Polyarylene polyethers with pendant vinyl and ethynyl groups and process for preparation thereof

• US 4,806,601 A
• Filed: 12/31/1986
• Issued: 02/21/1989
• Est. Priority Date: 11/08/1984
• Status: Expired due to Fees

• Current Assignee: Goodrich Corporation (Rtx Corporation)
• Original Assignee: Goodrich Corporation (Rtx Corporation)
• Inventors: Percec, Virgil
• Primary Examiner(s): Welsh, Maurice J.
• Assistant Examiner(s): ACQUAH, SAMUEL A
• Application Number:
  US06/948,245
• Time in Patent Office: 783 Days
• Field of Search: 528/171, 525/391, 525/392, 525/534, 525/535, 568/33, 568/49, 568/636
• US Class Current: 525/391
• CPC Class Codes: C08G 65/48 Polymers modified by chemical after-treatment
• CPC Class Codes: C08G 75/23 Polyethersulfones

Abstract

A method for the synthesis of polyarylene polyether (PAPE) oligomers with pendant vinyl groups is presented. Aromatic polyether sulfone (APS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) backbones are used for specific examples. Terminal vinyl groups may also be provided on the APS by forming the α, ω-di(benzyl)APS before the first step of a synthesis to form a pendant groups which step involves the chloromethylation of APS and PPO to provide oligomers with chloromethyl groups. PPO containing bromomethyl groups was obtained by radical bromination of the PPO methyl groups. Both chloromethylated and bromomethylated starting materials are converted to their phosphonium salts, and then subjected to a phase transfer catalyzed Wittig reaction to provide the pendant vinyl groups. An APS containing pendant ethynyl groups is prepared by bromination of the APS with pendant vinyl groups, followed by a phase transfer catalyzed dehydrobromination. Differential scanning calorimetry analysis of the thermal curing of the oligomers containing pendant vinyl groups, and, ethynyl groups, showed that the curing reaction is much faster for the former. The resulting network polymers were flexible when the starting oligomer contained pendant vinyl groups, and very rigid when it contained pendant ethynyl groups.

Claims

1. A polyfunctionalized substantially linear crosslinkable thermoplastic polyarylene polyether oligomer, or polyarylene polythioether (PAPE) oligomer having at least two pendant vinyl groups in said oligomer represented by a formula selected from:

wherein,

R represents O or S in an ether linkage with R^e or R^e'"'"' ;

R^e represents the residuum of a terminal dihydric phenol or dihydric thiophenol DH(T)P monomer having a terminal phenol, thiophenol or halophenyl group;

R^e'"'"' represents the residuum of a terminal monohydric phenol MHP monomer having a terminal substituted phenol group;

"PAPE" represents the residuum of the PAPE oligomer which is selected from the group consisting of an oligomer of a monohydric 2,6-disubstituted phenol, and an oligomer of at least one mononuclear or polynuclear DH(T)P monomer in which oligomer each phenyl ring is connected to another through an O, Si, C or S atom; and

,

the vinyl group (--CH═

CH₂) is connected to an electron-rich phenyl ring in the backbone of said PAPE.

2. The crosslinkable PAPE oligomer of claim 1 wherein said "PAPE" represents the residuum of said DH(T)P optionally substituted with inert substituents, so that said crosslinkable oligomer is represented by the formula:

##STR18## wherein, n is an integer in the range from 2 to about 100, and there is present from about 0.2 to about 2 vinyl groups per repeating unit in the oligomer'"'"'s chain;

R and R³ have the same connotation as hereinbefore; and

,

["DH(T)P"] is the residuum of DH(T)P moieties linked through a linking residue R^s so as to form a repeating unit

space="preserve" listing-type="equation">[DH(T)P-R.sup.s ]

wherein DH(T)P is a residuum of a structure selected from ##STR19## X represents a bond between aromatic carbon atoms or a divalent connecting radical selected from the group consisting of C═

