4 and evaporated. The crude product is purified on a silica gel column (hexane/ethyl acetate 8:2) to afford 8.27 g of the NOR regulator II as a light yellow resin. MS for C.sub.34H.sub.64N.sub.4O.sub.6 (622.90) found M.sup.+=622.

(17) Intermediate 3: Living Controlled Mono-OH Functional Poly(nBA): HO-PnBA35-NOR

(18) The mixture of 89.6 g nBA (0.7 mol), and 3.5 g of NOR regulator III (0.01 mol) (described as intermediate for compound 3 of WO 2005/118651, page 26) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until the SC of 51%. Residual n-BA monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish free-flowing living controlled poly(nBA) is obtained (SC of 98%). GPC: Mn=5000 g/mol, PD=1.20; OH functionality: 1.0.

(19) NOR Regulator III:

(20) ##STR00031##

(21) Intermediate 4: Living Controlled Poly(nBA-b-Styrene): PnBA30-b-PSt10-NOR

(22) The mixture of 71.0 g Intermediate 1 (0.02 mol), and 41.6 g styrene (St, 0.4 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until the SC of 82%. Residual St monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish viscous living controlled poly(nBA-b-St) is obtained (SC of 98%). GPC: Mn=4350 g/mol, PD=1.25.

(23) Intermediate 5: Living Controlled Mono-OH Functional Poly(nBA): HO-PnBA270-NOR

(24) The mixture of 691 g nBA (5.4 mol), and 3.5 g of NOR regulator III (0.01 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until a SC of 51% is reached. Residual n-BA monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish viscous living controlled poly(nBA) is obtained (SC of 98%). GPC: Mn=28,000 g/mol, PD=1.30; OH functionality: 1.0.

(25) Intermediate 6: Living Controlled Mono-OH Functional Poly(nBA-b-Styrene): HO-PnBA35-b-PSt10-NOR

(26) The mixture of 100 g Intermediate 3 (0.02 mol), and 41.6 g St (0.4 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 125 C. until a SC of 85% is reached. Residual St monomer is removed under 5 mbar vacuum (at 60 C. for 2 hr). Finally, a yellowish viscous living controlled HO-poly(nBA-b-St)-NOR is obtained (SC of 98%). GPC: Mn=6100 g/mol, PD=1.25. OH functionality: 1.0.

(27) The table 1 below shows the residues of polymers of the formula 1 wherein R.sub.1 is hydrogen and A is oxygen, M is (CH.sub.2).sub.4, Z.sub.n is nBA and X is

(28) ##STR00032##

(29) The following general polymer is obtained.

(30) TABLE-US-00001 Ex. R.sub.2 Y 1 OH 3, 12 OH 6 HOOCCH.sub.2CH.sub.2COO* 7 CH.sub.2CHCOO* 8 9, 13 (EtO).sub.3Si(CH.sub.2).sub.3NHCOO* 0 14 CH.sub.2C(CH.sub.3)COO* 15 CH.sub.2CHCOO*

Example 1: Controlled Poly(nBA30) End Functionalized with OH Group

(31) A Polymer of the Formula (1)

(32) The mixture of 35.5 g Intermediate 1 (0.01 mol), and 11.6 g 1,4-butanediol vinyl ether (0.1 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish free-flowing controlled poly(nBA30) end functionalized with OH group is obtained (SC of 99%). GPC: Mn=3750 g/mol, PD=1.23. OH functionality: 1.1.

Example 2: Controlled OH Telechelic Poly(nBA30)

(33) Compound of Formula 2, R.sub.2 is OH

(34) The mixture of 36.5 g Intermediate 2 (0.01 mol), and 23.2 g 1,4-butanediol vinyl ether (0.2 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish free-flowing controlled OH telechelic poly(nBA30) is obtained (SC of 99%). GPC: Mn=3850 g/mol, PD=1.27. OH functionality: 2.1.

