Polyphenylene ether resin comprising chloroform extractable/nonextractable polyphenylene ether resin

• US 4,923,932 A
• Filed: 09/09/1988
• Issued: 05/08/1990
• Est. Priority Date: 09/09/1987
• Status: Expired due to Term

• Current Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Inventors: Oda, Hiroji, Katayose, Teruo
• Primary Examiner(s): ANDERSON, HAROLD
• Application Number:
  US07/242,234
• Time in Patent Office: 606 Days
• Field of Search: 525/391, 525/390, 525/392, 525/534, 525/535
• US Class Current: 525/391
• CPC Class Codes: C08F 283/08 on to polyphenylene oxides
• CPC Class Codes: C08G 65/44 by oxidation of phenols
• CPC Class Codes: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 71/12 Polyphenylene oxides
• CPC Class Codes: C08L 71/126 modified by chemical after-treatment

Abstract

A novel cured polyphenylene ether resin is disclosed comprising a chloroform nonextractable polyphenylene ether and a chloroform extractable polyphenylene ether. By subjecting the resin to pyrolysis gas chromatography, the resin is decomposed to form 3,5-dimethylphenol specifically. The chloroform extractable polyphenylene ether is contained in the resin in an amount of 0.01 to 20% by weight and comprises polyphenylene ether units substituted by an alkenyl group and/or an alkynyl group. The novel cured polyphenylene ether resin has excellent mechanical properties, electrical properties, heat resistance and chemical resistance. The cured polyphexylene ether resin is prepared by curing a novel curable polyphenylene ether resin comprising polyphenylene ether units substituted with an alkenyl groups and/or an alkynyl groups at a specific average substitution degree. The novel curable polyphenylene ether resin has not only excellent mechanical properties and desired electric properties such as a low dielectric constant and a low dielectric dissipation factor, but also excellent melt processability and storage properties.

Claims

1. A cured polyphenylene ether resin comprising a chloroform nonextractable polyphenylene ether and a chloroform extractable polyphenylene ether,

said resin being decomposable by pyrolysis gas chromatography to form (a) 2-methylphenol, (b) 2,6-dimethylphenol, (c) 2,4-dimethylphenol, (d) 3,5-dimethylphenol and (e) 2,4,6-trimethylphenol in proportions such that said components (a), (b), (c), (d) and (e) satisfy the following inequality:

##EQU6## wherein A, B, C, D and E represent the areas of peaks on a pyrolysis gas chromatogram attributed to said components (a), (b), (c), (d) and (e), respectively,

said chloroform extractable polyphenylene ether being present in an amount of from 0.01 to 20 % by weight, based on the weight of said resin, as determined from the amount of a chloroform extract obtained by treating the resin with chloroform at 23°

C. for 12 hours,

said chloroform extractable polyphenylene ether containing units of the formula;

##STR39## wherein R¹, R², R³ and R⁴ each independently represent a hydrogen atom, an alkenyl group represented by the formula;

##STR40## wherein l is an integer of from 1 to 4, and R⁵, R⁶ and R⁷ each independently represent a hydrogen atom or a methyl group,

or an alkynyl group represented by the formula;

space="preserve" listing-type="equation">(CH.sub.2).sub.k C.tbd.C--R.sup.8 (III)

wherein k is an integer of from 1 to 4 and R⁸ represents a hydrogen atom, a methyl group or an ethyl group,

at least one of R¹, R², R³ and R⁴ being other than hydrogen,

with the proviso that each unit is the same or different.

2. The cured polyphenylene ether resin according to claim 1, wherein said chloroform extractable polyphenylene ether is present in an amount of from 0.01 to 10% by weight, based on the weight of said resin.

3. The cured polyphenylene ether resin according to claim 1 or 2, wherein said alkenyl group is an allyl group.

4. The cured polyphenylene ether resin according to claim 1 or 2, wherein said alkynyl group is a propargyl group.

5. The cured polyphenylene ether resin according to claim 1, wherein said chloroform extractable polyphenylene ether has a viscosity number (η

sp/c) of from 0.05 to 1.0 as measured in a 0.5 g/dl chloroform solution of the chloroform extractable polyphenylene ether at 30°

C.

6. A curable polyphenylene ether resin comprising at least one polyphenylene ether represented by the formula:

space="preserve" listing-type="equation">Q'"'"'--J--H].sub.m (IV)

wherein m is an integer of from 1 to 6, J is a polyphenylene ether chain comprising units of the formula;

##STR41## wherein R¹, R², R³ and R⁴ each independently represent a hydrogen atom, an alkenyl group represented by the formula;

##STR42## wherein l is an integer of from 1 to 4, and R⁵, R⁶ and R⁷ each independently represent a hydrogen atom or a methyl group;

or an alkynyl group represented by the formula;

space="preserve" listing-type="equation">--CH.sub.2 --.sub.k C.tbd.C--R.sup.8 (III)

wherein k is an integer of from 1 to 4 and R⁸ represents a hydrogen atom, a methyl group or an ethyl group,

at least one of R¹, R², R³, and R⁴ being other than hydrogen, and

Q'"'"' represents a hydrogen atom when m is 1, and Q'"'"' in each polyphenylene ether independently represents Q or Q substituted with at least one substituent selected from the group consisting of an alkenyl group as defined above and an alkynyl group as defined above when m is greater than 1,

said Q representing the residue of a polyfunctional phenol having from 2 to 6 phenolic hydroxyl groups and having unpolymerizable substituents at the ortho and para positions with respect to the phenolic hydroxyl groups,

with the proviso that each polyphenylene ether chain is the same or different,

said curable polyphenylene ether resin having an average substitution degree of alkenyl and alkynyl groups of from 0.1 to 100 % by mole as defined by the formula;

##EQU7## the ratio of the total number of moles of alkenyl and alkynyl groups to the number of moles of phenyl groups being determined in terms of the ratio of the total area of peaks attributed to the protons of alkenyl and alkynyl groups to the area of peak attributed to the protons of phenyl groups on a ¹ H-NMR spectrum of the curable polyphenylene ether resin.

7. The curable polyphenylene ether resin according to claim 6, having a viscosity number (η

sp/c) of from 0.2 to 1.0 as measured in a 0.5 g/dl chloroform solution of the resin at 30°

C.

8. The curable polyphenylene ether resin according to claim 6 or 7, wherein said average substitution degree is from 0.5 to 50% by mole.

9. The curable polyphenylene ether resin according to claim 6, wherein m is 1 and Q'"'"' represents a hydrogen atom.

10. The curable polyphenylene ether resin according to claim 6, wherein m is 2 and Q represents a bifunctional phenol residue.

11. The curable polyphenylene ether resin according to claim 10, wherein said bifunctional phenol residue is represented by the formula:

##STR43##

12. The curable polyphenylene ether resin according to claim 10, wherein said bifunctional phenol residue is represented by the formula:

##STR44##

13. The curable polyphenylene ether resin according to claim 10, wherein said bifunctional phenol residue is represented by the formula:

##STR45##

14. The curable polyphenylene ether resin according to claim 6, wherein m is 3 and Q represents a trifunctional phenol residue.

15. The curable polyphenylene ether resin according to claim 14, wherein said trifunctional phenol residue is represented by the formula:

##STR46##

16. The curable polyphenylene ether resin according to any one of claims 6, wherein said alkenyl group is an allyl group.

17. The curable polyphenylene ether resin according to any one of claims 6, wherein said alkynyl group is a propargyl group.