Process for preparing high heat-distortion-temperature polyisocyanurate polymers

• US 4,670,346 A
• Filed: 06/02/1986
• Issued: 06/02/1987
• Est. Priority Date: 08/16/1985
• Status: Expired due to Fees

• Current Assignee: Linamar Machine Limited
• Original Assignee: The Thermocell Development Limited
• Inventors: Smith, Stuart B.
• Primary Examiner(s): Page, Thurman K.
• Application Number:
  US06/869,334
• Time in Patent Office: 365 Days
• Field of Search: 427/133, 427/385.5, 427/389.8, 427/393.5, 427/426, 428/423.1, 428/423.3, 428/423.7, 428/424.2, 521/78, 521/125, 521/129, 521/131, 521/902, 521/903, 521/912, 528/48, 528/52, 528/53, 528/57, 528/68, 528/73, 528/83
• US Class Current: 428/422.8
• CPC Class Codes: C08G 18/092 oligomerisation to isocyanurate groups
• 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: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/4841 containing oxyethylene end groups
• CPC Class Codes: C08G 18/7664 containing alkylene polyphenyl groups
• CPC Class Codes: C08G 2120/00 Compositions for reaction injection moulding processes
• CPC Class Codes: C08G 73/0655 from polycyanurates
• CPC Class Codes: Y10S 521/902 Cellular polymer containing an isocyanurate structure
• CPC Class Codes: Y10S 521/903 Cellular polymer having reduced smoke or gas generation
• CPC Class Codes: Y10S 521/912 Separated reactive materials utilized in preparing cellular product
• CPC Class Codes: Y10T 428/31547 Of polyisocyanurate
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31554 Next to second layer of polyamidoester
• CPC Class Codes: Y10T 428/31565 Next to polyester [polyethylene terephthalate, etc.]
• CPC Class Codes: Y10T 428/31573 Next to addition polymer of ethylenically unsaturated monomer

Abstract

A process for preparing a slow-burning, low-smoking, high heat-distortion-temperature polyisocyanurate polymer and the polymer produced thereby, which process comprises reacting an MDI prepolymer with a caprolactone polyol in the presence of a trimerization catalyst, wherein the MDI prepolymer is prepared from an MDI having a functionality of about 2.4 or less, and particularly a 2.4 isomer, and with an ethylene-oxide-capped polypropylene oxide polyol, the process providing for the formation of a rigid, high heat-distortion RIM or an open-spray molded part.

Claims

1. A process for preparing a high heat-distortion-temperature polyisocyanurate polymer, which process comprises:

reacting 100 parts of an MDI prepolymer with from about 5 to 50 parts by weight of a caprolactone polyester polyol in the presence of a catalytic amount of a trimerization catalyst, and wherein the MDI prepolymer is prepared by reacting 100 parts of an MDI, having a functionality of about 2.4 or less, with from about 35 to 75 parts of an ethylene-oxide-capped, polypropylene oxide polyol.

2. The process of claim 1 wherein the MDI employed in preparing the prepolymer comprises a 2.4 isomer MDI.

3. The process of claim 1 wherein the prepolymer has an NCO percentage content ranging from about 15% to 25% by weight.

4. The process of claim 1 wherein the caprolactone polyester polyol has a hydroxyl number ranging from about 300 to 600.

5. The process of claim 1 wherein the caprolactone polyester polyol is a trifunctional polyol having a melting point of less than about 20°

C.

6. The process of claim 1 which includes reacting from about 35 to 50 parts of the caprolactone polyester polyol with 100 parts of the MDI prepolymer.

7. The process of claim 1 wherein the trimerization catalyst comprises an organo metal salt, a quaternary-ammonium salt or a triazene compound.

8. The process of claim 1 wherein the catalyst is present in an amount ranging from about 0.1 to 2 parts by weight per 100 parts of the MDI prepolymer.

9. The process of claim 1 which includes carrying out the reaction in the presence of a blowing amount of a blowing agent, to provide a foam polyisocyanurate polymer.