O, --O--, --S--, --S--S--, --SO₂ --, --Si-- and divalent organic hydrocarbon radicals such as alkylene, alkylidene, cycloaliphatic, or the halogen, alkyl, aryl, or like substituted alkylene, alkylidene and cycloaliphatic radicals as well as alkarylene, cycloalkyl and aromatic radicals, and a ring fused to both Ar groups;

R¹, R², R³, and R⁴ are inert substituents, which if present on any phenyl ring, may each be the same or different and represent halogen, particularly chlorine or bromine;

NO₂ ;

alkyl having from 1 to about 18 carbon atoms, without regard for the spatial configuration such as normal, iso or tertiary;

alkoxy having from 1 to about 18 carbon atoms; and

, hydrogen; and

,

R^s represents the residuum of a reactive linking group selected from the group consisting of the same or another [DH(T)P];

a α

,ω

-dihaloalkane having from 1 to about 18 carbon atoms;

phosgene;

alkyl and aryl diacid halides including dihaloaryl having six ring carbon atoms;

dihalophenyl phosphonate;

bis(haloalkoxy) alkane having from 3 to about 20 carbon atoms; and

, dihalocycloalkanes having from 3 to 7 ring carbon atoms;

so that the molecular weight Mn of said crosslinkable oligomer is in the range from about 1000 to about 100,000.

3. The PAPE oligomer of claim 1 wherein R represents O.

4. The PAPE oligomer of claim 1 wherein R represents S.

5. The PAPE oligomer of claim 1 wherein said R^e'"'"' represents the residuum of 2,6-dimethylphenol.

6. The PAPE oligomer of claim 1 wherein said R represents O, and said R^e represents the residuum of a dihydric phenol having a chain end selected from a phenol group and a halophenyl group.

7. The PAPE oligomer of claim 2 wherein said [DH(T)P] is chain extended with the residuum R^s of said reactive linking group so that said crosslinkable oligomer is represented by the formula:

##STR20## wherein, R^s represents the residuum of a reactant, or, reactive solvent, which residuum links two [DH(T)P] moieties which may be the same or different.

8. The PAPE oligomer of claim 2 wherein DH(T)P and R^s are each residua of a dihydric phenol ("DHP") selected from the group consisting of a dihydric polynuclear phenol and a dihydric mononuclear phenol.

9. The PAPE oligomer of claim 8 wherein said polynuclear DHP is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane;

2,2-bis(4-hydroxyphenyl)silane;

diphenyl sulfone;

diphenyl sulfide;

diphenyl ketone and diphenyl ether; and

said mononuclear DHP is a 1,4-dihydroxy benzene.

10. The PAPE oligomer of claim 9 wherein the combinations of the following DHPs are present as residua in the repeating unit:

(i) 2,2-bis(4-hydroxyphenyl)propane and diphenyl sulfone;

(ii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ketone;

(iii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ether;

(iv) diphenyl sulfone and diphenyl ketone;

(v) diphenyl ketone and diphenyl ether;

(vi) diphenyl sulfone and diphenyl ether;

(vii) diphenyl sulfone and 1,4-dihydroxy benzene;

(viii) diphenyl sulfide and diphenyl sulfone;

(ix) 2,2-bis(4-hydroxyphenyl)propane, diphenyl sulfone and 1,4-dihydroxy benzene; and

,

(x) diphenyl sulfone and 1,4-dihydroxy benzene.

11. The PAPE oligomer of claim 5 wherein said "PAPE" is the residuum of an oligomer of 2,6-dimethylphenol having a mol wt in the range from 1000 to about 10,000 and the O ether atom of one phenyl ring is connected to the phenyl ring of the next succeeding ring in said "PAPE".

12. The PAPE oligomer of claim 7 wherein R^s is a residuum selected from the group consisting of alkenyl having from 1 to about 20 carbon atoms, dihalophenyl phosphonate, and aralkenyl having from 7 to about 27 carbon atoms.

