Polyurethane polymer

• US 6,992,138 B2
• Filed: 05/14/2002
• Issued: 01/31/2006
• Est. Priority Date: 05/31/2001
• Status: Expired due to Fees

• Current Assignee: Kaneka Corporation
• Original Assignee: Kaneka Corporation
• Inventors: Tsuji, Ryotaro, Hiiro, Tomoki
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US10/478,315
• Publication Number:
  US 20040171765A1
• Time in Patent Office: 1,358 Days
• Field of Search: 525/123, 525/131, 526/222, 526/224, 528/75
• US Class Current: 525/131
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08G 18/0895 Manufacture of polymers by continuous processes C08G18/0838 takes precedence
• 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 18/3206 aliphatic
• CPC Class Codes: C08G 18/6287 Polymers of sulfur containing compounds having carbon-to-carbon double bonds
• CPC Class Codes: D01F 6/70 from polyurethanes

Abstract

Provided is a polyurethane polymer which is excellent in oil resistance, weatherability, light resistance, heat resistance, hot water resistance, hydrolysis resistance, strength, chlorine resistance, and chemical resistance, and which can be produced simply and economically. The polyurethane polymer is produced by polymerizing at least two components: a vinyl polymer (A) having a mercapto group at each end of the molecular chain produced by a reversible addition-fragmentation chain transfer polymerization method, and an organic polyisocyanate (B). Also provided are polyurethane-based materials containing the polyurethane polymer, and polyurethane elastic fiber.

Claims

1. A polyurethane polymer produced by polymerizing at least two components:

a vinyl polymer (A) having a mercapto group at each end of the molecular chain, the vinyl polymer being prepared by reversible addition-fragmentation chain transfer polymerization, the molecular weight distribution (Mw/Mn) of the vinyl polymer being 2 or less, the molecular weight distribution being determined by gel permeation chromatography (GPC) analysis; and

an organic polyisocyanate (B).

2. The polyurethane polymer according to claim 1, wherein the vinyl polymer (A) having the mercapto group at each end of the molecular chain is prepared by a process comprising the steps of:

radically polymerizing a radically polymerizable vinyl monomer in the presence of a thiocarbonylthio group-containing compound to produce a thiocarbonylthio group-containing polymer, the thiocarbonylthio group-containing compound being represented by general formula (1);

(wherein R¹ is a p-valent organic group of 1 or more carbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen, silicon, phosphorus, and metal atoms, or which may be a polymer;

each Z¹ is a hydrogen atom, halogen atom, or monovalent organic group of 1 or more carbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen, silicon, and phosphorus atoms, or which may be a polymer;

plural Z¹s may be the same or different; and

p is an integer of 2 or more); and

converting the thiocarbonylthio group of the polymer into the mercapto group.

3. The polyurethane polymer according to claim 2, wherein the thiocarbonylthio group-containing compound is a compound represented by general formula (2):

(wherein R² is a divalent organic group which may contain one of nitrogen, oxygen, sulfur, halogen, silicon, phosphorus, and metal atoms, or which may be a polymer;

each Z¹ is a hydrogen atom, halogen atom, or monovalent organic group of 1 or more carbon atoms which may contain one of nitrogen, oxygen, sulfur, halogen, silicon, and phosphorus atoms, or which may be a polymer; and

two Z¹s may be the same or different).

4. The polyurethane polymer according to claim 2, wherein the radically polymerizable vinyl monomer is at least one compound selected from the group consisting of styrene, α

-methylstyrene, vinyl chloride, methacrylate esters, acrylate esters, acrylonitrile, and vinyl acetate.

5. The polyurethane polymer according to claim 2, wherein the thiocarbonylthio group of the thiocarbonylthio group-containing polymer is converted into the mercapto group by a reaction with a processing agent comprising at least one compound selected from the group consisting of bases and acids.

6. The polyurethane polymer according to claim 2, wherein the thiocarbonylthio group of the thiocarbonylthio group-containing polymer is converted into the mercapto group by a reaction with a processing agent comprising at least one compound selected from the group consisting of ammonia, hydrazine, primary amine compounds, and secondary amine compounds.

7. The polyurethane polymer according to claim 6, wherein the processing agent is at least one compound selected from the group consisting of primary amine compounds with a boiling point of 100°

C. or less, secondary amine compounds with a boiling point of 100°

C. or less, and hindered amine light stabilizers (HALSs).

8. The polyurethane polymer according to claim 1, wherein the number-average molecular weight of the vinyl polymer (A) having the mercapto group at each end of the molecular chain is in the range of 2,500 to 1,000,000, the number-average molecular weight being determined by gel permeation chromatography (GPC) analysis.

9. The polyurethane polymer according to claim 1, wherein the organic polyisocyanate (B) is an aliphatic polyvalent isocyanate compound.

12. A polyurethane-based material comprising the polyurethane polymer according to claim 1.

13. The polyurethane-based material according to claim 12, further comprising at least one additive selected from the group consisting of surfactants, blowing agents, fire retardants, fillers, hydrolysis inhibitors, antioxidants, ultraviolet absorbers, aging resisters, plasticizers, antistatic agents, colorants, tackifiers, silane coupling agents, mildewproofing agents, and release agents.

10. A polyurethane polymer produced by polymerizing at least two components:

a vinyl polymer (A) having a mercapto group at each end of the molecular chain, the vinyl polymer being prepared by reversible addition-fragmentation chain transfer polymerization; and

an organic polyisocyanate (B), and further comprising

a chain extender (C) as a polymer component.

11. The polyurethane polymer according to claim 10, wherein the chain extender (C) is a compound having at least two active hydrogen groups in each molecule, each active hydrogen group being selected from the group consisting of a hydroxyl group and an amino group.

14. An elastic fiber comprising a polyurethane polymer produced by polymerizing at least two components:

a vinyl polymer (A) having a mercapto group at each end of the molecular chain, the vinyl polymer being prepared by reversible addition-fragmentation chain transfer polymerization; and

an organic polyisocyanate (B).

15. The elastic fiber according to claim 14, wherein the vinyl polymer (A) having the mercapto group at each end of the molecular chain has a glass transition temperature of 30°

C. or less.

16. The elastic fiber according to claim 14, wherein the vinyl polymer (A) having the mercapto group at each end of the molecular chain is prepared by radically polymerizing 50% to 100% by weight of an acrylate ester monomer and 50% to 0% by weight of at least one monomer selected from the group consisting of styrene, α

-methylstyrene, vinyl chloride, methacrylate esters, acrylonitrile, and vinyl acetate.

17. The elastic fiber according to claim 14, further comprising at least one additive selected from the group consisting of antioxidants, ultraviolet absorbers, light stabilizers, dye sticking agents, dyes, pigments, and lubricants.