Halogenated acrylates and polymers derived therefrom
Assignee3M Innovative Properties Company
InventorsGeorge G.I. Moore, Fred B. McCormick, Mita Chattoraj, Elisa M. Cross, Junkang Jacob Liu, Ralph R. Roberts, Jay F. Schulz
Life of this patent
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Abstract
Acrylates having a high degree of halogenation, as well as polymers that include one or more mer units derived from such acrylates provide materials having tailorable optical and physical properties. The polymers find utility particularly in optical devices including optical waveguides and interconnecting devices.
Claims29
A halogenated acrylate having the general formula
- 20
- wherein
- M is H, CH3, F, Cl, Br, I, or CF3,
- A is oxygen or sulfur, and
- Z is a group having at most 150 carbon atoms selected from the group consisting of
- 21
- in which each R1 independently is F, Cl, or Br;
- 22
- in which each R2 independently is
- (a) a perfluorinated, perchlorinated, or per(chlorofluoro) group (i), (ii), (iii), (iv), or (v) wherein
- (i) is a C1-C20 aliphatic group,
- (ii) is a C3 to C20 cycloaliphatic alkyl group,
- (iii) is a C6-C20 aryl group,
- (iv) is a C7-C20 aralkyl group, and
- (v) is a C7-C20 alkaryl group,
- (b) F, Cl, Br, I, Q (defined below), R4COO—, R4O—, —COOR4, —OSO2R4, or —SO2OR4, wherein R4 is any group from (a)(i), (a)(ii), (a)(iii), (a)(iv), and (a)(v),
- or any two adjacent R2 groups together can form a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic or aromatic ring moiety which optionally can further include n R2 groups where n is a whole number in the range of 0 to 25 that describes the number of free sites on the ring moiety, wherein Q is
- 23
- in which A is as defined as above, with the proviso that all R2 groups in the molecule can be the same only when R2 is not Cl, F, Br or I;
- and each R3 independently can be
- (a) a perfluorinated, perchlorinated, or per(chlorofluoro)
- (i) C1-C20 aliphatic group,
- (ii) C3-C20 cycloaliphatic group,
- (iii) C6-C20 aryl group,
- (iv) C7-C20 aralkyl group, and
- (v) C7-C20 alkaryl group,
- (b) F, Cl, Br, I, Q (defined above), R4COO—, R4O—, —COOR4, —OSO2R4, or
- —SO2OR4, wherein R4 is any group from (a)(i), (a)(ii), (a)(iii), (a)(iv), and (a)(v),
- or any two adjacent R3 groups together can form a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic or aromatic ring moiety which optionally can further include n R3 groups where n is a whole number in the range of 0 to 25 that describes the number of free sites on the ring moiety;
- (3) —C(Rf)2E in which
- both Rf groups together are part of a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic ring group or independently are perfluorinated, perchlorinated, or per(chlorofluoro)
- (a) C1-C20 aliphatic groups,
- (b) C3-C20 cycloaliphatic groups,
- (c) C6-C20 aryl groups,
- (d) C7-C20 aralkyl groups, or
- (e) C7-C20 alkaryl groups,
- (f) C4-C20 heteroaryl groups,
- (g) C4-C20 heteroaralkyl groups,
- (h) C4-C20 heteroalkaryl groups,
- wherein heteroatoms can be one or more of O, N, and S atoms, with the proviso that at least one Rf group includes one or more of (i) at least one straight-chain C4-C20 aliphatic or C4-C20 cycloaliphatic group, (ii) at least one ether oxygen atom, and (iii) at least one branched C3-C20 aliphatic group, and
- E is Rf,
- 24
- wherein R1, R2, and Rf, and Q are defined as above, and
- (4) —CRf(E)2,
- wherein each E independently is as defined above, and Rf is as defined above.
