Title of Invention	A PROCESS FOR PRODUCTION MULTICYANATE ESTER
Abstract	The present Invention relates to a process or preparing mulucyanat.e esters by: a) reacting an adduct of a tertiary amine and a phenol- formaldehyde oligomer vvith cyanogen halide in a solvent to form a reaction prod1.Jct stream containing at least one compound selected &om the group consistiJ~g of tertiary amine-hydrohalide salt, solvent, and impurities" and based upon the total weight of the reaction product stream excluding the weight of said tertiary amine-hydrohalide salt, from about 10 percent 1:0 about 40 percent of a multicyanate ester; b) recycling a portion of said reaction product stream into the Juixture of step a; and c) separating and recovering said solvent and tertiary amine from said reaction product stream. The multi cyanate ester prod1..cts are useful as bonding agents in friction materials, molding luaterials, coatings and adhesives.

Title of Invention

A PROCESS FOR PRODUCTION MULTICYANATE ESTER

Abstract

The present Invention relates to a process or preparing mulucyanat.e esters by: a) reacting an adduct of a tertiary amine and a phenol- formaldehyde oligomer vvith cyanogen halide in a solvent to form a reaction prod1.Jct stream containing at least one compound selected &om the group consistiJ~g of tertiary amine-hydrohalide salt, solvent, and impurities" and based upon the total weight of the reaction product stream excluding the weight of said tertiary amine-hydrohalide salt, from about 10 percent 1:0 about 40 percent of a multicyanate ester; b) recycling a portion of said reaction product stream into the Juixture of step a; and c) separating and recovering said solvent and tertiary amine from said reaction product stream. The multi cyanate ester prod1..cts are useful as bonding agents in friction materials, molding luaterials, coatings and adhesives.

