Low temperature, compatible mixtures of polyether prepolymers and flow modifiers

• US 4,797,226 A
• Filed: 05/05/1987
• Issued: 01/10/1989
• Est. Priority Date: 09/24/1985
• Status: Expired due to Fees

• Current Assignee: Fritz Hostettler
• Original Assignee: Fritz Hostettler
• Inventors: Hostettler, Fritz
• Primary Examiner(s): CLINGMAN, A
• Application Number:
  US07/048,455
• Time in Patent Office: 616 Days
• Field of Search: 252/182
• US Class Current: 252/182.2
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08K 5/10 Esters; Ether-esters
• CPC Class Codes: C08K 5/205 Compounds containing groups, e.g. carbamates
• CPC Class Codes: C08L 75/08 from polyethers

Abstract

There are provided low temperature, storage stable, liquid mixtures of (1) isocyanato-containing prepolymers obtained from the reaction of linear and/or slightly branched polyetherpolyols and a polyisocyanate characterized by a methylene group --CH₂ -- bonded to two benzenoid nuclei, and (2) a non-hydroxyl-containing flow modifier which is compatible with the said prepolymer. Novel liquid mixtures thus prepared exhibit little tendency to crystallize or phase separate when stored for prolonged periods of time, i.e., well below room temperature for several days.

Claims

1. A stable, compatible liquid mixture which does not phase separate when stored for several days at temperatures substantially below normal room temperature consisting essentially of:

(a) an isocyanato-containing prepolymer obtained from the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 60 to about 2250 and an average hydroxyl functionality of from 2 to about 3, said diisocyanate and said polyetherpolyol being used in such quantities so as to provide at least about 2.5 NCO equivalents per OH equivalent, and

(b) from about 3 to about 35 parts by weight, per 100 parts by weight of said prepolymer, of a non-hydroxyl flow modifier, said flow modifier having the following characteristics;

(i) a boiling point above about 150°

C., (ii) normally-liquid at 20°

C. or relatively low melting solid which forms a compatible liquid mixture with said prepolymer, (iii) an average molecular weight of from about 100 to approximately 3000, and (iv) consisting essentially of carbon and hydrogen atoms in the form of monovalent or polyvalent hydrocarbon groups or mixtures of such groups;

etheric oxygen in the form of oxyalkylene, all terminal oxyalkylene groups being satisfied by acyclic, alicyclic or aromatic groups which are monovalently bonded to the oxy moiety of the terminal oxyalkylene groups; and

at least one group having the following structural configuration;

##STR27## each R₁, individually, being hydrogen or a monovalent hydrocarbon group, and R being a hydrocarbyl group; and

wherein each of the unsatisfied bonds of the above structural units are monovalently bonded to separate carbon atoms of the flow modifier molecule, said flow modifier being further characterized by the absence of groups which are normally reactive with an isocyanato group.

2. The liquid mixture of claim 1 wherein:

(a) said polyetherpolyols have hydroxyl equivalent weights of from about 200 to about 2000;

(b) said flow modifier is characterized by (i) at least one group consisting of oxyethylene, oxypropylene and mixtures thereof, and (ii) an average molecular weight of from about 135 to about 1000; and

(c) said liquid mixture contains from about 5 to about 30 parts of said flow modifier per 100 parts of said prepolymer.

3. The liquid mixture of claim 2 wherein:

(a) said isocyanato-containing prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols which have hydroxyl equivalent weights of from about 500 to about 1500 and an average hydroxyl functonality of from about 2 to about 2.5;

said diisocyanate and said polyetherpolyol being used in such quantities so as to provide from about 2.7 to about 24 NCO equivalents per OH equivalent,

(b) said non-hydroxy flow modifier has an average molecular weight of about 150 to about 750, and

(c) said liquid mixture contains from about 7 parts to about 25 parts of said flow modifier per 100 parts of said prepolymer.

4. The liquid mixture of claim 2 wherein said flow modifier is of the group consisting of compounds of the following seven formulas:

##STR28## wherein the oxyalkylene group contains from 2 to 4 carbon atoms in the oxyalkylene chain;

wherein each R individually is of the group consisting of a monovalent acyclic group containing up to 17 carbon atoms, a monovalent alicyclic group containing from 5 to 7 carbon atoms in the alicyclic nucleus and up to 2 carbon atoms in any substituent monovalently bonded to the alicyclic nucleus, and a monovalent aromatic group containing 1 to 2 benzenoid nuclei;

wherein x has a value of at least 1;

wherein z has a value of 1 to 5; and

wherein R₂ is of the group consisting of an acyclic group containing up to 17 carbon atoms, an alicyclic group containing from 5 to 7 carbon atoms in the alicyclic nucleus and up to 2 carbon atoms in any substituent monovalently bonded to the alicyclic nucleus, and an aromatic group containing up to 12 carbon atoms and from 1 to 2 benzenoid nuclei, the valence of R₂ being equal to the value of z;

