Arylsulfinate salts in initiator systems for polymeric reactions
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-002/48
C08F-002/46
C08F-002/50
C08F-004/00
출원번호
US-0275830
(2006-01-31)
등록번호
US-7329692
(2008-02-12)
발명자
/ 주소
Kalgutkar,Rajdeep S.
Palazzotto,Michael C.
출원인 / 주소
3M Innovative Properties Company
대리인 / 주소
Lown,Jean A.
인용정보
피인용 횟수 :
2인용 특허 :
71
초록▼
Compositions are provided that that can be used as an initiator system for free radical polymerization reactions. More specifically, the initiator systems include an electron acceptor and an electron donor. The electron donors are arylsulfinate salts having a cation that contains at least one carbon
Compositions are provided that that can be used as an initiator system for free radical polymerization reactions. More specifically, the initiator systems include an electron acceptor and an electron donor. The electron donors are arylsulfinate salts having a cation that contains at least one carbon atom and either a positively charged nitrogen atom or a positively charged phosphorus atom. Methods of polymerization are also provided that can be used to prepare polymeric material with the initiator systems. The initiator systems can be thermal initiator systems, photoinitiator systems, or combinations thereof.
대표청구항▼
We claim: 1. A composition comprising: an electron donor comprising an arylsulfinate salt having a anion of Formula I description="In-line Formulae" end="lead"Ar1--SO2- Idescription="In-line Formulae" end="tail" and a cation having at least one carbon atom and either a positively charged nitro
We claim: 1. A composition comprising: an electron donor comprising an arylsulfinate salt having a anion of Formula I description="In-line Formulae" end="lead"Ar1--SO2- Idescription="In-line Formulae" end="tail" and a cation having at least one carbon atom and either a positively charged nitrogen atom or a positively charged phosphorus atom, said electron donor having an oxidation potential in N,N-dimethylformamide of 0.0 to +0.4 volts versus a silver/silver nitrate reference electrode, wherein Ar1 is a substituted phenyl, an unsubstituted or substituted C7-30 aryl, or an unsubstituted or substituted C3-30 heteroaryl, said substituted Ar1 having a substituent that is an electron withdrawing group or an electron withdrawing group in combination with an electron donating group, wherein the electron withdrawing group is selected from cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, formyl carbonyl, sulfo, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, aminocarbonyl, or combinations thereof; and an electron acceptor comprising a diaryliodonium salt, a hexaarylbisimidazole, or combinations thereof. 2. The composition of claim 1 wherein the Ar1 group of the arylsulfinate salt is anthryl, naphthyl, acenaphtyl, phenanthryl, phenanthrenyl, perylenyl, anthracenyl, anthraquinonyl, anthronyl, biphenyl, terphenyl, 9,10-(dihydroanthracenyl, or fluorenyl, said Ar1 group being unsubstituted or substituted with an electron withdrawing group or an electron withdrawing group in combination with an electron donating group. 3. The composition of claim 1 wherein the Ar1 group of the arylsulfinate salt is quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, benzofuranyl, benzomercaptophenyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, phthalazinyl, benzothiadiazolyl, benzotriazinyl, phenazinyl, phenanthridinyl, acridinyl, or indazolyl, said Ar1 group being unsubstituted or substituted with an electron withdrawing group or an electron withdrawing group in combination with an electron donating group. 4. The composition of claim 1, wherein the Ar1 group of the arylsulfinate salt is a substituted phenyl, an unsubstituted or substituted naphthyl, or an unsubstituted or substituted anthraquinonyl, said substituted Ar1 having a substituent that is an electron withdrawing group or an electron withdrawing group in combination with an electron donating group. 5. The composition of claim 1, wherein the Ar1 group us phenyl substituted with an electron withdrawing group selected from cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, halocarbonyl, formyl, carbonyl, sulfo, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, aminocarbonyl, or combinations thereof. 6. The composition of claim 1, wherein the cation of the arylsulfinate salt is ring structure comprising a 4 to 12 member heterocyclic group having positively charged nitrogen atom, said heterocyclic being saturated or unsaturated and having up to 3 heteroatoms selected from oxygen, sulfur, nitrogen, or combinations thereof, wherein said ring structure is unsubstituted or substituted with a substituent selected from an alkyl, aryl, acyl, alkoxy, aryloxy, mercapto, amino, hydroxy, azo, cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, or combinations thereof. 7. The composition of claim 1, wherein the cation of the arylsulfinate salt is of Formula II where R1 is an unsubstituted alkyl, an alkyl substituted with a hydroxy, an unsubstituted aryl, or an aryl substituted with an alkyl, hydroxy, or combinations thereof; and each R4 is independently hydrogen, an unsubstituted alkyl, an alkyl, substituted with a hydroxy, an unsubstituted aryl, or an aryl substituted with an alkyl, hydroxy or combination thereof. 8. The composition of claim 1, wherein the cation of the arylsulfinate salt is a tetraalkylammonium ion, wherein each alkyl group has 4 to 30 carbon atoms. 9. The composition of claim 1, wherein the cation of the arylsulfinate salt is of Formula III where each R2 is independently an unsubstituted alkyl, an alkyl substituted with a hydroxy, an unsubstituted aryl, or an aryl substituted with an alkyl, hydroxy, or combinations thereof. 10. The composition of claim 1 further comprising a sensitizing compound capable of absorbing a wavelength of actinic radiation in the range of 250 to 1000 nanometers. 