Oxetane compound, oxetane copolymer, and process for producing the oxetane compound

• US 6,495,636 B2
• Filed: 01/09/2001
• Issued: 12/17/2002
• Est. Priority Date: 07/09/1998
• Status: Expired due to Fees

• Current Assignee: JSR Corporation
• Original Assignee: JSR Corporation
• Inventors: Sugiyama, Naoki, Sekiguchi, Manabu, Sato, Hozumi
• Primary Examiner(s): Lambkin, Deborah C.
• Application Number:
  US09/756,220
• Publication Number:
  US 20010002423A1
• Time in Patent Office: 707 Days
• Field of Search: 549/50, 528/111, 525/326.3
• US Class Current: 525/326.3
• CPC Class Codes: C07D 305/06 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
• CPC Class Codes: C07D 407/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 409/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C08F 16/26 Monomers containing oxygen atoms in addition to the ether oxygen
• CPC Class Codes: C08F 216/14 Monomers containing only one unsaturated aliphatic radical
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 65/18 Oxetanes
• CPC Class Codes: C08G 65/22 Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring

Abstract

Oxetane compounds represented by general formula (1), which are excellent in radical polymerizability and cationic polymerizability and in compatibility and copolymerizability with other copolymerizable monomers; a process for producing the compounds; and an oxetane copolymer which is excellent in compatibility among the monomer units and has a low water absorption and excellent transparency.

[In general formula (1), substituent R¹ is hydrogen, alkyl, fluorine, fluoroalkyl, allyl, aryl, furyl, or thienyl; substituents R², R³, and R⁴ each independently is hydrogen or C_1-6 alkyl; and m and n each is an integer of 1 to 10 (provided that not all of R², R³, and R⁴ are hydrogen)].

Claims

1. An oxetane compound represented by the following formula (1):

wherein substituent R¹ is hydrogen, alkyl, fluorine, fluoroalkyl, ally, aryl, furyl or thienyl;

substituents R², R³ and R⁴ each independently is hydrogen or alkyl having 1 to 6 carbon atoms; and

m and n each is an integer of 1 to 10, provided that not all of substituents R², R³ and R⁴ are hydrogen.

6. The oxetane compound according to claim 1, wherein R¹ is C₁-C₄ alkyl.

7. The oxetane compound according to claim 6, wherein R¹ is methyl or ethyl.

8. The oxetane compound according to claim 1, wherein each of R², R³ and R⁴ is hydrogen.

9. The oxetane compound according to claim 1, wherein m is 1 to 4.

10. The oxetane compound according to claim 1, wherein n is 2 to 5.

2. An oxetane copolymer obtained by radical-polymerizing an oxetane compound represented by the following formula (1), its number average molecular weight converted to polystyrene, which is measured by GPC, being in the range of 1,000 to 1,000,000,

wherein substituent R¹ is hydrogen, alkyl, fluorine, fluoroalkyl, ally, aryl, furyl or thienyl;

substituents R², R³ and R⁴ each independently is hydrogen or alkyl having 1 to 6 carbon atoms; and

m and n each is an integer of 1 to 10.

3. The oxetane copolymer according to claim 2, which is represented by the following formula (2):

wherein substituent R¹ is hydrogen, alkyl, fluorine, fluoroalkyl, ally, aryl, furyl or thienyl;

substituents R², R³ and R⁴ each independently is hydrogen or alkyl having 1 to 6 carbon atoms;

R⁵ is hydrogen, fluorine or chlorine;

R⁶ is hydrogen, fluorine, fluoroalkyl, alkoxy or fluorinated alkoxy;

m and n each is an integer of 1 to 10; and

a and b each is in the range of 0.1 to 99.9% by mole.

4. The oxetane copolymer according to claim 2, which comprises, as a monomer component, a fluorine compound represented by the following general formula (3):

wherein substituent R⁵ is hydrogen, fluorine or chlorine; and

substituent R⁶ is hydrogen, fluorine, fluoroalkyl, alkoxy, or fluorinated alkoxy.

