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US4417034A
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Living polymers and process for their preparation
Assignee: EIDP Inc
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Filing: 1982-06-17
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Granted: 1983-11-22
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Expires: 2002-06-17
Abstract
Abstract "Living" polymers and their preparation from acrylic-type or maleimide monomers and organosilicon, -tin or -germanium initiators.
Inventors
- 👤 Owen W. Webster
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 21:19
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/72; C08F8/00
Claims Analysis
Total Claims: 59
Claim 1
Independent Claim
314 words
Process of polymerizing the monomer selected from the group consisting of ##STR25## 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 ##STR26## 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 ##STR27## M is Sn or Ge; and (ii) a co-catalyst which is a source of fluoride, cyanide or azide ions or a suitable Lewis acid, to produce "living" polymer having repeat units of the one or more monomers.
Claim 2
Dependent Claim
314 words
Process of polymerizing the monomer selected from the group consisting of ##STR25## 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 ##STR26## 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 ##STR27## M is Sn or Ge; and (ii) a co-catalyst which is a source of fluoride, cyanide or azide ions or a suitable Lewis acid, 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
34 words
Process of claim 1 wherein the monomer is CH 2 ═C(Y)X, M is Si, and the co-catalyst is a source of fluoride or cyanide ions, ZnI 2 , ZnBr 2 or ZnCl 2 .
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
16 words
Process of claim 7 wherein R is substituted with at least one --OC(R)(R)OR, --OC(H)(R)OR or ##STR28##
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 7 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 X 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 ##STR29##
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
248 words
"Living" polymer of the formula: ##STR30## wherein: Z" is selected from the group consisting of ##STR31## each of a and b is independently selected from 0 or a number in the range 1 to about 100,000, provided, however, (a+b) is at least 3; Q is the divalent radical selected from the group consisting of ##STR32## and mixtures thereof; 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 or C 6-20 cycloalkyl, aryl, alkaryl or aralkyl, any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally 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; each of R 2 and R 3 is independently selected from H; C 1-10 alkyl and alkenyl; and C 6-10 aryl, alkaryl, and aralkyl, any of said groups except H optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents; Z' is O or N; m is 2, 3 or 4; n is 3, 4 or 5; and M is Si, Sn, or Ge.
Claim 31
Dependent Claim
248 words
"Living" polymer of the formula: ##STR30## wherein: Z" is selected from the group consisting of ##STR31## each of a and b is independently selected from 0 or a number in the range 1 to about 100,000, provided, however, (a+b) is at least 3; Q is the divalent radical selected from the group consisting of ##STR32## and mixtures thereof; 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 or C 6-20 cycloalkyl, aryl, alkaryl or aralkyl, any of said groups optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally 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; each of R 2 and R 3 is independently selected from H; C 1-10 alkyl and alkenyl; and C 6-10 aryl, alkaryl, and aralkyl, any of said groups except H optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents; Z' is O or N; m is 2, 3 or 4; n is 3, 4 or 5; and M is Si, Sn, or Ge.
Claim 32
Dependent Claim
29 words
Polymer of claim 29 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 33
Dependent Claim
29 words
Polymer of claim 29 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 34
Dependent Claim
12 words
Polymer of claim 29 wherein a is O and M is Si.
Claim 35
Dependent Claim
8 words
Polymer of claim 32 wherein X is --C(O)X'.
Claim 36
Dependent Claim
12 words
Polymer of claim 33 wherein Y is --H or --CH 3 .
Claim 37
Dependent Claim
8 words
Polymer of claim 34 wherein X' is --OR.
Claim 38
Dependent Claim
19 words
Polymer of claim 35 wherein R is substituted with at least one --OSi(R 1 ) 3 or --C(O)OR group.
Claim 39
Dependent Claim
16 words
Polymer of claim 35 wherein R is substituted with at least one --OC(R)(R)OR, --OC(H)(R)OR or ##STR33##
Claim 40
Dependent Claim
10 words
Polymer of claim 35 wherein R is substituted with oxiranyl.
Claim 41
Dependent Claim
17 words
Polymer of claim 35 wherein R is C 1-20 alkyl, sorbyl, 2-methacryloxyethyl, 2-[(1-propenyl)oxy]ethyl, allyl, 2-(dimethylamino)ethyl or amino.
Claim 42
Dependent Claim
8 words
Polymer of claim 32 wherein X is --CN.
Claim 43
Dependent Claim
8 words
Polymer of claim 32 wherein Z" is --CN.
Claim 44
Dependent Claim
12 words
Polymer of claim 32 wherein Z" is --C(R 2 )(R 3 )CN.
Claim 45
Dependent Claim
16 words
Polymer of claim 42 wherein at least one of R 2 and R 3 is --H.
Claim 46
Dependent Claim
12 words
Polymer of claim 32 wherein Z" is --C(R 2 )(R 3 )--C(O)X'.
Claim 47
Dependent Claim
16 words
Polymer of claim 44 wherein at least one of R 2 and R 3 is H.
Claim 48
Dependent Claim
14 words
Polymer of claim 44 wherein R 2 and R 3 are CH 3 .
Claim 49
Dependent Claim
14 words
Polymer of claim 46 wherein X' in Z" is --OSi(CH 3 ) 3 .
Claim 50
Dependent Claim
12 words
Polymer of claim 46 wherein X' in Z" is --OCH 3 .
Claim 51
Dependent Claim
8 words
Polymer of claim 33 wherein Z" is ##STR34##
Claim 52
Dependent Claim
16 words
Polymer of claim 49 wherein Z' is oxygen, R 2 is H and m is 2.
Claim 53
Dependent Claim
28 words
Polymer of claim 47 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 54
Dependent Claim
28 words
Polymer of claim 48 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 55
Dependent Claim
11 words
Polymer of claim 29 wherein R 1 is --CH 3 .
Claim 56
Dependent Claim
8 words
Polymer of claim 53 wherein Z" is --CN.
Claim 57
Dependent Claim
12 words
Solution of the polymer of claim 29 dissolved in an aprotic solvent.
Claim 58
Dependent Claim
14 words
Film of the polymer of claim 29, prepared from the solution of claim 55.
Claim 59
Dependent Claim
14 words
Fiber of the polymer of claim 29, prepared from the solution of claim 55.
References Cited (Backward Citations)
US3272786A
Cited
US3393182A
Cited
US3458491A
Cited
US3773694A
Cited
US4011385A
Cited
US4041227A
Cited
SU715583A1
Cited
SU717057A1
Cited
US4233231A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1986-11-21 | 1987-05-23 | 1987-11-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-21 | 1991-05-23 | 1991-11-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-21 | 1995-05-23 | 1995-11-22 | $7700.00 | Window Closed / Lapsed |