10. The process of claim 9 wherein the blowing agent comprises from about 0.1 to 15 parts by weight per 100 parts of MDI of a halocarbon.

11. The process of claim 1 which includes carrying out the reaction in the presence of a water-scavenging amount of a water-scavenging agent, to prevent foaming of the reaction mixture, due to the presence of moisture.

12. The process of claim 9 which includes carrying out the reaction in the presence of a cell-control amount of a silicone agent.

13. The process of claim 1 which includes carrying out the reaction in the presence of a flame-retardant agent.

14. The process of claim 13 which includes carrying out the reaction in the presence of a trichloro phosphate ester flame-retardant agent present in an amount ranging from about 0.1 to 15 parts by weight per 100 parts of the MDI prepolymer.

15. The process of claim 1 which includes preparing an A-side composition containing the MDI prepolymer and a B-side composition containing the caprolactone polyester polyol and the trimerization catalyst, and spraying the A- and B-side compositions together onto a substrate.

16. The process of claim 15 which includes spraying the A- and B-side compositions and employing the spraying reaction in a glass-fiber strengthening amount of glass fibers introduced into the reaction mixture.

17. The process of claim 15 which includes spraying the A- and B-side compositions onto a substrate, which substrate comprises a polyester resin gel-coat layer and an acrylic resin or an aliphatic urethane polymer in an open mold.

18. The process of claim 15 which includes spraying substantially equal volumes of the A- and B-side compositions together onto a substrate, which substrate contains glass fibers.

19. The polyisocyanurate polymer prepared by the process of claim 1.

20. The polyisocyanurate polymer prepared by the process of claim 1, which polymer has a heat-distortion temperature of about 400°

F. or more.

21. The polyisocyanurate polymer prepared by the process of claim 1, wherein the gel time is less than about 10 seconds and the cure time is less than about 5 minutes, and which polymer has a heat-distortion temperature of about 400°

F. or more.

22. The process of claim 1 which includes spraying the A- and B-side compositions onto a substrate, which substrate comprises a polyester resin gel-coat layer and an acrylic resin or an aliphatic urethane polymer in an open mold.

30. The process of claim 1 wherein the caprolactone polyol comprises a combination of a trifunctional and a difunctional caprolactone polyols which both have an average molecular weight of less than about 600.

31. The polyisocyanurate polymer prepared by the process of claim 30.

32. The process of claim 1 wherein the polylactone polyol comprises a combination of a trifunctional and a difunctional polylactone polyols.

33. The polyisocyanurate polymer prepared by the process of claim 32.

23. A process for preparing a slow-burning, low-smoking, high heat-distortion-temperature polyisocyanurate polymer, which process comprises:

preparing A- and B-side compositions and spraying together the A- and B-side compositions onto a substrate, wherein the A-side composition comprises 100 parts of an MDI prepolymer, the prepolymer prepared by reacting 100 parts of an MDI of a 2.4 isomer, having a functionality of about 2.4 or less, with from about 35 to 75 parts of an ethylene-oxide-capped polypropylene oxide polyol, having a hydroxyl number of less than about 50, and the B-side composition comprises from about 5 to 50 parts of a caprolactone polyester polyol, having a hydroxyl number ranging from about 300 to 600, and which includes a catalytic amount of a trimerization catalyst, the polyisocyanurate polymer so prepared having a heat-distortion temperature of about 400°

F. or more.

24. The process of claim 23 which includes adding to the B-side composition up to about 15 parts by weight of a phosphate flame-retardant agent.

25. The polyisocyanurate polymer prepared by the process of claim 23.

26. The process of claim 23 which includes spraying the A and B compositions together onto a polymeric substrate in an open mold.

27. The polyisocyanurate-coated substrate prepared by the process of claim 23.

28. The process of claim 23 which includes introducing chopped fiberglass into the A and B sprayed compositions, to prepare a glass-fiber polyisocyanurate polymer.

29. The glass-fiber-containing polyisocyanurate polymer prepared by the process of claim 23.