Polyisocyanurate resin and process for making the same

• US 4,299,924 A
• Filed: 07/17/1980
• Issued: 11/10/1981
• Est. Priority Date: 08/10/1979
• Status: Expired due to Term

• Current Assignee: Sanyo Chemical Industries Limited 11-1 Ichinohashi Nomoto-Cho Higashiyama-Ku Kyoto Japan, Toyota Jidosha Kabushiki Kaisha 1 Toyota-Cho Toyota-Shi Aichi-Ken Japan
• Original Assignee: Sanyo Chemical Industries Limited, Toyota Jidosha Kogyo Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Nomura, Takao, Nagata, Kozaburo, Isaka, Takuji, Taguchi, Yoshio
• Primary Examiner(s): Welsh, Maurice J.
• Application Number:
  US06/169,809
• Time in Patent Office: 481 Days
• Field of Search: 521/131, 521/174, 521/176, 528/75, 528/76, 528/77
• US Class Current: 521/131
• CPC Class Codes: C08G 18/092 oligomerisation to isocyanurate groups
• CPC Class Codes: C08G 18/63 Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
• CPC Class Codes: C08G 2110/0025 rigid
• CPC Class Codes: C08G 2110/0066 ≥ 150kg/m3
• CPC Class Codes: C08G 2110/0083 prepared using water as the sole blowing agent
• CPC Class Codes: C08G 2120/00 Compositions for reaction injection moulding processes

Abstract

High-density polyisocyanurate resins having improved rigidity, heat resistance and/or impact resistance can be obtained by reacting a polyisocyanate with a polymer polyol derived from a polyol having a molecular weight of at least 4500, and optionally a crosslinker, in the presence of trimerization catalyst, using isocyanate index of 200-5000.

Claims

1. A process for producing a cellular or noncellular polyisocyanurate resin, which comprises reacting an organic polyisocyanate with at least one high-molecular weight polyhydroxyl compound with or without a cross-linker, in the presence of trimerization catalyst, in the presence of or in the absence of a blowing agent, wherein (1) at least a part of said polyhydroxyl compound is a polymer polyol derived from a high-molecular weight polyol having a molecular weight of at least 4500 and an ethylenically unsaturated monomer, (2) isocyanate index is 200-5000, and (3) the resin has a density of at least 0.5 g/cm³.

2. The process of claim 1, wherein a noncellular polyisocyanurate resin is produced by carrying out the reaction substantially in the absence of the blowing agent.

3. The process of claim 1, wherein a cellular polyisocyanurate resin is produced by carrying out the reaction in the presence of water, a halogen-substituted aliphatic hydrocarbon blowing agent, or a combination thereof.

4. The process of claim 3, wherein the reaction is carried out in the presence of at most 5×

x% of the halogene-substituted aliphatic hydrocarbon blowing agent and at most 1×

y% of water, based on the total weight of said polyisocyanate, said polyhydroxyl compound and the crosslinker, wherein x and y are optional numbers of 0-1 which satisfy the equation;

x+y=1.

5. The process of claim 1, wherein the isocyanate index is 500-5000.

6. The process of claim 1 or 5, wherein equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is at least 15;

1.

7. The process of claim 1 or 5, wherein equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is at least 20;

1.

8. The process of claim 1, wherein equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is between 15;

1 and 25;

1.

9. The process of claim 1, wherein equivalent ratio of said polyisocyanate:

the crosslinker is at least 84;

at most 16.

10. The process of claim 1, wherein said high-molecular weight polyol is a polyetherpolyol.

11. The process of claim 1, wherein said high-molecular weight polyol has a primary OH content of 10-80%.

12. The process of claim 1, wherein said high-molecular weight polyol is a polyether polyol having a terminal oxyethylene content of 5-50% by weight.

13. The process of claim 1, wherein the crosslinker has a equivalent weight of 30-140.

14. The process of claim 1, wherein the crosslinker is at least one selected from low-molecular weight polyols, polyamines and aminoalcohols.

15. The process of claim 1, wherein the polymer polyol is used in an amount of 70-90% by weight based on the total weight of said polyhydroxyl compound and the crosslinker.

16. The process of claim 1, wherein a polyisocyanurate resin molded article is formed by reaction injection molding.

17. A high-density polyisocyanurate resin, which has been obtained by the process of claim 1.

18. A high-density polyisocyanurate resin molded article, which has been obtained by the process of claim 16.

19. A high-density polyisocyanurate resin having improved rigidity, heat resistance and impact resistance, which has been obtained by reacting an organic polyisocyanate with at least one high-molecular weight polyhydroxyl compound, in the presence of trimerization catalyst in the presence of or in the absence of a blowing agent, wherein (1) at least a part of said polyhydroxyl compound is a polymer polyol derived from a high-molecular weight polyol having a molecular weight of at least 4500 and an ethylenically unsaturated monomer, (2) isocyanate index is 1500-5000, and (3) the resin has a density of at least 0.5 g/cm³.

20. The resin of claim 19, which has a flexural modulus of at least 8000 Kg/cm², a heat distortion temperature of at least 100°

C. and an unnoched Izod impact strength of at least 8 Kg.cm/cm².

21. A high-density polyisocyanurate resin having an improved heat resistance and rigidity, which has been obtained by reacting an organic polyisocyanate with at least one high-molecular weight polyhydroxyl compound and a crosslinker, in the presence of a trimerization catalyst with or without a blowing agent, wherein (1) at least a part of said polyhydroxyl compound is a polymer polyol derived from a high-molecular weight polyol having an equivalent weight of 500-3000 and an ethylenically unsaturated monomer, (2) isocyanate index is 500-5000, and (3) equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is at least 20;

1.

22. The resin of claim 21, which has a heat distortion temperature of at least 120°

C. and a flexural modulus of at least 10000 Kg/cm².

23. A high-density polyisocyanurate resin having an improved impact resistance, which has been obtained by reacting an organic polyisocyanate with at least one high-molecular weight polyhydroxyl compound and a crosslinker, in the presence of a trimerization catalyst with or without a blowing agent, wherein (1) at least a part of said polyhydroxyl compound is a polymer polyol derived from a high-molecular weight polyol having an equivalent weight of 500-3000 and an ethylenically unsaturated monomer (2) isocyanate index is at least 200, and (3) equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is at most 20;

1.

24. The resin of claim 23, which has unnoched Izod impact resistance of at least 10 Kg.cm/cm².

25. A high-density polyisocyanurate resin having an improved rigidity, which has been obtained by reacting an organic polyisocyanate with at least one high-molecular weight polyhydroxyl compound and a crosslinker, in the presence of a trimerization catalyst with or without a blowing agent, wherein (1) at least a part of said polyhydroxyl compound is a polymer polyol derived from a high-molecular weight polyol having an equivalent of 500-3000 and an ethylenically unsaturated monomer, (2) isocyanate index is 200-500, (3) equivalent ratio of (said polyisocyanate+the crosslinker):

said polyhydroxyl compound is at least 20;

1, and (4) the resin has a density of at least 0.5 g/cm³.

26. The resin of claim 25, which has flexural modulus of at least 10000 Kg/cm².

27. The resin of claim 26, wherein said polyisocyanate is a 1:

1 mixture (free NCO content;

26%) of a carbodiimide--modified diphenyl--methane-4,4'"'"'-diisocyanate (MDI) with a prepolymer prepared from 745 parts of MDI and 100 parts of triethylene glycol.