Polymerization method and polymers formed therewith
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08G-075/00
C08J-005/18
C08G-064/06
C08G-065/40
C08G-064/24
출원번호
US-0649428
(2013-12-03)
등록번호
US-9447243
(2016-09-20)
국제출원번호
PCT/US2013/072871
(2013-12-03)
국제공개번호
WO2014/089078
(2014-06-12)
발명자
/ 주소
Dong, Jiajia
Fokin, Valery
Krasnova, Larisa
Kwisnek, Luke R.
Oakdale, James S.
Sharpless, K. Barry
출원인 / 주소
The Scripps Research Institute
대리인 / 주소
Olson & Cepuritis, Ltd.
인용정보
피인용 횟수 :
0인용 특허 :
5
초록▼
Condensation of fluoro-substituted and silyl-substituted monomers provides polymers suitable for use, e.g., as engineering polymers. A monomer composition is condensed in the presence of a basic catalyst. The monomer composition contains a compound of formula F—X—F and a compound of formula (R1)3Si—
Condensation of fluoro-substituted and silyl-substituted monomers provides polymers suitable for use, e.g., as engineering polymers. A monomer composition is condensed in the presence of a basic catalyst. The monomer composition contains a compound of formula F—X—F and a compound of formula (R1)3Si—Z—Si(R1)3, and forms an alternating X—Z polymer chain and a silyl fluoride byproduct. X has the formula -A(-R2-A)n-; each A is SO2, C(═O), or Het; R2 is an organic moiety; n is 0 or 1; Het is an aromatic nitrogen heterocycle; Z has the formula -L-R3-L-; each L is O, S, or N(R4); and each R3 is an organic moiety, and R4 comprises H or an organic moiety.
대표청구항▼
1. A polymerization method comprising the step of contacting a liquid monomer composition with a basic catalyst, wherein the monomer composition comprises at least one compound of formula F—X—F and at least one compound of formula (R1)3Si—Z—Si(R1)3; wherein: each R1 independently is a hydrocarbyl gr
1. A polymerization method comprising the step of contacting a liquid monomer composition with a basic catalyst, wherein the monomer composition comprises at least one compound of formula F—X—F and at least one compound of formula (R1)3Si—Z—Si(R1)3; wherein: each R1 independently is a hydrocarbyl group;X has the formula -A(-R2-A)n-;each A independently is SO2, C(═O), or Het;R2 comprises a first organic moiety;n is 0 or 1;Het is an aromatic heterocycle comprising at least two carbon atoms and at least one nitrogen atom in a heteroaromatic ring thereof, and when A is Het, the F substituent is attached to a carbon atom of the heteroaromatic ring thereof;Z has the formula -L-R3-L-;each L independently is O, S, or N(R4);R3 comprises a second organic moiety;each R4 independently is H or a third organic moiety; andwherein the F and (R1)3Si substituents form a silyl fluoride byproduct of formula (R1)3Si—F as the respective A and L groups of the monomers condense to form an X—Z polymer chain; and wherein the basic catalyst comprises at least one material selected from the group consisting of an amidine, a guanidine, a phosphazene, a nitrogen heterocyclic carbene, a tertiary alkoxide, and a fluoride salt;and wherein the basic catalyst is selected from the group consisting of:(a) 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU);(b) at least one phosphazene selected from the group consisting of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) and 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ5,4λ5-catenadi(phosphazene) (P4-t-Bu);(c) at least one guanidine selected from the group consisting of 1,1,3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD); and(d) at least one nitrogen-heterocyclic carbene selected from the group consisting of an imidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and an imidazolin-2-ylidene. 2. The method of claim 1 wherein: each R1 independently is an alkyl or aryl group;X has the formula -A(-R2-A)n-;each A is SO2;R2 comprises a first organic moiety;n is 0 or 1;Z has the formula -L-R3-L-;each L independently is 0; andR3 comprises a second organic moiety comprising at least one aryl or heteroaryl group directly bonded to each L. 3. The method of claim 1 wherein the n is 0. 4. The method of claim 1 wherein Het is a 1,3,5-triazine. 5. The method of claim 1 wherein the monomer composition includes a compound in which X includes an additional F substituent on a sulfonyl, carbonyl, or heteroaryl activating group, such that the additional F substituent also reacts with a (R1)3Si substituent on an oxygen, sulfur or nitrogen atom linking group, to form a silyl fluoride, and the activating group condenses with the linking group to introduce a branch point in the polymer. 