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WO2022032552A1 - Polyurethane compositions, foams prepared with same and preparation methods thereof - Google Patents

Polyurethane compositions, foams prepared with same and preparation methods thereof Download PDF

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Publication number
WO2022032552A1
WO2022032552A1 PCT/CN2020/108790 CN2020108790W WO2022032552A1 WO 2022032552 A1 WO2022032552 A1 WO 2022032552A1 CN 2020108790 W CN2020108790 W CN 2020108790W WO 2022032552 A1 WO2022032552 A1 WO 2022032552A1
Authority
WO
WIPO (PCT)
Prior art keywords
diol
isocyanate
polyurethane
group
polyol
Prior art date
Application number
PCT/CN2020/108790
Other languages
French (fr)
Inventor
Tao Wang
Yanbin FAN
Hongyu Chen
Kang Chen
Xiaolin Huang
Original Assignee
Dow Global Technologies Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Priority to PCT/CN2020/108790 priority Critical patent/WO2022032552A1/en
Publication of WO2022032552A1 publication Critical patent/WO2022032552A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3

Definitions

  • the present disclosure relates to a polyurethane composition, a polyurethane material, preferably a polyurethane foam prepared by using the composition, and a method for preparing the polyurethane material.
  • the polyurethane composition has a particularly designed formulation so as to produce a polyurethane foam exhibiting excellent properties such as inhibited internal heat buildup, enhanced thermal resistance, tear strength, among others.
  • Microcellular polyurethane foams are foamed polyurethane materials with a density of about 100-900 kg/m 3 and are usually fabricated via a two-component process of reacting Component A (polyols, chain extenders, foaming agents, catalysts, surfactants, etc. ) and Component B (monomeric isocyanate, prepolymer of polyols and isocyanates, or blend thereof) .
  • Component A polyols, chain extenders, foaming agents, catalysts, surfactants, etc.
  • Component B monomeric isocyanate, prepolymer of polyols and isocyanates, or blend thereof
  • the two components are usually blended at high speed and then transferred into varied molds with desired shapes.
  • microcellular polyurethane foams have been employed in a wide range of end use applications like shoemaking (e.g., soles) and automotive industries (e.g., bumpers and arm rests of integral skin foams) .
  • the uses of polyurethane in tire applications have been challenging due to inherent attributes of polyurethanes to generate “internal heat” .
  • the internal heat buildup originates from transition of mechanical energy into heat inside polyurethanes and is characterized by significant augmentation of the tire temperature during rolling especially under high speed and load. With increasing temperature, material failures including fatigue cracking and/or melting are usually observed. Thus the upper limits of speed and load under which a polyurethane tire can operate are determined by internal heat buildup, and of course, thermal stability of the polyurethane tire.
  • Significant efforts have been made to increase the thermal stability of polyurethanes by introduction of functional moieties e.g.
  • polyester polyols can impart polyurethanes with higher tear strength due to higher cohesive energy thereof, but their processing and durability are poor due to their high viscosity and insufficient resistance to hydrolytic attack, respectively.
  • the present disclosure provides a unique polyurethane composition, a polyurethane material, preferably a polyurethane foam, prepared by using the composition, a method for preparing the polyurethane material and a method for improving the performance properties of the polyurethane material.
  • the present disclosure provides a polyurethane composition, comprising
  • each of R 1 and R 4 is independently selected from the group consisting of covalent bond, C 1 to C 6 alkylene group, C 2 -C 6 alkenylene group, C 6 -C 12 cycloalkylene group, and C 6 -C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl group;
  • polyurethane composition does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into a polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component.
  • the polyurethane composition can be used for preparing a polyurethane material comprising a plurality of polyurethane backbones, wherein the unsaturated linear diol of formula I forms at least part of the repeating units in the polyurethane backbones, and there is no ethylenically unsaturated side chain linked to the polyurethane backbones.
  • the unsaturated linear diol represented by Formula I is selected from a group consisting of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, 2, 4-hexadiene-1, 6-diol, 2-heptene-1, 7-diol, 3-heptene-1, 7-diol, 2, 4-heptadiene-1, 7-diol, 2, 5-heptadiene-1, 7-diol, 2-octene-1, 8-diol, 3-octene-1, 8-diol, 4-octene-1, 8-diol, 2, 4-octadiene-1, 8-diol, 2, 5-octadiene-1, 8-diol, 2, 6-octadiene-1, 8-diol, 1, 2-bis (4-hydroxylcyclohex
  • the content of the unsaturated linear diol represented by Formula I is from 1%to 20%by weight, based on the total weight of the isocyanate-reactive component (A) .
