Patent US2567227A successfully refreshed from Google Patents.
Patent US4414372A successfully refreshed from Google Patents.
US4414372A
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Process for preparing living polymers
Assignee: EIDP Inc
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Filing: 1982-06-17
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Granted: 1983-11-08
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Expires: 2002-06-17
Abstract
Abstract Process for preparing "living" polymers from acrylic-type or maleimide monomers and organosilicon, -tin or -germanium initiators.
Inventors
- 👤 William B. Farnham
- 👤 Dotsevi Y. Sogah
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 05:46
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F293/00; C08F293/005
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
312 words
Process of polymerizing the monomer selected from the group consisting of CH 2 ═C(Y)X, ##STR23## and mixtures thereof wherein: X is --CN, --CH═CHC(O)X' or --C(O)X'; Y is --H, --CH 3 , --CN or --CO 2 R, provided, however, when X is CH═CHC(O)X', Y is --H or --CH 3 ; X' is --OSi(R 1 ) 3 , --R, --OR or --NR'R"; each R 1 is independently selected from C 1-10 alkyl and C 6-10 aryl or alkaryl; R is C 1-20 alkyl, alkenyl, or alkadienyl; C 6-20 cycloalkyl, aryl, alkaryl or aralkyl; any of said groups containing one or more ether oxygen atoms within aliphatic segments thereof; and any of all the aforesaid groups containing one or more functional substituents that are unreactive under polymerizing conditions; and each of R' and R" is independently selected from C 1-4 alkyl by contacting the one or more monomers under polymerizing conditions with: (i) the initiator of the formula (R 1 ) 3 MZ wherein: R 1 is as defined above; Z is an activating substituent selected from the group consisting of ##STR24## and mixtures thereof wherein: X' is as defined above; each of R 2 and R 3 is independently selected from H; C 1-10 alkyl and alkenyl; C 6-10 aryl, alkaryl, and aralkyl; any of said groups except H containing one or more ether oxygen atoms within aliphatic segments thereof; and any of all the aforesaid groups except H containing one or more functional substituents that are unreactive under polymerizing conditions; and Z' is O or N; m is 2, 3 or 4; n is 3, 4 or 5; and M is Si, Sn, or Ge, provided, however, when Z is ##STR25## M is Sn or Ge; and (ii) a co-catalyst which is a source of bifluoride ions HF 2 31 to produce "living" polymer having repeat units of the one or more monomers.
Claim 2
Dependent Claim
312 words
Process of polymerizing the monomer selected from the group consisting of CH 2 ═C(Y)X, ##STR23## and mixtures thereof wherein: X is --CN, --CH═CHC(O)X' or --C(O)X'; Y is --H, --CH 3 , --CN or --CO 2 R, provided, however, when X is CH═CHC(O)X', Y is --H or --CH 3 ; X' is --OSi(R 1 ) 3 , --R, --OR or --NR'R"; each R 1 is independently selected from C 1-10 alkyl and C 6-10 aryl or alkaryl; R is C 1-20 alkyl, alkenyl, or alkadienyl; C 6-20 cycloalkyl, aryl, alkaryl or aralkyl; any of said groups containing one or more ether oxygen atoms within aliphatic segments thereof; and any of all the aforesaid groups containing one or more functional substituents that are unreactive under polymerizing conditions; and each of R' and R" is independently selected from C 1-4 alkyl by contacting the one or more monomers under polymerizing conditions with: (i) the initiator of the formula (R 1 ) 3 MZ wherein: R 1 is as defined above; Z is an activating substituent selected from the group consisting of ##STR24## and mixtures thereof wherein: X' is as defined above; each of R 2 and R 3 is independently selected from H; C 1-10 alkyl and alkenyl; C 6-10 aryl, alkaryl, and aralkyl; any of said groups except H containing one or more ether oxygen atoms within aliphatic segments thereof; and any of all the aforesaid groups except H containing one or more functional substituents that are unreactive under polymerizing conditions; and Z' is O or N; m is 2, 3 or 4; n is 3, 4 or 5; and M is Si, Sn, or Ge, provided, however, when Z is ##STR25## M is Sn or Ge; and (ii) a co-catalyst which is a source of bifluoride ions HF 2 31 to produce "living" polymer having repeat units of the one or more monomers.