11. The oxetane copolymer according to claim 4, wherein said fluorine compound represented by the formula (3) is selected from a first group fluorine compound consisting of tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, chlorotrifluorethylene and fluorinated vinylidene.

12. The oxetane copolymer according to claim 4, wherein said fluorine compound represented by the formula (3) is selected from a second group fluorine compound consisting of alkyl perfluorovinyl ethers, alkoxyalkyl perfluorovinyl ethers;

perfluoro (alkyl vinyl ethers) and perfluoro (alkoxy alkyl vinyl ethers).

13. The oxetane copolymer according to claim 12, wherein said perfluoro (alkyl vinyl ethers) are selected from the group consisting of perfluoro (methyl vinyl ethers), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether) and perfluoro (isobutylvinyl ether).

14. The oxetane copolymer according to claim 12, wherein said perfluoro (alkoxyalkyl vinyl ether) is perfluoro (propoxypropyl vinyl ether).

15. The oxetane copolymer according to claim 4, which comprises from 0.1 to 2,000 parts by weight of the fluorine compound per 100 parts by weight of the oxetane compound.

16. The oxetane copolymer according to claim 2, wherein said radical-polymerizing is effected in the presence of a radical generator, which is polysiloxane compound containing an azo group.

17. The oxetane copolymer according to claim 2, which has a number average molecular weight of from 5,000 to 500,000.

18. The oxetane copolymer according to claim 2, which has a water absorption of 0.1 to 7% by weight.

19. The oxetane copolymer according to claim 2, which further contains units obtained from an unsaturated monomer having an epoxy group.

20. The oxetane copolymer according to claim 2, which further contains units obtained from an unsaturated monomer having a hydroxy group.

5. A process for producing an oxetane compound represented by the general formula (1), by reacting an oxetane alcohol compound represented by the following formula (4) with a halogenated vinyl ether compound represented by the following formula (5) in the presence of a phase transfer catalyst:

wherein substituent R¹ is hydrogen, alkyl, fluorine, fluoroalkyl, ally, aryl, furyl or thienyl;

substituents R², R³ and R⁴ each independently is hydrogen or alkyl having 1 to 6 carbon atoms; and

m and n each is an integer of 1 to 10,

wherein substituent R¹ and repetition number m are the same in the formula (1),

wherein substituents R², R³ and R⁴ and repetition number n each is the same in the formula (1), and X is a halogen atom.

21. The process according to claim 5, wherein said compound of the formula (4) is selected from the group consisting of 3-methyl-3-oxetane methanol, 3-methyl-3-oxetane ethanol, 3-methyl-3-oxetane propanol, 3-ethyl-3-oxetane methanol, 3-ethyl-3-oxetane propanol, 3-propyl-3-oxetane methanol, 3-propyl-3-oxetane ethanol and 3-propyl-3-oxetane propanol.

22. The process according to claim 5, wherein said compound of the formula (5) is selected from the group consisting of 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, 3-chloropropyl vinyl ether, 3-bromopropyl vinyl ether, 4-chlorobutyl vinyl ether and 4-bromobutyl vinyl ether.

23. The process according to claim 5, wherein 0.1 to 10 moles of the halogenated vinyl ether compound of the formula (5) is reacted with 1 mole of the oxetane alcohol compound of the formula (4).

24. The process according to claim 5, which is effected at a temperature of 0 to 100°

C.

25. The process according to claim 5, which is effected at a temperature of 10 to 90°

C.

26. The process according to claim 5, which is effected at a pH of from 5 to 14.

27. The process according to claim 26, which is effected at a pH of from 6 to 14.

28. The process according to claim 27, which is effected at a pH of from 7 to 14.

29. The process according to claim 5, which is effected in the presence of a phase transfer catalyst.

30. The process according to claim 29, wherein said phase transfer catalyst is selected from the group consisting of a quaternary ammonium salt and a quaternary phosphonium salt.