  • the second polyol is selected from the group consisting of C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof.
  • the second polyol optionally includes at least one saturated linear C 2 -C 12 aliphatic diol, and the weight ratio between the saturated linear C 2 -C 12 aliphatic diol and the unsaturated linear diol is from 0: 20 to 10: 1. According to another embodiment, the weight ratio between the saturated linear C 2 -C 12 aliphatic diol and the unsaturated linear diol is from 1: 1 to 1: 3.
  • the first isocyanate compound is selected from the group consisting of C 4 -C 12 aliphatic isocyanate comprising at least two isocyanate groups, C 6 -C 15 cycloaliphatic or aromatic isocyanate comprising at least two isocyanate groups, C 7 -C 15 araliphatic isocyanate comprising at least two isocyanate groups, a prepolymer comprising at least two isocyanate groups, and any combinations thereof.
  • the polyurethane composition further comprises at least one additive selected from the group consisting of chain extender, crosslinker, blowing agent, foam stabilizer, tackifier, plasticizer, rheology modifier, antioxidant, UV-absorbent, light-stabilizer, catalyst, cocatalyst, filler, colorant, pigment, water scavenger, surfactant, solvent, diluent, flame retardant, slippery-resistance agent, antistatic agent, preservative, biocide and any combinations thereof.
  • at least one additive selected from the group consisting of chain extender, crosslinker, blowing agent, foam stabilizer, tackifier, plasticizer, rheology modifier, antioxidant, UV-absorbent, light-stabilizer, catalyst, cocatalyst, filler, colorant, pigment, water scavenger, surfactant, solvent, diluent, flame retardant, slippery-resistance agent, antistatic agent, preservative, biocide and any combinations thereof.
  • the present disclosure provides a polyurethane material prepared with the polyurethane composition as stated above, wherein the polyurethane material comprises polyurethane main chains derived from the reaction of
  • each of R 1 and R 4 is independently selected from the group consisting of direct bond, C 1 to C 6 alkylene group, C 2 -C 6 alkenylene group, C 6 -C 12 cycloalkylene group, and C 6 -C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl group;
  • repeating units derived from the unsaturated linear diol constitute at least part of the polyurethane backbone, and none of the polyurethane backbone in the polyurethane material comprises an ethylenically unsaturated side chain.
  • the polyurethane material is a microcellular polyurethane foam.
  • the present disclosure provides a method for preparing said polyurethane material (foam) , comprising a step of reacting the isocyanate-reactive component (A) with the (B) isocyanate component to form the polyurethane material (foam) .
  • the present disclosure provides a method for improving the performance property of said polyurethane material, comprising the step of introducing repeating units derived from an unsaturated linear diol represented by Formula I into at least part of polyurethane main chains in the polyurethane material,
  • the performance property includes at least one of internal heat buildup, thermal stability, tear strength, viscosity, abrasion resistance and hydrolysis resistance.
  • the polyurethane composition is a "two-component” , “two-part” or “two-package” composition comprising an isocyanate-reactive component (A) and an isocyanate component (B) .
  • the isocyanate-reactive component (A) and the isocyanate component (B) are transported and stored separately, combined shortly or immediately before being applied during the manufacture of the polyurethane foam, such as solid tire. Once combined, the isocyanate groups in component (B) reacts with the isocyanate-reactive groups (particularly, hydroxyl group) in component (A) to form polyurethane.
  • the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I,
  • each of R 1 and R 4 is independently selected from the group consisting of covalent bond, C 1 to C 6 alkylene group, C 2 -C 6 alkenylene group, C 6 -C 12 cycloalkylene group, and C 6 -C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1 -C 6 alkyl group.
  • the unsaturated linear diol represented by Formula I can be selected from the group consisting of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, 2, 4-hexadiene-1, 6-diol, 2-heptene-1, 7-diol, 3-heptene-1, 7-diol, 2, 4-heptadiene-1, 7-diol, 2, 5-heptadiene-1, 7-diol, 2-octene-1, 8-diol, 3-octene-1, 8-diol, 4-octene-1, 8-diol, 2, 4-octadiene-1, 8-diol, 2, 5-octadiene-1, 8-diol, 2, 6-octadiene-1, 8-diol, 1, 2-bis (4-hydroxylcyclohexy
  • the unsaturated linear diol represented by Formula I is 2-butene-1, 4-diol, which is also known as butenediol (BEDO) in the context of the present disclosure.
  • the content of the above said unsaturated linear diol represented by Formula I is from 1%to 20%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt
  • the isocyanate-reactive component (A) does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into the polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component, thus none of the polyurethane backbones in the polyurethane material comprises an ethylenically unsaturated side chain.