Claim 3
Dependent Claim
29 words
Process of claim 1 wherein at least one of said R, R 2 and R 3 groups contains one or more ether oxygen atoms within any aliphatic segment thereof.
Claim 4
Dependent Claim
29 words
Process of claim 1 wherein at least one of said R, R 2 and R 3 groups contains at least one functional substituent that is unreactive under polymerizing conditions.
Claim 5
Dependent Claim
15 words
Process of claim 1 wherein the monomer is CH 2 ═C(Y)X and M is Si.
Claim 6
Dependent Claim
8 words
Process of claim 4 wherein X is --C(O)X'.
Claim 7
Dependent Claim
12 words
Process of claim 5 wherein Y is --H or --CH 3 .
Claim 8
Dependent Claim
8 words
Process of claim 6 wherein X' is --OR.
Claim 9
Dependent Claim
19 words
Process of claim 7 wherein R is substituted with at least one --OSi(R 1 ) 3 or --C(O)OR group.
Claim 10
Dependent Claim
17 words
Process of claim 7 wherein R is substituted with at least one --OC(R)(R)OR, --OC(H)(R)OR or ##STR26## group.
Claim 11
Dependent Claim
10 words
Process of claim 7 wherein R is substituted with oxiranyl.
Claim 12
Dependent Claim
17 words
Process of claim 17 wherein R is C 1-20 alkyl, sorbyl, 2-methacryloxyethyl, 2-[(1-propenyl)oxy]ethyl, allyl, 2-(dimethylamino)ethyl or amino.
Claim 13
Dependent Claim
8 words
Process of claim 4 wherein X is --CN.
Claim 14
Dependent Claim
8 words
Process of claim 4 wherein Z is --CN.
Claim 15
Dependent Claim
12 words
Process of claim 4 wherein Z is --C(R 2 )(R 3 )CN.
Claim 16
Dependent Claim
16 words
Process of claim 14 wherein at least one of R 2 and R 3 is --H.
Claim 17
Dependent Claim
18 words
Process of claim 4 wherein Z is --C(R 2 )(R 3 )--(C(O)X' or --OCX'═C(R 2 )(R 3 ).
Claim 18
Dependent Claim
16 words
Process of claim 16 wherein at least one of R 2 and R 3 is H.
Claim 19
Dependent Claim
14 words
Process of claim 16 wherein R 2 and R 3 are CH 3 .
Claim 20
Dependent Claim
15 words
Process of claim 18 wherein X' in the initiator is --OSi(CH 3 ) 3 .
Claim 21
Dependent Claim
13 words
Process of claim 18 wherein X' in the initiator is --OCH 3 .
Claim 22
Dependent Claim
8 words
Process of claim 5 wherein Z is ##STR27##
Claim 23
Dependent Claim
16 words
Process of claim 21 wherein Z' is oxygen, R 2 is H and m is 2.
Claim 24
Dependent Claim
28 words
Process of claim 19 wherein at least one of R 2 and R 3 is substituted with at least one functional group that is unreactive under polymerizing conditions.
Claim 25
Dependent Claim
28 words
Process of claim 20 wherein at least one of R 2 and R 3 is substituted with at least one functional group that is unreactive under polymerizing conditions.
Claim 26
Dependent Claim
11 words
Process of claim 1 wherein R 1 is --CH 3 .
Claim 27
Dependent Claim
8 words
Process of claim 25 wherein Z is --CN.
Claim 28
Dependent Claim
14 words
Process of claim 1 carried out at about -100° C. to about 150° C.
Claim 29
Dependent Claim
12 words
Process of claim 27 carried out at 0° C. to 50° C.
Claim 30
Dependent Claim
11 words
Process of claim 1 wherein the bifluoride is a tetraalkylammonium bifluoride.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-11-07 | 1987-05-09 | 1987-11-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-07 | 1991-05-09 | 1991-11-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-07 | 1995-05-09 | 1995-11-08 | $7700.00 | Window Closed / Lapsed |