11. The composition of claim 10, wherein the composition further comprises a hydroxy-containing material selected from an alcohol, a hydroxy-containing monomer, or combinations thereof. 12. The composition of claim 1, further comprising an ethylenically unsaturated monomer. 13. The composition of claim 12 wherein the ethylenically unsaturated monomer comprises a monoacrylate, monomethacrylate, diacrylate, dimethacrylate, polyacrylate, polymethacrylate or combinations thereof, wherein said monomer is unsubstituted or substituted with a hydroxy. 14. A method of photopolymerization comprising irradiating a photopolymerizable composition with actinic radiation until the photopolymerizable composition gels or hardens, said photopolymerizable composition comprising: an ethylenically unsaturated monomer; a sensitizing compound capable of absorbing a wavelength of actinic radiation in the range of 250 to 1000 nanometers; an electron donor having an oxidation potential in N,N-dimethylformamide of 0.0 to +0.4 volts versus a silver/silver nitrate reference electrode, said electron donor comprising an arylsulfinate salt having an anion of Formula I description="In-line Formulae" end="lead"Ar1--SO231 Idescription="In-line Formulae" end="tail" and a cation comprising at least one carbon atom and either a positively charged nitrogen atom or a positively charged phosphorus atom, wherein Ar1 is a substituted phenyl, an unsubstituted or substituted C7-31 aryl, or an unsubstituted or substituted C3-30 heteroaryl, said substituted Ar1 having a substituent that is an electron withdrawing group or an electron withdrawing group in combination with an electron donating group, wherein the electron withdrawing group is selected from cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, formyl, carbonyl, sulfo, alkoxysulfonyl, aryloxsulfonyl, alkylsufonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, aminocarbonyl, or combinations thereof; and an electron acceptor comprising an iodonium salt, a hexaarylbisimidazole, or combinations thereof. 15. The method of claim 14, wherein the arylsulfinate salt has an anion that is a benzenesulfinate substituted with an electron withdrawing group electron selected from cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, formyl, carbonyl, sulfo, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, aminocarbonyl, or combinations thereof and the cation is a tetraalkylammonium ion. 16. The method of claim 14, wherein the electron acceptor is a diaryliodonium salt. 17. The method of claim 14, wherein the ethylenically unsaturated monomer comprises a hydroxy-containing monomer. 18. The method of claim 14, wherein the photopolymerizable composition further comprises an alcohol. 19. A method of polymerization comprising: forming a polymerizable composition comprising an ethylenically unsaturated monomer; an electron donor having an oxidation potential in N,N-dimethylformamide of 0.0 to +0.4 volts versus a silver/silver nitrate reference electrode, said electron donor comprising an arylsulfinate salt having an anion of Formula I description="In-line Formulae" end="lead"Ar1--SO2- Idescription="In-line Formulae" end="tail" and a cation comprising at least one carbon atom and a positively charged phosphorus atom or comprising a 4 to 12 member heterocyclic group having a positively charged nitrogen atom, wherein Ar1 is a substituted phenyl an unsubstituted or substituted C7-30 aryl, or an unsubstituted or substituted C3-30 heteroaryl, said substituted Ar1 having a substituent that is an electron withdrawing group or an electron withdrawing group in combination with an electron donating group, wherein the electron withdrawing group is selected from cyano, carboxy, alkoxycarbonyl, aryloxycarbonyl, formyl, carbonyl, sulfo, alkoxysulfonyl, aryloxysulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, aminocarbonyl, or combinations thereof; an electron acceptor having a reduction potential in N,N-dimethylformamide of 0.4 to-1.0 volts versus a silver/silver nitrate reference electrode; and reacting the polymerizable composition. 20. A composition comprising: an electron donor comprising an arylsulfinate salt having a anion of Formula I description="In-line Formulae" end="lead"Ar1--SO2- Idescription="In-line Formulae" end="tail" and a cation having at least one carbon atom and either a positively charged nitrogen atom or a positively charged phosphorus atom, said electron donor having an oxidation potential in N,N-dimethylformamide of 0.0 to +0.4 volts versus a silver/silver nitrate reference electrode, wherein Ar1 is an unsubstituted or substituted C7-30 aryl or an unsubstituted or substituted C3-30 heteroaryl, said substituted Ar1 having a substituent that is an electron withdrawing group or an electron withdrawing group in combination with an electron donating group; and an electron acceptor comprising a diaryliodonium salt, a hexaarylbisimidazole, or combinations thereof. 21. A composition comprising: an electron donor comprising an arylsulfinate salt having a anion of Formula IV and a cation having at least one carbon atom and either a positively charged nitrogen atom or a positively charged phosphorus atom, said electron donor having an oxidation potential in N,N-dimethylformamide of 0.0 to +0.4 volts versus a silver/silver nitrate reference electrode, wherein R3 is selected from a halo, cyano, fluoroalkyl, perfluoroalkyl, formyl, carbonyl. sulfo, alkoxysulfonyl, aryloxysulfonyl, perfluoroalkylsulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, or aminocarbonyl; and an electron acceptor comprising a diaryliodonium salt, a hexaarylbisimidazole, or combinations thereof. 22. The composition of claim 21 wherein the anion of the arylsulfinate salt is 4-chlorobenzenesulfinate, 4-cyanobenzenesulfinate, 4-ethoxycarbonylbenzenesulfinate, 4trifluoromethylbenzenesulfinate, 3-trifluoromethylbenzenesulfinate, 1-anthraquinone sulfinate, 1-naphthalenesulfinate, or 2-napthalenesulfinate.
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