Example 3: Controlled OH Telechelic Poly(nBA35)

(35) The mixture of 50 g Intermediate 3 (0.01 mol), and 11.6 g 1,4-butanediol vinyl ether (0.1 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish free-flowing controlled OH telechelic poly(nBA35) is obtained (SC of 99%). GPC: Mn=5350 g/mol, PD=1.23. OH functionality: 2.1.

Example 4: Controlled Poly(nBA30-b-St10) End Functionalized with OH Group

(36) Compound of Formula 1 Wherein Z.sub.n is a Copolymer, R.sub.2 is OH

(37) The mixture of 43.5 g Intermediate 4 (0.01 mol), and 23.2 g 1,4-butanediol vinyl ether (0.1 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish viscous controlled poly(nBA30-b-St10) end functionalized with OH group is obtained (SC of 99%). GPC: Mn=4550 g/mol, PD=1.30. OH functionality: 1.0.

Example 5: Controlled Vinyl Telechelic Poly(nBA30)

(38) Compound of Formula 2, R.sub.2 is OCHCH.sub.2

(39) The mixture of 36.5 g Intermediate 2 (0.01 mol), and 28.4 g 1,4-butanediol divinyl ether (0.2 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol divinyl ether monomer is removed under 1 mbar vacuum (at 140 C. for 2 hr). Finally, a yellowish free-flowing controlled vinyl telechelic poly(nBA30) is obtained (SC of 99%). GPC: Mn=3950 g/mol, PD=1.28. Vinyl functionality: 2.1.

Example 6: Controlled COOH Telechelic Poly(nBA35)

(40) The mixture of 53.5 g Example 3 (0.01 mol), 2.0 g succinic anhydride (0.02 mol), and 0.1 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 90 C. for 15 hr. A yellowish free-flowing controlled COOH telechelic poly(nBA35) is obtained (SC of 99%). GPC: Mn=5250 g/mol, PD=1.35. COOH functionality: 1.9.

Example 7: Controlled Alkenyl Telechelic Poly(nBA35)

(41) The mixture of 53.5 g Example 3 (0.01 mol), 2.52 g acrylic anhydride (0.02 mol), 50 mL dried xylene, and 0.1 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 90 C. for 15 hr. Xylene is removed under 10 mbar vacuum (at 100 C. for 2 hr). Finally, a yellowish free-flowing controlled alkenyl telechelic poly(nBA35) is obtained (SC of 99%). GPC: Mn=5550 g/mol, PD=1.36. Alkenyl functionality: 2.0.

Example 8: Controlled Alkenyl Telechelic Poly(nBA35)

(42) The mixture of 53.5 g Example 3 (0.01 mol), 4.44 g isophorone diisocyanate (0.02 mol), 50 mL dried xylene, and 0.1 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min, and heated at 60 C. for 4 hr. Then, 2.32 g 2-hydroxyethyl acrylate (0.02 mol) is added and heated at 90 C. for 15 hr. Xylene is removed under 10 mbar vacuum (at 100 C. for 2 hr). Finally, a yellowish viscous controlled alkenyl telechelic poly(nBA35) is obtained (SC of 99%). GPC: Mn=5600 g/mol, PD=1.38. Alkenyl functionality: 1.9.

Example 9: Controlled Silyl Telechelic Poly(nBA35)

(43) The mixture of 53.5 g Example 3 (0.01 mol), 4.95 g triethoxy(3-isocyanatorpropyl) silane (0.02 mol), and 0.1 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 90 C. for 15 hr. Finally, a yellowish viscous controlled silyl telechelic poly(nBA35) is obtained. GPC: Mn=5600 g/mol, PD=1.35. Silyl functionality: 1.9.