Full Text	0034-MAS-1996 WE CLAIM: 1. A process for producing multicyanate esters comprising the steps of a) feeding to a reaction vessel a first feed stream comprising a reaction medium comprising a solvent, an adduct of a tertiary amine and a phenol-formaldehyde oligomer or derivative thereof the formula: wherein: n is a positive whole number equal to or greater than 1; q and r are the same or different at each occurrence and are whole numbers from 0 to 3 with the proviso that the sum of q and r at each occurrence is equal to 3; o and p are the same or different at each occurrence are whole number • from 0 to 4, with the proviso that the- sum of o to p at each, occurrence is equal to 4; -X- is a divalent organic radical; A is selected from the group consisting of hydrogen chlorine, bromine, alkyl having from 1 to 10 carbons, epoxide, alkoxy having froni 1 to 10 carbons, cresol-type resins and mixtures thereof; and R3 is the same or different at each occurrence and is a substituent other than hydrogen which is unreactive under conditions necessary to completely cure the copolymer; b) feeding to said reaction vessel a second feedstream comprising a cyanogen halide in a reaction medium comprising a solvent; c) feeding to said reaction vessel a recycle stream comprising at least one of the following compounds selected from the group consisting of tertiary amine-hydrohalide salt, solvent, impurities, multicyanate ester and mixtures thereof; d) reacting said first, second, and recycle streams in said reaction vessel to form a reaction product stream comprising at least one of the following compounds selected from the group consisting of tertiary amine- hydrohalide salt, solvent and impurities and based upon the total weight of the reaction product stream excluding the weight of said tertiary amine- hydrohalide salt, from 10 percent to 40 percent of a multicyanate ester; and e) removing a portion of said reaction product stream to produce said recycle stream such that the volume ratio of said recycle stream to said product stream is 100 : 1 to 25 : 1, and recovered in a manner as herein described. 2. The process as claimed in claim 1, wherein said oligomer has a number average molecular weight of from 300 to 2000. 3. The process as claimed in claim 1, wherein said oligomer is a novolac resin and: n is 1 to about 8 ; q is 0 ; O is 0 and 4. The process as claimed in claim 1, wherein said tertiary amine is triethylamine. 5. The process as claimed in claim 1, wherein th'e weight ratio of oligomer to tertiary amine is from 1:1 to 1:1 20. 6. The process as claimed in claim 1 wherein said cyanogen halide is cyanogen bromide or cyanogen chloride. 7. The process as claimed in claim 1, wherein said solvent is selected from the group consisting of a water miscible solvent, water immiscible solvent and. mixtures thereof. 8. The process as claimed in claim 1, wherein said solvent is tetrahydrofliran or methylene chloride. 9. The process as claimed in claim 1, wherein the molar ratio of cynogen halide to oligomer repeat unit in said oligomer is from 1.02 : 1 to about 1.15:1. 10. The process as claimed in claim 1, wherein said reaction vessel is comprised of two loop reactors each having a residence time of from 10 to 25 minutes. 11. The process as claimed in claim 1, wherein the temperature in said reaction vessel is less than about -5°C. 12. The process as claimed in claim 1 wherein the multicyanate ester is extracted and recovered by quenching said reaction product stream with a water stream to produce an organic phase stream comprising said multicyanate ester and an aqueous phase stream; separating said organic phase stream comprising said multicyanate ester from said aqueous phase stream; and washing said organic phase stream with water to further remove said by-products and impurities from said multicyanate ester product stream. 13. The process as claimed in claim 12, wherein said solvent is tetrahydrofliran and the weight ratio of said water stream to said feedstock or organic phase stream is about 1:4. 14. The process as claimed in claim 13, wherein from 25 to 30 percent of said impurities, based upon the total weight of said feedstock, is removed therefrom during each of step a and step c. 15. The process as claimed in claim 1 comprises the steps of f) introducing said reaction product stream to a salt isolation and washing zone to separate said reaction product stream into an organic stream and an aqueous stream, said organic stream comprising said multicyanate ester and at least one of the following components selected from the group consisting of water, solvent, impurities and mixtures thereof and said aqueous stream comprising said tertiary amine hydrohalide salt and at least one of the following components selected from the group consisting of water, solvent, impurities and mixtures thereof; g) introducing said organic stream into a devolatilization zone to separate said organic stream into a multicyanate ester stream and a devolatilization zone solvent stream; h) introducing said devolatilization zone solvent stream and said aqueous stream from said salt isolation and washing zone into a solvent recovery zone to form a solvent recovery zone mixture; i)in said solvent recovery zone, separating said solvent recovery zone mixture into a solvent recovery zone overhead solvent stream and a solvent recovery zone bottoms stream comprising at least one of the components selected from the group consisting of tertiary amine hydrohalide salt, water, dicyanamide, cyanogen halide, and other organics ; j) introducing said solvent recovery zone bottoms stream and basic solution stream into a tertiary amine recovery zone to form a tertiary amine recovery zone mixture; and k) in said tertiary amine recovery zone, separating said tertiary amine from said tertiary amine recovery zone mixture. 16. The process as claimed in claim 15, wherein said solvent is a water miscible solvent or mixture of water miscible and water immiscible solvent, said mixture having a solubility greater than 10 percent in water. 17. The process as claimed in claim 15, wherein said devolatilization zone is comprised of: a first and second devolatilization means arranged in series; and a regulating means between said first and second devolatilization means, whereby said regulating means prevents flashing of said solvent in said first devolatilization means. 18. The process as claimed in claim 1 comprises the steps of ; f) introducing said reaction product stream to a salt isolation and washing zone to separate said reaction product stream into an organic stream and an aqueous stream, said organic stream comprising said multicyanate ester and at least one of the following components selected from the group consisting of water, solvent, by-products, and mixtures thereof, and said aqueous stream comprising said tertiary amine hydrohalide salt and at least one of the following components selected from the group consisting of water, solvent, impurities, and mixtures thereof; g) introducing said organic stream into a devolatilization zone to separate said organic stream into a multicyanate ester stream and a devolatilization zone solvent stream; h) introducing said devolatilization zone solvent stream, said aqueous stream fi-om said salt isolation and washing zone and a stream containing a basic solution into a tertiary amine recovery zone to form a tertiary amine recovery zone mixture; and i)in said tertiary amine recovery zone, separating said tertiary amine from said tertiary amine recovery zone mixture. 19. The process as claimed in claim 18, wherein said solvent is a water immiscible solvent or a mixture of a water immiscible solvent and a water miscible solvent, said mixture having a solubility less than or equal to 10 percent in water. 20. A process for producing multicyanate ester, substantially as herein described with reference to the accompanying drawings.

