Halogenated acrylates and polymers derived therefrom

• US 6,005,137 A
• Filed: 06/10/1997
• Issued: 12/21/1999
• Est. Priority Date: 06/10/1997
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: McCormick, Fred B., Moore, George G. I., Roberts, Ralph R., Cross, Elisa M., Schulz, Jay F., Chattoraj, Mita, Liu, Junkang Jacob
• Primary Examiner(s): ZITOMER, FRED
• Assistant Examiner(s): ZITOMER, FRED
• Application Number:
  US08/872,235
• Time in Patent Office: 924 Days
• Field of Search: 560/139, 560/140, 526/243
• US Class Current: 560/139
• CPC Class Codes: C07C 45/455 with carboxylic acids or their derivatives
• CPC Class Codes: C07C 49/84 containing ether groups, groups, groups, or groups
• CPC Class Codes: C07C 69/653 Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
• CPC Class Codes: C07D 213/64 attached in position 2 or 6
• CPC Class Codes: C08F 20/22 Esters containing halogen
• CPC Class Codes: C08F 20/34 Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 20/38 Esters containing sulfur

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.

Claims

1. A halogenated acrylate having the general formula ##STR21## wherein M is H,

A is oxygen or sulfur, and

Z is a group having at most 150 carbon atoms selected from the group consisting of ##STR22## in which each R¹ independently is F, Cl, or Br;

(2) ##STR23## 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), R⁴ COO--, R⁴ O--, --COOR⁴, --OSO₂ R⁴, or --SO₂ OR⁴, 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 ##STR24## 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), R⁴ COO--, R⁴ O--, --COOR⁴, --OSO₂ R⁴, or

--SO₂ OR⁴, 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) --(R_f)₂ E in which

both R_f 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 -C₂ 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 R_f 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 R_f, ##STR25## wherein R¹, R², and R_f, and Q are defined as above, and (4) --CR_f (E)₂,

wherein each E independently is as defined above, and R_f is as defined above.

2. The halogenated acrylate according to claim 1 wherein A is oxygen.

3. The halogenated acrylate according to claim 1 wherein Z is --C(R_f)₂ E, wherein each R_f group independently and E are as defined above.

4. The halogenated acrylate according to claim 1 wherein A is O (oxygen) and Z is ##STR26## wherein Q is ##STR27## and each R² and R³ is independently one of F, Cl, and CF₃.

5. The halogenated acrylate according to claim 1 wherein Z is ##STR28## wherein each R² is as previously defined.

6. The halogenated acrylate according to claim 2 wherein Z is --C(R_f)₂ E and wherein each R_f independently and E are as previously defined.

7. The halogenated acrylate according to claim 2 wherein Z is ##STR29## wherein each R² is as previously defined.

8. The halogenated acrylate according to claim 6 having the formula ##STR30## wherein one R_f group comprises a C₄ -C₂₀ aliphatic or C₄ -C₂₀ cycloaliphatic group and the second R_f group comprises at least one ether oxygen atom or a C₃ -C₂₀ branched aliphatic group, and E is as previously defined.

9. The halogenated acrylate according to claim 6 wherein E is ##STR31## and R² is previously defined.

10. The halogenated acrylate according to claim 8 wherein each R_f group independently is a perhalogenated phenyl group and E is a C₁ -C₂₀ perhalogenated aliphatic group comprising at least one ether oxygen atom.

11. The halogenated acylate of claim 8 wherein both R_f groups together form a perhalogenated cyclohexyl group and E is a perhalogenated phenyl group.

12. The halogenated acrylate according to claim 9 wherein each R² is F.

13. The halogenated acrylate according to claim 5 wherein at least one R² is selected from the group consisting of F, OC₆ F₅, SC₆ F₄ CF₃, OC(O)C₆ F₅, and OSO₂ C₄ F₉.

14. The halogenated acrylate according to claim 7, wherein at least one R² is selected from the group consisting of F, OC₆ F₅, SC₆ F₄ CF₃, OC(O)CF₃, and OSO₂ CF₃.

15. A halogenated acrylate having structure selected from the group consisting of ##STR32##

16. A halogenated acrylate having a structure selected from the group consisting of

17. A polymer comprising at least one mer unit derived by polymerization of the olefinic bond from a halogenated acrylate having the general formula wherein A is oxygen or sulfur, and Z is a group having at most 150 carbon atoms selected from the group consisting of ##STR33## in which each R¹ independently is F, Cl, or Br;

##STR34## 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), R⁴ COO--, R⁴ O--, --COOR⁴, --OSO₂ R⁴, or --SO₂ OR⁴, 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 ##STR35## 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, 1, Q (defined above), R⁴ COO--, R⁴ O--, --COOR⁴, --OSO₂ R⁴, or

--SO₂ OR⁴, 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) --(R_f)₂ E

wherein both R_f 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 R_f 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 R_f, ##STR36## wherein R¹, R ², and R_f, and Q are defined as above, and (4) --CR_f (E)₂,

wherein each E independently is as defined above, and R_f is as defined above.

18. An optical device comprising a polymer according to claim 17.