6. The method of claim 1 wherein the monomer composition includes a compound in which Z includes an additional silyl substituent, (R1)3Si, on an oxygen, sulfur or nitrogen atom linking group, such that the additional silyl substituent also reacts with a F substituent on a sulfonyl, carbonyl, or heteroaryl activating group, to form a silyl fluoride and the linking group condenses with the activating group to introduce a branch point in the polymer. 7. The method of claim 1 wherein n is 1; R2 is -L1-R5-L1-; each L1 independently is selected from the group consisting of O, S, and N(R4); and each R4 independently is H or the third organic moiety, and R5 comprises an organic moiety. 8. The method of claim 1 wherein the basic catalyst comprises is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). 9. The method of claim 1 wherein the basic catalyst is at least one phosphazene selected from the group consisting of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) and 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2λ5,4λ5-catenadi(phosphazene) (P4-t-Bu). 10. The method of claim 1 wherein the basic catalyst is at least one guanidine selected from the group consisting of 1,1,3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 7-methyl-1,5,7-triazabicyclo-[4.4.0]dec-5-ene (MTBD). 11. The method of claim 1 wherein the basic catalyst is at least one nitrogen-heterocyclic carbene selected from the group consisting of an imidazole-2-ylidene, a 1,2,4-triazole-5-ylidene, a thiazole-2-ylidene, and an imidazolin-2-ylidene. 12. The method of claim 1 wherein each A is SO2. 13. The method of claim 1 wherein each R2 comprises an aryl or heteroaryl moiety either directly bonded to A or bonded to A via an oxygen atom attached to the aryl or heteroaryl moiety. 14. The method of claim 1 wherein the polymer comprises a polymeric chain represented by a formula selected from the group consisting of: (-A(-R2-A)n-L-R3-L)x-; Formula (I)(-A-R2-A-L-R3-L)y-; Formula (II)(-A-L1-R5-A-L1-A-L-R3-L)z-; Formula (III)(A-L1-R5-A-L-R3-L)m-; Formula (IV)(-A-L-R3-L)p-; Formula (V)and(-A-R2-A-L-R3-L)a-(-A-L1-R5-L1-A-L-R3-L)b-(A-L1-R5-A-L-R3-L)c-(-A-L-R3-L)d-; Formula (VI)wherein:each A independently is SO2, C(═O), or Het;each L and L1 independently is O, S, or N(R4);each R2 and R5 independently comprises a first organic moiety;each R3 comprises a second organic moiety;each R4 independently is H or a third organic moiety;each n independently is 0 or 1;each Het independently is an aromatic heterocycle comprising at least two carbon atoms and at least one nitrogen atom in a heteroaromatic ring thereof, and when A is Het, the F substituent is attached to a carbon atom of the heteroaromatic ring thereof;each of x, y, z, m, and p is the average number of repeating units in the polymer and has a value of at least 10; andeach of a, b, c, and d is the average number of respective repeating units, and independently can be 0 or greater, provided the sum of a, b, c, and d is at least 10. 15. The method of claim 1 wherein one or more of the R2, R3, R4, and R5, comprises a moiety selected from the group consisting of a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptide analog, and a combination of two or more thereof. 16. The method of claim 1 wherein one or more of R1, R2, R3, R4, and R5 is substituted by at least one substituent selected from the group consisting of hydroxyl, halogen, nitro, —C(O)R6, —C(O)OR6, —C(O)N(R6)2, —CN, —SOvR6, —SOvN(R6)2, R6SOvN(R6)—, —N(R6)SOvR6, —SO3R6, —N(R6)2, —N(R6)OR6, —N(R6)C(O)R6, —N(R6)C(O)OR6, —N(R6)C(O)N(R6)2, —OC(O)N(R6)2, —OC(O)OR6, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, an amino acid, and a polypeptide; wherein each R6 independently is H, alkyl, or aryl, and v is 0, 1, or 2. 17. The method of claim 1 wherein the monomer composition comprises (a) two or more different compounds of formula F—X—F, (b) two or more different compounds of formula (R1)3Si—Z—Si(R1)3, or (c) c combination of both (a) and (b). 18. The method of claim 17 wherein the two or more different compounds of formula (R1)3Si—Z—Si(R1)3 differ by the selection of R1, Z, or both R1 and Z. 19. The method of claim 1 wherein the monomer composition comprises at least one compound of Formula VII and at least one compound of Formula VIII: wherein each R1 independently is an alkyl or aryl group, and each R9 independently is a covalent bond, C(CH3)2, C(CF3)2, or SO2. 