Full Text

0034-MAS-1996

WE CLAIM:
1. A process for producing multicyanate esters comprising the steps of a) feeding to a reaction vessel a first feed stream comprising a reaction medium comprising a solvent, an adduct of a tertiary amine and a phenol-formaldehyde oligomer or derivative thereof the formula:

wherein:
n is a positive whole number equal to or greater than 1;
q and r are the same or different at each occurrence and are whole numbers from 0 to 3 with the proviso that the sum of q and r at each occurrence is equal to 3;
o and p are the same or different at each occurrence are whole number • from 0 to 4, with the proviso that the- sum of o to p at each, occurrence is equal to 4;
-X- is a divalent organic radical;
A is selected from the group consisting of hydrogen chlorine, bromine, alkyl having from 1 to 10 carbons, epoxide, alkoxy having froni 1 to 10 carbons, cresol-type resins and mixtures thereof; and

R3 is the same or different at each occurrence and is a substituent other than hydrogen which is unreactive under conditions necessary to completely cure the copolymer;
b) feeding to said reaction vessel a second feedstream comprising a cyanogen halide in a reaction medium comprising a solvent;
c) feeding to said reaction vessel a recycle stream comprising at least one of the following compounds selected from the group consisting of tertiary amine-hydrohalide salt, solvent, impurities, multicyanate ester and mixtures thereof;
d) reacting said first, second, and recycle streams in said reaction
vessel to form a reaction product stream comprising at least one of the
following compounds selected from the group consisting of tertiary amine-
hydrohalide salt, solvent and impurities and based upon the total weight of
the reaction product stream excluding the weight of said tertiary amine-
hydrohalide salt, from 10 percent to 40 percent of a multicyanate ester; and
e) removing a portion of said reaction product stream to produce said
recycle stream such that the volume ratio of said recycle stream to said
product stream is 100 : 1 to 25 : 1, and recovered in a manner as herein
described.
2. The process as claimed in claim 1, wherein said oligomer has a number average molecular weight of from 300 to 2000.
3. The process as claimed in claim 1, wherein said oligomer is a novolac resin and: n is 1 to about 8 ; q is 0 ; O is 0 and

4. The process as claimed in claim 1, wherein said tertiary amine
is triethylamine.
5. The process as claimed in claim 1, wherein th'e weight ratio of
oligomer to tertiary amine is from 1:1 to 1:1 20.
6. The process as claimed in claim 1 wherein said cyanogen halide
is cyanogen bromide or cyanogen chloride.
7. The process as claimed in claim 1, wherein said solvent is
selected from the group consisting of a water miscible solvent, water
immiscible solvent and. mixtures thereof.
8. The process as claimed in claim 1, wherein said solvent is
tetrahydrofliran or methylene chloride.

9. The process as claimed in claim 1, wherein the molar ratio of cynogen halide to oligomer repeat unit in said oligomer is from 1.02 : 1 to about 1.15:1.
10. The process as claimed in claim 1, wherein said reaction vessel is comprised of two loop reactors each having a residence time of from 10 to 25 minutes.
11. The process as claimed in claim 1, wherein the temperature in said reaction vessel is less than about -5°C.
12. The process as claimed in claim 1 wherein the multicyanate ester is extracted and recovered by quenching said reaction product stream with a water stream to produce an organic phase stream comprising said multicyanate ester and an aqueous phase stream; separating said organic phase stream comprising said multicyanate ester from said aqueous phase stream; and washing said organic phase stream with water to further remove said by-products and impurities from said multicyanate ester product stream.
13. The process as claimed in claim 12, wherein said solvent is tetrahydrofliran and the weight ratio of said water stream to said feedstock or organic phase stream is about 1:4.
14. The process as claimed in claim 13, wherein from 25 to 30 percent of said impurities, based upon the total weight of said feedstock, is removed therefrom during each of step a and step c.