Example 10: Controlled Silyl Telechelic Poly(nBA35)

(44) Compound of Formula 2, R.sub.2 is OCHCH.sub.2Si(CH.sub.3)(OCH.sub.3).sub.2

(45) The mixture of 55.0 g Example 5 (0.01 mol), 2.55 mL dimethoxymethylhydrosilane (0.02 mol), 0.4 mL dimethylorthoformate, and 10.sup.3 mmol chloroplatinic acid is stirred under nitrogen and heated at 100 C. for 3 hr. Finally, a yellowish free-flowing controlled silyl telechelic poly(nBA35) is obtained. GPC: Mn=5650 g/mol, PD=1.34). Silyl functionality: 1.9.

Example 11: Controlled Silyl Telechelic Poly(nBA30)

(46) A Polymer of the Formula (1) Wherein M is a Bond, a is SI and R.sub.2 is Methoxy

(47) The mixture of 36.5 g Intermediate 2 (0.01 mol), 29.6 g vinyltrimethoxysilane (0.2 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual vinyltrimethoxysilane monomer is removed under 5 mbar vacuum (at 100 C. for 2 hr). Finally, a yellowish free-flowing controlled silyl telechelic poly(nBA30) is obtained (SC of 99%). GPC: Mn=3750 g/mol, PD=1.28. Silyl functionality: 2.0.

(48) ##STR00043##

Example 12: Controlled OH Telechelic Poly(nBA270)

(49) The mixture of 268 g Intermediate 5 (0.01 mol), and 23.2 g 1,4-butanediol vinyl ether (0.2 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 3 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish viscous controlled OH telechelic poly(nBA270) is obtained (SC of 99%). GPC: Mn=32,000 g/mol, PD=1.35. OH functionality: 2.4.

Example 13: Controlled Silyl Telechelic Poly(nBA270)

(50) The mixture of 320 g Example 12 (0.01 mol), 7.42 g triethoxy(3-isocyanatopropyl) silane (0.03 mol), and 0.3 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 90 C. for 15 hr. Finally, a yellowish viscous controlled silyl telechelic poly(nBA270) is obtained. GPC: Mn=36,000 g/mol, PD=1.40. Silyl functionality: 2.4.

Example 14: Controlled Poly(nBA30) End Functionalized with Alkenyl Group

(51) The mixture of 37.5 g Example 1 (0.01 mol), 1.54 g methacrylic anhydride (0.01 mol), 50 mL dried xylene, and 0.1 g dibutyltin dilaurate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 90 C. for 15 hr. Xylene is removed under 10 mbar vacuum (at 100 C. for 2 hr). Finally, a yellowish free-flowing controlled poly(nBA30) end functionalized with alkenyl group is obtained (SC of 99%). GPC: Mn=3950 g/mol, PD=1.3. Alkenyl functionality: 1.0.

Example 15: Controlled Poly(nBA30) End Functionalized with Alkenyl Group

(52) The mixture of 37.5 g Example 1 (0.01 mol), 128 g n-butyl acrylate (1.0 mol) and 0.1 g tetrabutyl titanate is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 100 C. for 8 hr. The formed 1-butanol and residual n-butyl acrylate is slowly removed under 10 mbar vacuum (at 100 C. for 2 hr). Finally, a yellowish free-flowing controlled poly(nBA30) end functionalized with alkenyl group is obtained (SC of 99%). GPC: Mn=3850 g/mol, PD=1.3. Alkenyl functionality: 0.85.

Example 16: Controlled OH Telechelic Poly(nBA35-b-St10)

(53) The mixture of 61 g Intermediate 6 (0.01 mol), and 23.2 g 1,4-butanediol vinyl ether (0.2 mol) is stirred under nitrogen at room temperature for 30 min firstly, and then is heated at 130 C. for 6 hr. Residual 1,4-butanediol vinyl ether monomer is removed under 5 mbar vacuum (at 130 C. for 2 hr). Finally, a yellowish viscous controlled OH telechelic poly(nBA35-b-St10) is obtained (SC of 99%). GPC: Mn=6250 g/mol, PD=1.28. OH functionality: 2.3.