13. The PAPE oligomer of claim 7 wherein one said dihydric phenol moiety is derived from 4,4'"'"'-isopropylidenediphenol (BPA), and another dihydric phenol moiety is derived from a dihalophenylsulfone (DHPS) having the structure:

##STR21## wherein, X'"'"' represents halogen selected from the group consisting of fluorine, chlorine, bromine and iodine on one ring carbon atom; and

,

(s) represents inert substituents R¹ -R⁴ any of which if present on remaining positions on each ring, may each be the same or different and represent alkyl having from 1 to about 18 carbon atoms, without regard for the spatial configuration such as normal, iso or tertiary;

alkoxy having from 1 to about 18 carbon atoms;

nitro (NO₂) and, hydrogen.

14. The PAPE oligomer of claim 13 wherein the backbone consists essentially of an aromatic polyether sulfone (APS) having alternating bisphenol A "BPA(s)" and diphenyl sulfone "DPS(s)" residua, said APS being terminated with phenol or halophenyl units, optionally with each of said BPA(s), DPS(s) units having substituents, represented by formulae selected from:

space="preserve" listing-type="equation">(Ph)BPA(s)--O-DPS(s)--O--BPA(s)--.sub.n O--DPS(s)--BPA(s)(Ph)

space="preserve" listing-type="equation">and,

space="preserve" listing-type="equation">(HPh)DPS(s)--O--BPA(s)--O--DPS(s)--O--BPA(s)--.sub.n O--DPS(s)(HPh)

and the structures;

##STR22## wherein, (s) on any substitutable ring carbon atom represents H or R¹, R², R³ or R⁴ ;

(Ph) and (HPh) represent the phenol ##STR23## and halophenyl ##STR24## portions of the terminal BPA(s) and DPS(s) unit respectively;

R¹, R², R³ and R⁴ are inert substituents, any of which, if present on any phenyl ring, and R⁵, may each be the same or different, and are selected from the group consisting of halogen, alkyl having from 1 to about 18 carbon atoms, and alkoxy having from 1 to about 18 carbon atoms, said alkyl and alkoxy being each chosen without regard for the spatial configuration of the carbon atoms; and

,

n represents an integer in the range from about 2 to about 10.

15. The PAPE oligomer of claim 12 wherein one said dihydric phenol moiety is derived from 4,4'"'"'-isopropylidenediphenol (BPA), and another dihydric phenol moiety is derived from a dihalophenylsulfone (DHPS).

16. The PAPE oligomer of claim 1 wherein the backbone consists essentially of poly(2,6-dimethyl-1,4-phenylene oxide) terminated with a 2,6-dimethylphenol DMP unit, said backbone being represented by the structure:

##STR25## wherein, n represents an integer from about 5 to about 100, and there are from 2 to about 12 pendant vinyl group present in said backbone, and DMP represents dimethyl substituted phenol.

17. The PAPE oligomer of claim 1 having at least one terminal vinyl group in addition to said pendant vinyl groups, said oligomer being represented by a formula selected from:

##STR26## wherein, R, R^e, R^e'"'"' and "PAPE" have the same connotation as in claim 1.

18. The crosslinkable PAPE oligomer of claim 2 wherein said "PAPE" represents the residuum of said DH(T)P optionally substituted with inert substituents, so that said crosslinkable oligomer is represented by the formula:

##STR27## wherein, n is an integer in the range from 2 to about 100, and there is present from about 0.2 to about 1 vinyl group per repeating unit;

R and R^e have the same connotation as hereinbefore; and

["DH(T)P"] is the residuum of DH(T)P moieties linked through a linking residue R^s so as to form a repeating unit

space="preserve" listing-type="equation">[DH(T)P-R.sup.s ]

wherein DH(T)P is a residuum of a structure selected from the structures (I) and (II) so that the molecular weight Mn of said crosslinkable oligomer is in the range from about 1000 to about 10,000.