15. The process as claimed in claim 1 comprises the steps of f) introducing said reaction product stream to a salt isolation and washing zone to separate said reaction product stream into an organic stream and an aqueous stream, said organic stream comprising said multicyanate ester and at least one of the following components selected from the group consisting of water, solvent, impurities and mixtures thereof and said aqueous stream comprising said tertiary amine hydrohalide salt and at least one of the following components selected from the group consisting of water, solvent, impurities and mixtures thereof; g) introducing said organic stream into a devolatilization zone to separate said organic stream into a multicyanate ester stream and a devolatilization zone solvent stream; h) introducing said devolatilization zone solvent stream and said aqueous stream from said salt isolation and washing zone into a solvent recovery zone to form a solvent recovery zone mixture; i)in said solvent recovery zone, separating said solvent recovery zone mixture into a solvent recovery zone overhead solvent stream and a solvent recovery zone bottoms stream comprising at least one of the components selected from the group consisting of tertiary amine hydrohalide salt, water, dicyanamide, cyanogen halide, and other organics ; j) introducing said solvent recovery zone bottoms stream and basic solution stream into a tertiary amine recovery zone to form a tertiary amine recovery zone mixture; and k) in said tertiary amine recovery zone, separating said tertiary amine from said tertiary amine recovery zone mixture.

16. The process as claimed in claim 15, wherein said solvent is a water miscible solvent or mixture of water miscible and water immiscible solvent, said mixture having a solubility greater than 10 percent in water.
17. The process as claimed in claim 15, wherein said devolatilization zone is comprised of: a first and second devolatilization means arranged in series; and a regulating means between said first and second devolatilization means, whereby said regulating means prevents flashing of said solvent in said first devolatilization means.
18. The process as claimed in claim 1 comprises the steps of ; f) introducing said reaction product stream to a salt isolation and washing zone to separate said reaction product stream into an organic stream and an aqueous stream, said organic stream comprising said multicyanate ester and at least one of the following components selected from the group consisting of water, solvent, by-products, and mixtures thereof, and said aqueous stream comprising said tertiary amine hydrohalide salt and at least one of the following components selected from the group consisting of water, solvent, impurities, and mixtures thereof; g) introducing said organic stream into a devolatilization zone to separate said organic stream into a multicyanate ester stream and a devolatilization zone solvent stream; h) introducing said devolatilization zone solvent stream, said aqueous stream fi-om said salt isolation and washing zone and a stream containing a basic solution into a tertiary amine recovery zone to form a tertiary amine recovery zone mixture; and i)in said tertiary amine recovery zone, separating said tertiary amine from said tertiary amine recovery zone mixture.

19. The process as claimed in claim 18, wherein said solvent is a
water immiscible solvent or a mixture of a water immiscible solvent and a
water miscible solvent, said mixture having a solubility less than or equal to
10 percent in water.
20. A process for producing multicyanate ester, substantially as
herein described with reference to the accompanying drawings.

Documents:

0034-mas-1996 abstract.pdf

0034-mas-1996 claims.pdf

0034-mas-1996 correspondence others.pdf

0034-mas-1996 correspondence po.pdf

0034-mas-1996 description (complete).pdf

0034-mas-1996 drawings.pdf

0034-mas-1996 form-2.pdf

0034-mas-1996 form-26.pdf

0034-mas-1996 form-4.pdf

0034-mas-1996 form-6.pdf

0034-mas-1996 others.pdf

0034-mas-1996 petition.tif

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Patent Number

193396

Indian Patent Application Number

34/MAS/1996

PG Journal Number

02/2006

Publication Date

13-Jan-2006

Grant Date

10-Nov-2005

Date of Filing

09-Jan-1996

Name of Patentee

ALLIED SIGNAL INC

Applicant Address

MORRISTOWN, NEW JERSEY

Inventors:

#	Inventor's Name	Inventor's Address
1	DAVID W.H ROTH	MORRIS, NEW JERSEY
2	SAJAL DAS	MORRIS, NEW JERSEY

PCT International Classification Number

C08G8/28

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	08/379, 233	1995-01-27	U.S.A.