##STR29## wherein R, x and the oxyalklene group have the meanings assigned in Formula I supra;

wherein R₁ is an acyclic, alicyclic, or aromatic group having the meanings assigned to R₂ in Formula I supra, with the proviso that the valence of R₁ is equal to the sum of c plus y;

wherein each R₃ individually has the meanings assigned to R of Formula I supra;

wherein y has a value of 1 to 2; and

wherein c has a value of 1 to 2;

space="preserve" listing-type="equation">R.sub.4 --oxyalkylene).sub.x OR.sub.4 III

wherein x and the oxyalkylene group have the meanings assigned in Formula I supra; and

wherein each R₄ individually is of the group consisting of acyl and the meanings assigned to R in Formula I supra;

##STR30## wherein R, x and the oxyalkylene group have the meanings assigned in Formula I supra;

space="preserve" listing-type="equation">(R.sub.4 O).sub.m B--(oxyalkylene).sub.x OR.sub.4 ].sub.p V

wherein each R₄ individually has the meanings assigned in Formula III supra;

wherein x and the oxyalkylene group have the meanings assigned in Formula I supra;

wherein m has a value of 0 to 8;

wherein p has a value of 1 to 8;

wherein m plus p is 2 to 8; and

wherein B is a polyvalent acyclic, alicyclic or aromatic group and represents the remainder of a polyfunctional initiator compound without the active hydrogen groups and is composed of up to 12 carbon atoms, hydrogen, and optionally etheric oxygen, the valence of B being equal of m plus p;

##STR31## wherein R_" is a monovalent or polyvalent acyclic, alicyclic or aromatic group and represents the remainder of a functional initiator compound without the active hydrogen groups and is composed of up to 18 carbon atoms, hydrogen, and optionally etheric oxygen, the valence of R" being equal to the value of t;

wherein R is a monovalent group having the meanings in Formula I supra;

wherein x is at least 1 and upwards to 8;

wherein a is zero or x;

wherein y has a value of 1 to 3;

wherein r has a value of 1 to 3;

wherein t has a value of 1 to 5; and

wherein Z is the remainder, excluding the carboxyl groups of an acyclic, alicyclic or aromatic polycarboxylic acid of 2 to 10 carbon atoms, and having a valence equal to y+1;

##STR32## wherein R, x and the oxyalkylene group have the meanings in Formula I supra; and

wherein each R"'"'"' individually is hydrogen, a C₁ -C₈ alkyl or a C₅ -C₇ cycloalkyl.

5. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula I.

6. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula II.

7. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula III.

8. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula IV.

9. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula V.

10. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula VII.

11. The liquid mixture of claim 4 which is stable at a temperature of about 5°

C. for at least 100 hours and wherein (a) said prepolymer is obtained from the reaction of (i) a diphenylmethane diisocyanate containing at least 75 weight percent of the 4,4'"'"'-isomer and (ii) the said polyetherpolyol; and

wherein (b) said flow modifier is represented by Formula VII.

12. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR33## wherein each R'"'"' is C₁ -C₈ alkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, wherein A is C₁ -C₈ alkylene, a cyclohexylene, or a phenylene, and wherein each x has a value of 1 to 25; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

13. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR34## wherein each R'"'"' individually is C₁ -C₈ alkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, wherein A is C₁ -C₈ alkylene, a cyclohexylene, or a phenylene, and wherein each x has a value of 1 to 4; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

14. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

space="preserve" listing-type="equation">R'"'"'--oxyC.sub.2 -C.sub.3 alkylene).sub.x OR'"'"'

wherein each R'"'"' individually is C₁ -C₈ alkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, and wherein x has a value of 2 to 5; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

15. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR35## wherein each R₅ individually is C₁ -C₈ alkyl, a C₅ -C₇ cycloalkyl, aryl-C₁ -C₄ alkyl, or aryl, and wherein n is 2 to 4; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

16. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR36## wherein R'"'"' is C₁ -C₈ alkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, wherein x is 2 to 5, and wherein R₅ is C₁ -C₁₈ alkyl, a C₅ -C₇ cycloalkyl, aryl-C₁ -C₄ alkyl, or aryl; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent

17. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR37## wherein each R'"'"' individually is C₁ -C₈ cycloalkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, and wherein each x is 1 to 4; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

18. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

space="preserve" listing-type="equation">(R.sub.5 O).sub.q D[(oxyC.sub.2 -C.sub.3 alkylene).sub.x OR.sub.5 ].sub.r

wherein each R₅ individually is C₁ -C₁₈ alkyl, a C₅ -C₇ cycloalkyl, aryl-C₁ -C₄ alkyl, aryl, or ##STR38## the R₅ moiety of ##STR39## having the aforesaid meanings, wherein q has a value of 0 to 5, wherein r has a value of 1 to 6, wherein the sum of q+r equals 3 to 6, wherein x has an average value of 1 to about 3, and wherein D is a polyvalent acyclic, alicyclic or aromatic group and represents the remainder of a polyfunctional initiator compound without the active hydrogen groups and is composed of hydrogen and up to 12 carbon atoms, the valence of D being equal to q+r; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

19. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR40## wherein each R₅ individually is C₁ -C₁₈ alkyl, a C₅ -C₇ cycloalkyl, aryl-C₁ -C₄ alkyl, or aryl, wherein R₇ represents the remainder of a dicarboxylic acid having up to 10 carbon atoms and lacking the two carboxyl groups, and wherein x is 1 to 4; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

20. The compatible liquid mixture of claim 3 which is stable and liquid at a temperature of about 5°

C. for at least about one week wherein;

(a) said flow modifier conforms to the following formula;

##STR41## wherein each R°

individually is hydrogen, methyl, or ethyl, wherein each R'"'"' individually is C₁ -C₈ -cycloalkyl, a C₅ -C₇ cycloalkyl, or aryl-C₁ -C₃ alkyl, and wherein each x is 1 to 4; and

(b) said prepolymer is obtained by the reaction of a diphenylmethane diisocyanate which contains at least 75 weight percent of the 4,4'"'"'-isomer and the polyetherpolyol, the quantities of said diisocyanate and said polyetherpolyol being sufficient to provide from about 3.7 to about 12 NCO equivalents per OH equivalent.

21. The compatible liquid mixture of claim 7 which is stable and liquid at about 5°

C. for at least about one week

(a) wherein said flow modifier has the following formula;

##STR42## (b) wherein said prepolymer are the products of the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 750 to about 1250 and an average hydroxyl functionality of from 2 to about 2.2, the amounts of said diisocyanate and said polyetherpolyol used in the reaction providing from about 7 to about 12 NCO equivalents per OH equivalent.

22. The compatible liquid mixture of claim 7 which is stable and liquid at about 5°

C. for at least about one week

(a) wherein said flow modifier has the following formula;

##STR43## wherein x has a value of 3 to 4, and (b) wherein said prepolymers are the products of the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 750 to about 1250 and an average hydroxyl functionality of from 2 to about 2.2, the amounts of said diisocyanate and said polyetherpolyol used in the reaction providing from about 7 to about 12 NCO equivalents per OH equivalent.

23. The compatible liquid mixture of claim 10 which is stable and liquid at about 5°

C. for at least about one week

(a) wherein said flow modifier has the following formula;

##STR44## wherein Y is propylene, butylene, octylene, or ortho-phenylene, and (b) wherein said prepolymers are the products of the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 750 to about 1250 and an average hydroxyl functionality of from 2 to about 2.2, the amounts of said diisocyanate and said polyetherpolyol used in the reaction providing from about 7 to about 12 NCO equivalents per OH equivalent.

24. The compatible liquid mixture of claim 11 which is stable and liquid at about 5°

C. for at least about one week

(a) wherein said flow modifier has the following formula;

space="preserve" listing-type="equation">C.sub.4 H.sub.9 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.2 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9,

and

(b) wherein said prepolymers are the products of the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 750 to about 1250 and an average hydroxyl functionality of from 2 to about 2.2, the amounts of said diisocyanate and said polyetherpolyol used in the reaction providing from about 7 to about 12 NCO equivalents per OH equivalent.

25. The compatible liquid mixture of claim 5 which is stable and liquid at about 5°

C. for at least about one week

(a) wherein said flow modifier has the following formula;

##STR45## wherein R'"'"' is C₁ -C₆ alkyl or phenyl, and wherein x is at least 1, and

(b) wherein said prepolymers are the products of the reaction of (i) a diphenylmethane diisocyanate and (ii) linear or slightly branched polyetherpolyols having hydroxyl equivalent weights of from about 750 to about 1250 and an average hydroxyl functionality of from 2 to about 2.2, the amounts of said diisocyanate and said polyetherpolyol used in the reaction providing from about 7 to about 12 NCO equivalents per OH equivalent.

26. The compatible liquid mixture of claim 25 wherein the variables of the flow modifier have the following significance:

R'"'"' represents methyl, x equals 2, and the oxy-C₂ -C₃ alkylene group is oxyethylene.

27. The compatible liquid mixture of claim 25 wherein the variables of the flow modifier have the following significance:

R'"'"' represents butyl, x equals 2, and the oxy-C₂ -C₃ alkylene group is oxyethylene.

28. The compatible liquid mixture of claim 25 wherein the variables of the flow modifier have the following significance:

R'"'"' represents hexyl, x equals 2, and the oxy-C₂ -C₃ alkylene group is oxyethylene.

29. The compatible liquid mixture of claim 25 wherein the variables of the flow modifier have the following significance:

R'"'"' represents butyl, x equals 1, and the oxy-C₂ -C₃ alkylene group is oxypropylene.

30. The compatible liquid mixture of claim 25 wherein the variables of the flow modifer have the following significance:

R'"'"' represents propyl, x equals 1, and the oxy-C₂ -C₃ alkylene group is oxypropylene.

31. The compatible liquid mixture of claim 25 wherein the variables of the flow modifier have the following significance:

R'"'"' represents phenyl, x equals 1 or 2, and the oxy-C₂ -C₃ alkylene group is oxyethylene.