20. The method of claim 1 wherein the liquid monomer mixture comprises a mixture of the monomers dissolved in a solvent. 21. The method of claim 1 wherein the liquid monomer mixture comprises a melted mixture of the monomers. 22. The method of claim 1 wherein the F—X—F monomer comprises sulfuryl fluoride (FSO2F). 23. The method of claim 1 wherein the F—X—F monomer comprises a bisfluorosulfonyl monomer of formula F—SO2—CH2CH2—N(R11)—CH2CH2—SO2—F, wherein R11 comprises an organic moiety. 24. The method of claim 23 wherein R11 comprises a moiety selected from the group consisting of a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptide analog, and a combination of two or more thereof. 25. The method of claim 23 wherein is substituted by at least one substituent selected from the group consisting of hydroxyl, halogen, nitro, —C(O)R6, —C(O)OR6, —C(O)N(R6)2, —CN, —SOvR6, —SOvN(R6)2, R6SOvN(R6)—, —N(R6)SOvR6, —SO3R6, N(R6)2, —N(R6)OR6, —N(R6)C(O)R6, —N(R6)C(O)OR6, —N(R6)C(O)N(R6)2, —OC(O)N(R6)2, —OC(O)OR6, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, an amino acid, and a polypeptide; wherein each R6 independently is H, alkyl, or aryl, and v is 0, 1, or 2. 26. A polymer comprising a polymeric chain of (-A(-R2-A)n-L-R3-L)x-; Formula (I)wherein:A is SO2;each L independently is O, S, or N(R4);each R2 is —CH2CH2—N(R11)—CH2CH2—, wherein R11 comprises a first organic moiety;each R3 comprises a second organic moiety;each R4 independently is H or a third organic moiety;each n is 1;x is the average number of repeating units in the polymer and has a value of at least 10; andthe polymer includes a group of formula E-A- at one or both ends of the polymer chain, wherein each E independently is fluoro, OR8, NHR8, N(R8)2, azido, CN, or SR8, and each R8 independently is an organic moiety. 27. The polymer of claim 26 wherein one or more of the organic moieties R3, R4, R8 and R11 is selected from the group consisting of a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptide analog, and a combination of two or more thereof. 28. The polymer of claim 26 wherein one or more of R3, R4, R8 and R11 is substituted by at least one substituent selected from the group consisting of hydroxyl, halogen, nitro, —C(O)R6, —C(O)OR6, —C(O)N(R6)2, —CN, —SOvR6, —SOvN(R6)2, R6SOvN(R6)—, —N(R6)SOvR6, —SO3R6, —N(R6)2, —N(R6)OR6, —N(R6)C(O)R6, —N(R6)C(O)OR6, —N(R6)C(O)N(R6)2, —OC(O)N(R6)2, —OC(O)OR6, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, an amino acid, and a polypeptide; wherein each R6 independently is H, alkyl, or aryl, and v is 0, 1, or 2. 29. The polymer of claim 26 wherein R11 comprises a moiety selected from the group consisting of a hydrocarbon, a heterocycle, a carbohydrate, an amino acid, a polypeptide, a peptide analog, and a combination of two or more thereof. 30. The polymer of claim 26 wherein R11 is substituted by at least one substituent selected from the group consisting of hydroxyl, halogen, nitro, —C(O)R6, —C(O)OR6, —C(O)N(R6)2, —CN, —SOvR6, —SOvN(R6)2, R6SOvN(R6)—, —N(R6)SOvR6, SO3R6, —N(R6)2, —N(R6)OR6, —N(R6)C(O)R6, —N(R6)C(O)OR6, —N(R6)C(O)N(R6)2, —OC(O)N(R6)2, —OC(O)OR6, azido, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl, fluoroalkoxy, aryl, aryloxy, heteroaryl, poly(ethyleneoxy), alkynyl-terminated poly(ethyleneoxy), a fatty acid, a carbohydrate, an amino acid, and a polypeptide; wherein each R6 independently is H, alkyl, or aryl, and v is 0, 1, or 2. 31. The polymer of claim 26 wherein the polymer has a molecular weight polydispersity index (PDI) of less than about 2.2 based on gel permeation chromatography using polystyrene standards, and includes less than about 5 percent by weight of cyclic oligomers. 32. A method of preparing a transparent, substantially colorless poly(bisphenol A sulfate) film or sheet comprising pelletizing poly(bisphenol A sulfate) into pellets, and consolidating the pellets at an elevated pressure and at a temperature greater than the glass transition temperature thereof, wherein the elevated pressure is at least about 25,000 pounds-per-square inch (psi) and the temperature is in the range of about 200 to 250° C.
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이 특허에 인용된 특허 (5)
Hartsing ; Jr. Tyler F. (Westfield NJ), Cookware made from polyarylethersulfone.
Mark ; deceased Victor (late of Evansville IN by Carol M. Mark ; Ester H. Mark ; legal representatives) Peters Edward N. (Lenox MA), Polycarbonate exhibiting improved impact properties.
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