A halogenated acrylate having structure selected from the group consisting of
- 30
A halogenated acrylate having a structure selected from the group consisting of
- 31
A polymer comprising at least one mer unit derived by polymerization of the olefinic bond from a halogenated acrylate having the general formula
- 32
- wherein A is oxygen or sulfur, and Z is a group having at most 150 carbon atoms selected from the group consisting of (1)
- 33
- in which each R1 independently is F, Cl, or Br;
- (2)
- 34
- in which each R2 independently is
- (a) a perfluorinated, perchlorinated, or per(chlorofluoro) group (i), (ii), (iii), (iv), or (v) wherein
- (i) is a C1-C20 aliphatic group,
- (ii) is a C3 to C20 cycloaliphatic alkyl group,
- (iii) is a C6-C20 aryl group,
- (iv) is a C7-C20 aralkyl group, and
- (v) is a C7-C20 alkaryl group,
- (b) F, Cl, Br, I, Q (defined below), R4COO—, R4O—, —COOR4, —OSO2R4, or —SO2OR4, wherein R4 is any group from (a)(i), (a)(ii), (a)(iii), (a)(iv), and (a)(v),
- or any two adjacent R2 groups together can form a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic or aromatic ring moiety in which n fluoro or chloro groups optionally can be replaced by n R2 groups where n is a whole number in the range of 0 to 25, wherein Q is
- 35
- in which A is as defined as above, with the proviso that all R2 groups in the molecule can be the same only when R2 is not Cl, F, Br or I;
- and each R3 independently can be
- (a) a perfluorinated, perchlorinated, or per(chlorofluoro)
- (i) C1-C20 aliphatic group,
- (ii) C3-C20 cycloaliphatic group,
- (iii) C6-C20 aryl group,
- (iv) C7-C20 aralkyl group, and
- (v) C7-C20 alkaryl group,
- (b) F, Cl, Br, I, Q (defined above), R4COO—, R4O—, —COOR4, —OSO2R4, or
- —SO2OR4, wherein R4 is any group from (a)(i), (a)(ii), (a)(iii), (a)(iv), and (a)(v),
- or any two adjacent R3 groups together can form a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic or aromatic ring moiety in which n fluoro or chloro groups which can be replaced by n R3 groups wherein n is a whole number in the range of 0 to 25, and R3 is as defined above;
- (3) —C(Rf)2E
- wherein both Rf groups together comprise a perfluorinated, perchlorinated, or per(chlorofluoro) cycloaliphatic ring group or independently comprise perfluorinated, perchlorinated, or per(chlorofluoro)
- (a) C1-C20 aliphatic groups,
- (b) C3-C20 cycloaliphatic groups,
- (c) C6-C20 aryl groups,
- (d) C7-C20 aralkyl groups, or
- (e) C7-C20 alkaryl groups,
- (f) C4-C20 heteroaryl groups,
- (g) C4-C20 heteroaralkyl groups,
- (h) C4-C20 heteroalkaryl groups,
- wherein heteroatoms can be one or more of O, N, and S atoms, with the proviso that at least one Rf group includes one or more of (i) at least one straight-chain C4-C20 aliphatic or C4-C20 cycloaliphatic group, (ii) at least one ether oxygen atom, and (iii) at least one branched C3-C20 aliphatic group, and
- E is Rf,
- 36
- wherein R1, R2, and Rf, and Q are defined as above, and
- (4) —CRf(E)2,
- wherein each E independently is as defined above, and Rf is as defined above.
Polyfunctional halogenated acrylates having structures selected from the group consisting of
- 38 CF3CF(OC(O)CH═CH2)CF2O(CF2)4OCF2CF(OC(O)CH═CH2)CF3,and XXVIICF3CF(OC(O)CH═CH2)CF2OCF2CF(OC(O)CH═CH2)CF2OCF2CF(OC(O)CH═CH2)CF3, XXVIII
- and corresponding methacrylates of these structures.
A method of preparing ClCF2CFClOR8f and Cl2CFCFClOR8f comprising the step of direct fluorination of Cl2CHCH2OR8 and Cl3CCH2OR8, respectively, wherein R8 is a C1-C20 alkyl- or acyl-containing group optionally containing up to 5 ether oxygen atoms and R8f is the corresponding perfluoroalkyl or perfluoracyl-containing group, optionally containing up to 5 ether oxygen atoms.
A perfluorinated ketone having the structure R5fCF2COCF3, R5fOCF2COCF2Cl, or R5fOCF2COCF2OR5f, wherein R5f is a linear perfluoroalkyl or perfluorooxyalkyl group having in the range of 2 to 20 carbon atoms.
Dependencies are inferred from the claim text.