19. The PAPE oligomer of claim 18 wherein said R represents O, and said R^e represents the residuum of a dihydric phenol having a chain end selected from a phenol group and a halophenyl group.

20. The PAPE oligomer of claim 19 wherein DH(T)P and R^s are each residua of a dihydric phenol ("DHP") selected from the group consisting of a dihydric polynuclear phenol and a dihydric mononuclear phenol.

21. The PAPE oligomer of claim 20 wherein said polynuclear DHP is selected from the group consisting of 2,2-bis(4 hydroxyphenyl)propane;

2,2-bis(4-hydroxyphenyl)silane;

diphenyl sulfone;

diphenyl sulfide;

diphenyl ketone and diphenyl ether; and

said mononuclear DHP is a 1,4-dihydroxy benzene.

22. The PAPE oligomer of claim 21 wherein the combinations of the following DHPs are present as residua in the repeating unit:

(i) 2,2-bis(4-hydroxyphenyl)propane and diphenyl sulfone;

(ii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ketone;

(iii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ether;

(iv) diphenyl sulfone and diphenyl ketone;

(v) diphenyl ketone and diphenyl ether;

(vi) diphenyl sulfone and diphenyl ether;

(vii) diphenyl sulfone and 1,4-dihydroxy benzene;

(viii) diphenyl sulfide and diphenyl sulfone;

(ix) 2,2-bis(4-hydroxyphenyl)propane, diphenyl sulfone and 1,4-dihydroxy benzene; and

,

(x) diphenyl sulfone and 1,4-dihydroxy benzene.

23. The PAPE oligomer of claim 17 wherein the backbone consists essentially of poly(2,6-dimethyl-1,4-phenylene oxide) terminated with a 2,6-dimethylphenol DMP unit, said backbone being represented by the structure:

##STR28## wherein n represents an integer from about 5 to about 100, and there are from 2 to about 12 pendant vinyl groups present in said backbone, and DMP represents dimethyl-substituted phenol.

50. The process of claim 49 wherein said polyfunctionalized PAPE oligomer is represented by a formula in claim 1.

51. The process of claim 50 wherein said polyfunctionalized PAPE oligomer has a backbone consisting essentially of an aromatic polyether sulfone or aromatic polythioether sulfone oligomer ("APS") represented by the formula given in claim 14.

52. The process of claim 50 wherein said polyfunctionalized PAPE oligomer has a backbone consisting essentially of poly(2,6-dimethyl-1,4-phenylene oxide).

53. The process of claim 50 wherein step (a) is carried out at a temperature in the range from about room temperature to about the reflux temperature of said first solvent;

said Lewis acid is tin tetrachloride; and

said halomethylating agent is 1 chloromethoxy-4-chlorobutane.

54. The process of claim 50 wherein step (b) is carried out in the presence of a phase transfer catalyst at a temperature in the range from about room temperature to about the reflux temperature of said second solvent.

24. A polyfunctionalized substantially linear crosslinkable thermoplastic polyarylene polyether oligomer, or polyarylene polythioether (PAPE) oligomer having at least two pendant ethynyl groups in said oligomer represented by a formula selected from:

##STR29## wherein, R represents O or S in an ether linkage with R^e or R^e'"'"' ;

R^e represents the residuum of a terminal dihydric phenol or dihydric thiophenol DH(T)P monomer having a terminal phenol, thiophenol or halophenyl group;

R^e'"'"' represents the residuum of a terminal monohydric phenol MHP monomer having a terminal substituted phenol group;

"PAPE" represents the residuum of the PAPE oligomer which is selected from the group consisting of an oligomer of a monohydric 2,6-disubstituted phenol, and an oligomer of at least one mononuclear or polynuclear DH(T)P monomer in which oligomer each phenyl ring is connected to another through an O, Si, C or S atom; and

,

the ethynyl group (--C.tbd.CH) is connected to an electron-rich phenyl ring in the backbone of said PAPE.

