Durable formaldehyde-free phenolic resins, and method of preparing such resins

• US 5,367,043 A
• Filed: 11/06/1991
• Issued: 11/22/1994
• Est. Priority Date: 11/06/1991
• Status: Expired due to Term

• Current Assignee: Wiley Organics Inc.
• Original Assignee: Enzymol International, Inc.
• Inventors: Butler, John M., Brandon, Richard L.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): Jones, Richard
• Application Number:
  US07/788,791
• Time in Patent Office: 1,112 Days
• Field of Search: 528/193, 528/212, 528/218, 528/205
• US Class Current: 528/193
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C12P 7/22 aromatic

Abstract

A curable formaldehyde-free phenolic resin having formula (I): ##STR1## wherein a and b each represent an integer equal to or greater than 1, a+b multiplied by n is an integer of about 3 to 100; ##STR2## m is 0 or 1; and R is hydrogen, halogen, alkyl having about 1 to 12 carbon atoms, aryl having about 6 to 12 carbon atoms, allyl having 3 or 4 carbon atoms, aralkyl having about 7 to 13 carbon atoms, alkaryl having about 7 to 13 carbon atoms, alkoxy having about 1 to 4 carbon atoms, aryloxy having about 6 to 12 carbon atoms, or ##STR3## and methods for preparing such resin are described.

Claims

1. A curable formaldehyde-free phenolic resin having the formula (I):

##STR16## wherein a and b each represent an integer equal to or greater than 1, a+b multiplied by n is an integer of about 3 to 100;

##STR17## m is 0 or 1; and

R is hydrogen, halogen, alkyl having about 1 to 12 carbon atoms, aryl having about 6 to 12 carbon atoms, allyl having 3 or 4 carbon atoms, aralkyl having about 7 to 13 carbon atoms, alkaryl having about 7 to 13 carbon atoms, alkoxy having about 1 to 4 carbon atoms, aryloxy having about 6 to 12 carbon atoms, or ##STR18##

2. The resin of claim 1 wherein ##STR19## said resin being heated to a temperature of about 170°

to 180°

C. to cyclize the --OCH₂ C═

CH groups so as to form an oxygen-containing six member ring fused to the aromatic ring.

3. The resin of claim 1 having a formula (II)-(V):

##STR20## where a, b and R are defined as in claim 1;

##STR21## where a, b, R, X and m are defined as in claim 1;

##STR22## where a, b, X and m are defined as in claim 1.

4. The resin of claim 1 having a formula (VI)-(IX):

##STR23## where a, b and R are defined as in claim 1;

##STR24## where a, b, R, X and m are defined as in claim 1;

##STR25## where a, b, X and m are defined as in claim 1.

5. The resin of claim 2 having a formula (X)-(XII):

##STR26## where a, b and R are defined as in claim 1;

##STR27## where a, b, R, X and m are defined as in claim 1;

##STR28## where a, b, X and m are defined as in claim 1;

or ##STR29## where a, b, X and m are defined as in claim 1.

6. A method for preparing a curable formaldehyde-free phenolic resin having the formula ##STR30## wherein a and b each represent an integer equal to or greater than 1, a+b multiplied by n is an integer of about 3 to 100;

##STR31## m is 0 or 1; and

R is hydrogen, halogen, alkyl having about 1 to 12 carbon atoms, aryl having about 6 to 12 carbon atoms, allyl having 3 or 4 carbon atoms, aralkyl having about 7 to 13 carbon atoms, alkaryl having about 7 to 13 carbon atoms, alkoxy having about 1 to 4 carbon atoms, aryloxy having about 6 to 12 carbon atoms, or ##STR32## said method comprising;

reacting a first phenol having the structure (B) as defined in formula (I) or a mixture thereof with a propargyl halide to form one or more propargyloxyphenols, or reacting said phenol or mixture thereof with an allyl halide to form one or more allyloxyphenols;

copolymerizing said one or more propargyloxyphenols or said one or more allyloxyphenols with a second phenol having the structure (B) as defined in formula (I), said first phenol and said second phenol being the same or different, to provide said curable formaldehyde-free phenolic resin; and

recovering said curable formaldehyde-free phenolic resin.

7. The method of claim 6 which comprises reacting said first phenol with less than the stoichiometric amount of said propargyl halide or said allyl halide to form a mixture containing a pre-determined ratio of said first phenol to said propargyloxyphenol or said allyloxyphenol;

copolymerizing said mixture of phenol and propargaryloxyphenol or allyloxyphenol to provide a curable formaldehyde-free phenolic resin containing a pre-determined ratio of phenolic groups to propargyloxyphenolic groups or allyloxyphenolic group; and

recovering the curable formaldehyde-free phenolic resin.

8. The method of claim 6 wherein said curable formaldehyde-free phenolic resin is prepared by enzymatic oxidative coupling of said propargyl oxyphenol or said allyl oxyphenol with said phenol.

9. The method of claim 6 wherein said curable formaldehyde-free phenolic resin is capable of being cured catalytically or thermally at a temperature of about 200°

to 250°

C. to provide a cured resin which exhibits high oxidation and thermal stability.

10. The method of claim 6 wherein said curable formaldehyde-free phenolic resin is prepared by the reaction of said first phenol and said allyl halide, said resin capable of being co-cured in the presence of a maleimide.

11. The method of claim 6 wherein said curable formaldehyde-free phenolic resin is prepared by the reaction of said first phenol and said propargyl halide.

12. The method of claim 11 wherein said curable formaldehyde-free phenolic resin is heated to a temperature of about 170°

to 180°

C. to cyclize the --O CH₂ C═

CH groups to form an oxygen-containing six member ring fused to the aromatic ring.