Claims
- 1. Polymerization process for preparing a "living" polymer, said process comprising contacting at least one polar acrylic or maleimide monomer with a tetracoordinate organosilicon polymerization initiator having at least one initiating site in the absence of a co-catalyst and at a pressure greater than about 50 MPa, wherein the initiator is of the formula (Q').sub.3 MZ.sup.1, (Q').sub.2 M(Z.sup.1).sub.2 (Z.sup.1 (Q').sub.2 M).sub.2 O or (Q').sub.3 MZ.sup.2 wherein:
- each Q', independently, is selected from R.sup.1, OR.sup.1, SR.sup.1 and N(R.sup.1).sub.2
- M is Si;
- Z.sup.1 is ##STR12## Z.sup.2 is --CN or --NC; X.sup.2 is --OSi(R.sup.1 .sub.1), --R.sup.6, --OR.sup.6 or --NR'R";
- R.sup.6 is
- (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms;
- (b) a polymeric radical containing at least 20 carbon atoms;
- (c) a radical of (a) or (b) containing one of more ether oxygen atoms within aliphatic segments thereof;
- (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or
- (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites;
- each R.sup.1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R.sup.1 group is not --H;
- each of R.sup.2 and R.sup.3 is independently selected from --H and hydrocarbyl, defined as for R.sup.6 above, subparagraphs (a) to (e); and
- each of R' and R" is independently selected from C.sub.1-4 alkyl.
- 2. Process of claim 1 wherein the pressure is from about 100 MPa to about 500 MPa.
- 3. Process of claim 2 wherein the pressure is from about 250 MPa to about 350 MPa.
- 4. Process of claim 3 wherein the process is conducted at a temperature of from about 25.degree. C. to about 110.degree. C.
- 5. Process of claim 1 wherein the monomer is a polar acrylic monomer selected from the group consisting of CH.sub.2 .dbd.C(Y)X wherein:
- X is --CN, --CH.dbd.CHC(O)X' or --C(O)X';
- Y is --H, --CH.sub.3, --CN or --CO.sub.2 R, provided, however,
- when X is --CH.dbd.CHC(O)X', Y is --H or --CH.sub.3 ;
- X' is --OSi(R.sup.1).sub.3, --R, --OR or --NR'R";
- each R.sup.1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R.sup.1 group is not --H;
- R is:
- (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms;
- (b) a polymeric radical containing at least 20 carbon atoms;
- (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof;
- (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or
- (e) a radical of (a), (b), (c) or (d) containing one or more reactive substituents of the formula --Z'(O)C--C(Y.sup.1).dbd.CH.sub.2 wherein Y.sup.1 is --H or --CH.sub.3 and Z' is O or NR'; and
- each of R' and R" is independently selected from C.sub.1-4 alkyl.
- 6. Process of claim 5, wherein R is a radical containing one or more reactive substituents of the formula --Z'(O)C--C(Y.sup.1).dbd.CH.sub.2 wherein Y.sup.1 is --H or --CH.sub.3, Z' is O or NR', and R' is selected from C.sub.1-4 alkyl.
- 7. Process of claim 5 wherein the pressure is from about 100 MPa to about 500 MPa.
- 8. Process of claim 7 wherein the pressure is from about 250 MPa to about 350 MPa.
- 9. Process of claim 8 wherein the process is conducted at a temperature of from about 25.degree. C. to about 110.degree. C.
- 10. Process of claim 5, wherein the initiator is a tetracoordinate organosilicon polymerization initiator having more than one initiating site.
- 11. Process of claim 5, wherein the initiator is at least one selected from the group consisting of [(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane; [(2-methyl-1-propenylidene)bis(oxy)bis[trimethylsilane]; and [(2-methyl-1-[2-(trimethylsiloxy)ethoxy]-1-propenyl)oxy]trimethylsilane.
- 12. Process of claim 10, wherein the initiator is at least one selected from the group consisting of trimethyl a,a'a"-tris(trimethylsilyl)-1,3,5-benzenetriacetate, dimethyl a,a'-bis(trimethylsilyl)-1,3-benzenediacetate, 1,6-dimethoxy-1,5-hexadiene-1,6-diylbis(oxy)bis[trimethylsilane], and bis[(1-methoxy-2-methyl-1-propenyl)oxy]methylsilane.
- 13. Process of claim 5, wherein X.sup.2 is --OR.sup.6 and R.sup.6 is --CH.sub.3 ; Q' is --OR.sup.1 or --N(R.sup.1).sub.2 ; R.sup.1 is --CH.sub.3 or --C.sub.2 H.sub.5 ; and R.sup.2 and R.sup.3 are, independently, --H or --CH.sub.3.
- 14. Process of claim 10 wherein the pressure is from about 100 MPa to about 500 MPa.
- 15. Process of claim 14 wherein the pressure is from about 250 MPa to about 350 MPa.
- 16. Process of claim 15 wherein the process is conducted at a temperature of from about 25.degree. C. to about 110.degree. C.
- 17. Process of preparing a block polymer from the "living polymer" produced by the process of claim 1 by the addition of monomers active in "Group Transfer Polymerization" to said "living polymer" of claim 1.
- 18. Process comprising quenching of the "living" polymer prepared by the process of claim 1 with an active hydrogen source.
CROSS REFERENCE TO RELATED APPLICATION
This is a continuation-in-part of application Ser. No. 883,320 filed July 8, 1986 now abandoned.
US Referenced Citations (14)
Non-Patent Literature Citations (1)
Entry |
Webster et al., J. Ameri. Chem. Soc., 105, 5706 (1983). |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
883320 |
Jul 1986 |
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