25. The crosslinkable PAPE oligomer of claim 24 wherein said "PAPE" represents the residuum of said DH(T)P optionally substituted with inert substituents, so that said crosslinkable oligomer is represented by the formula:

##STR30## wherein, n is an integer in the range from 2 to about 100, and there is present from about 0.2 to about 1 ethynyl group per repeating unit in the oligomer'"'"'s chain;

R and R^e have the same connotation as hereinbefore; and

,

["DH(T)P"] is the residuum of DH(T)P moieties linked through a linking residue R^s so as to form a repeating unit

space="preserve" listing-type="equation">[DH(T)P-R.sup.s ]

wherein DH(T)P is a residuum of a structure selected from the structures (I) and (II) and R^s represents the residuum of a reactive linking group selected from the group consisting of the same or another [DH(T)P];

a, w-dihaloalkane having from 1 to about 18 carbon atoms;

phosgene;

alkyl and aryl diacid halides including dihaloaryl having six carbon atoms;

dihalophenyl phosphonate;

bis(haloakloxy)alkane having from 3 to about 20 carbon atoms; and

, dihalocycloalkanes having from 3 to 7 ring carbon atoms;

so that the molecular weight Mn of said crosslinkable oligomer is in the range from about 1000 to about 100,000.

26. The PAPE oligomer of claim 24 wherein R represents O.

27. The PAPE oligomer of claim 24 wherein R represents S.

28. The PAPE oligomer of claim 24 wherein said R^e'"'"' represents the residuum of 2,6-dimethylphenol.

29. The PAPE oligomer of claim 24 wherein said R represents O, and said R^e represents the residuum of a dihydric phenol having a chain end selected from a phenol group and a halophenyl group.

30. The PAPE oligomer of claim 25 wherein said [DH(T)P] is chain extended with the residuum R^s of said reactive linkage group so that said crosslinkable oligomer is represented by the formula:

##STR31## wherein, R^s represents the residuum of a reactant, or, reactive solvent, which residuum links two [DH(T)P] moieties which may be the same or different.

31. The PAPE oligomer of claim 25 wherein DH(T)P and R^s are each a residuum of a dihydric phenol ("DHP") selected from the group consisting of a dihydric polynuclear phenol and a dihydric mononuclear phenol.

32. The PAPE oligomer of claim 31 wherein said polynuclear DHP is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane;

2,2-bis(4-hydroxyphenyl)silane;

diphenyl sulfone;

diphenyl sulfide;

diphenyl ketone and diphenyl ether; and

said mononuclear DHP is a 1,4-dihydroxy benzene.

33. The PAPE oligomer of claim 32 wherein the combinations of the following DHPs are present as residua in the repeating unit:

(i) 2,2-bis(4-hydroxyphenyl)propane and diphenyl sulfone;

(ii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ketone;

(iii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ether;

(iv) diphenyl sulfone and diphenyl ketone;

(v) diphenyl ketone and diphenyl ether;

(vi) diphenyl sulfone and diphenyl ether;

(vii) diphenyl sulfone and 1,4-dihydroxy benzene;

(viii) diphenyl sulfide and diphenyl sulfone;

(ix) 2,2-bis(4-hydroxyphenyl)propane, diphenyl sulfone and 1,4-dihydroxy benzene; and

,

(x) diphenyl sulfone and 1,4-dihydroxy benzene.

34. The PAPE oligomer of claim 30 wherein R^s is a residuum selected from the group consisting of alkenyl having from 1 to about 20 carbon atoms, dihalophenyl phosphonate, and aralkenyl having from 7 to about 27 carbon atoms.

35. The PAPE oligomer of claim 30 wherein one said dihydric phenol moiety is derived from 4,4'"'"'-isopropylidenediphenol (BPA), and another dihydric phenol moiety is derived from a dihalophenylsulfone (DHPS) having the structure:

##STR32## wherein, X'"'"' represents halogen selected from the group consisting of fluorine, chlorine, bromine and iodine; and

,

(s) represents inert substituents R¹ -R⁴ any of which if present on remaining positions on each ring, may each be the same or different and represent alkyl having from 1 to about 18 carbon atoms, without regard for the spatial configuration such as normal, iso or tertiary;

alkoxy having from 1 to about 18 carbon atoms;

nitro (NO₂) and, hydrogen.

36. The PAPE oligomer of claim 35 wherein the backbone consists essentially of an aromatic polyether sulfone (APS) having alternating bisphenol A "BPA(s)" and diphenyl sulfone "DPS(s)" residua, said APS being terminated with phenol or halophenyl units, optionally with each of said BPA(s), DPS(s) units having substituents, represented by formulae selected from:

space="preserve" listing-type="equation">(Ph)BPA(s)--O-DPS(s)--O--BPA(s)--.sub.n O--DPS(s)--BPA(s)(Ph)

space="preserve" listing-type="equation">and,

space="preserve" listing-type="equation">(HPh)DPS(s)--O--BPA(s)--O-DPS(s)--O--BPA(s)--.sub.n O--DPS(s)(HPh)

and the structures;

##STR33## wherein, (s) represents H or R¹, R², R³ or R⁴ ;

(Ph) and (HPh) represent the phenyl and halophenyl portions of the terminal BPA(s) and DPS(s) units respectively;

R¹, R², R³ and R⁴ are inert substituents, any of which, if present on any phenyl ring, and R⁵, may each be the same or different, and are selected from the group consisting of halogen, alkyl having from 1 to about 18 carbon atoms, and alkoxy having from 1 to about 18 carbon atoms, said alkyl and alkoxy being each chosen without regard for the spatial configuration of the carbon atoms; and

,

n represents an integer in the range from about 2 to about 10.

37. The PAPE oligomer of claim 36 wherein said R⁵ are each methyl, and the remaining substituents are each hydrogen;

and, said Mn is in the range from about 1000 to about 5000.

38. The PAPE oligomer of claim 34 wherein one said dihydric phenol moiety is derived from 4,4'"'"'-isopropylidenediphenol (BPA), and another dihydric phenol moiety is derived from a dihalophenylsulfone (DHPS).

39. The PAPE oligomer of claim 24 wherein the backbone consists essentially of poly(2,6-dimethyl-1,4-phenylene oxide) terminated with a 2,6-dimethylphenol DMP unit, said backbone being represented by the structure:

##STR34## wherein n represents an integer from about 5 to about 100, and there are from 2 to about 12 pendant ethynyl groups present in said backbone, and DMP represents dimethyl-substituted phenol.

40. The PAPE oligomer of claim 24 having at least one terminal ethynyl group in addition to said pendant ethynyl groups, said oligomer being represented by a formula selected from:

##STR35## wherein, R, R^e, R^e'"'"' and "PAPE" have the same connotation as in claim 25.

41. The crosslinkable PAPE oligomer of claim 40 wherein said "PAPE" represents the residuum of said DH(T)P optionally substituted with inert substituents, so that said crosslinkable oligomer is represented by the formula:

##STR36## wherein, n is an integer in the range from 2 to about 100, and there is present from 0.2 to about 1 ethynyl group per repeating unit;

R and R^e have the same connotation as hereinbefore; and

,

["DH(T)P"] is the residuum of DH(T)P moieties linked through a linking residue R^s so as to form a repeating unit

space="preserve" listing-type="equation">[DH(T)P-R.sup.s ]

wherein DH(T)P is a residuum of a structure selected from the structures (I) and (II) and R^s represents the residuum of a reactive linking group selected from the group consisting of the same or another [DH(T)P];

a, w-dihaloalkane having from 1 to about 18 carbon atoms;

phosgene;

alkyl and aryl diacid halides including dihaloaryl having six carbon atoms;

dihalophenyl phosphate;

bis(haloalkoxy)alkane having from 3 to 20 carbon atoms; and

, dihaloxycloalkanes having from 3 to 7 ring carbon atoms so that the molecular weight Mn of said crosslinkable oligomer is in the range from about 1000 to about 10,000.

42. The PAPE oligomer of claim 40 wherein R represents O.

43. The PAPE oligomer of claim 41 wherein said R represents O, and said R^e represents the residuum of a dihydric phenol having a chain end selected from a phenol group and a halophenyl group.

44. The PAPE oligomer of claim 42 wherein DH(T)P and R^s are each residua of a dihydric phenol ("DHP") selected from the group consisting of a dihydric polynuclear phenol and a dihydric mononuclear phenol.

45. The PAPE oligomer of claim 44 wherein said polynuclear DHP is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane;

2,2-bis(4-hydroxyphenyl)silane;

diphenyl sulfone;

diphenyl sulfide;

diphenyl ketone and diphenyl ether; and

said mononuclear DHP is a 1,4-dihydroxy benzene.

46. The PAPE oligomer of claim 45 wherein the combinations of the following DHPs are present as residua in the repeating unit:

(i) 2,2-bis(4-hydroxyphenyl)propane and diphenyl sulfone;

(ii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ketone;

(iii) 2,2-bis(4-hydroxyphenyl)propane and diphenyl ether;

(iv) diphenyl sulfone and diphenyl ketone;

(v) diphenyl ketone and diphenyl ether;

(vi) diphenyl sulfone and diphenyl ether;

(vii) diphenyl sulfone and 1,4-dihydroxy benzene;

(viii) diphenyl sulfide and diphenyl sulfone;

(ix) 2,2-bis(4-hydroxyphenyl)propane, diphenyl sulfone and 1,4-dihydroxy benzene; and

,

(x) diphenyl sulfone and 1,4-dihydroxy benzene.

47. The PAPE oligomer of claim 40 wherein the backbone consists essentially of poly(2,6-dimethyl-1,4-phenylene oxide) terminated with a 2,6-dimethylphenol DMP unit, said backbone being represented by the structure:

##STR37## wherein n represents an integer from about 5 to about 100, and there are from 2 to about 12 ethynyl groups present in said backbone.

48. The PAPE oligomer of claim 45 wherein said DHP is chain extended with at least one --CH₂ -- group.

49. A process for forming a polyfunctionalized substantially linear crosslinkable thermoplastic polyarylene polyether oligomer, or polyarylene polythioether oligomer, (PAPE oligomer), having pendant vinyl groups in each oligomer chain, said process comprising,

(a) reacting a PAPE oligomer having a molecular weight Mn in the range from about 1000 to about 100,000, with a halomethylating agent in a first solvent for said PAPE oligomer and said halomethyalting agent, in the presence of a Lewis acid catalyst so as to introduce at least two pendant halomethyl groups on electron-rich phenyl groups in said PAPE oligomer and yield a halomethylated PAPE oligomer;

(b) reacting said halomethylated PAPE oligomer with triphenyl phosphine in solution with a second solvent, the same as or different from said first solvent, so as to yield the phosphonium salt of said halomethylated PAPE oligomer;

(c) reacting said phosphonium salt with a lower aliphatic aldehyde in the presence of aqueous alkali and an organic phase solvent for said phosphonium salt so as to yield at least two pendant vinyl groups on the backbone of said PAPE oligomer;

(d) precipitating said polyfunctionalized PAPE oligomer from said organic phase; and

,

(e) recovering said polyfunctionalized PAPE oligomer.

55. The process of claim 49 in which said PAPE oligomer has phenol terminal groups as the chain ends, and prior to step (a), reacting said PAPE oligomer with an α

-aralkyl compound in an organic solvent in the presence of concentrated aqueous alkali metal hydroxide solution and a phase transfer catalyst at a temperature below the reflux temperature of the solvent, so that said poylfunctionalized oligomer has terminal vinyl groups in addition to pendant vinyl groups.