  • polyurethane backbone refers to the main chain or the longest linear polymeric chain contained in the polyurethane material or polyurethane foam prepared by reacting component (A) with component (B) of the present disclosure.
  • the polyurethane backbone is formed with repeating units (residual moieties) derived from the isocyanate compounds contained in the isocyanate component (B) , various polyols, such as the unsaturated linear diol represented by Formula I, the saturated linear C 2 -C 12 aliphatic diol, and any other polyols contained in the isocyanate-reactive component (A) , and any other additive which comprises at least two isocyanate-reactive groups and may be included in the polyurethane backbone.
  • the residual moiety derived from the isocyanate compound and the residual moiety derived from the isocyanate-reactive compounds (polyol, chain extender, crosslinker, etc.
  • an unsaturated compound which will introduce an ethylenically unsaturated side chain into the polyurethane backbone refers to a compound whose molecular chain containing one or more ethylenically unsaturated functionalities (carbon-carbon double bond) is not terminated at both ends with a isocyanate-reactive (such as hydroxyl group, amine group, carboxyl group, etc. ) , and thus the ethylenically unsaturated functionality will be linked to the polyurethane backbone in the form of a side chain rather than as part of the linear polyurethane backbone.
  • a isocyanate-reactive such as hydroxyl group, amine group, carboxyl group, etc.
  • 3- (allyloxy) propane-1, 2-diol whose molecular structure is shown in Formula II, is a typical unsaturated compound which “will form an ethylenically unsaturated side chain” attached to the polyurethane backbone, hence such a compound and any analogs shall be particularly excluded from the polyurethane composition of the present disclosure.
  • one or more of the isocyanate compound, the unsaturated linear diol represented by Formula I, the second polyol, and the additives may introduce at least one side chain to the polyurethane backbone, but none of the said chain comprises an ethylenically unsaturated functionality.
  • the isocyanate-reactive component (A) further comprises at least one second polyol other than the unsaturated linear diol represented by Formula I.
  • the second polyol can be selected from the group consisting of C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof.
  • the second polyol includes at least one saturated linear C 2 -C 12 aliphatic diol and at least one additional polyol, i.e. the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2 -C 12 aliphatic diol, and at least one additional polyol which is different from either one of the above diols.
  • the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2 -C 12 aliphatic diol, and at least one additional polyol which is different from either one of the above diols.
  • the saturated linear C 2 -C 12 aliphatic diol can be selected from the group consisting of ethylene glycol (ethane diol) , propylene glycol (propane diol) , tetramethylene glycol (1, 4-butane diol) , and 2-methyl-1, 3-propane glycol (1, 3-butane diol) , and is more preferably 1, 4-butane diol.
  • the content of the above said saturated linear C 2 -C 12 aliphatic diol is from 0.5%to 40%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14
  • the weight ratio between the saturated linear C 2 -C 12 aliphatic diol and the unsaturated linear diol represented by Formula I is from 0: 20 to 20: 1, such as from 1: 10 to 10: 1, or from 1: 1 to 1: 3, such as in the numerical range obtained by combining any two of the following ratios: 0: 20, 1: 20, 1: 18, 1: 15, 1: 10, 1: 8, 1: 7, 1: 6, 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 3: 2, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1, 19: 1, and 20: 1.
  • the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2 -C 12 aliphatic diol, and at least one additional polyol, wherein the at least one additional polyol is different from either one of the above diols and is selected from the group consisting of C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase
  • the at least one additional polyol is different from either one of the above diols and is selected from the group consisting of C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, dimer of the C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, trimer of the C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxy groups, polyester polyols having a molecular weight from 500 to 5,000, polycarbonate polyols having an average functionality of 2 to 5 and a molecular weight from 200 to 5,000, polyether polyols having an average functionality of 2 to 5 and an average molecular weight of 200 to 12,000, C 2 -C 10 alkanolamine comprising at least one
  • the polyether polyol used for component (A) has a molecular weight of 100 to 10,000 g/mol, and may have a molecular weight in the numerical range obtained by combining any two of the following end point values: 120, 150, 180, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, 8000, 8200, 8
  • the polyether polyol used for component (A) has an average hydroxyl functionality of 1.0 to 8.0, or from 1.5 to 5.0, and may have an average hydroxyl functionality in the numerical range obtained by combining any two of the following end point values: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5
  • the polyether polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) and any copolymers thereof, such as poly (ethylene oxide-propylene oxide) glycol.
  • the polyether polyol can be polytetramethylene glycol (PTMEG) having a molecular weight of 200 to 3,000 and a hydroxyl functionality of 1.0 to 3.0.
  • starting material polyether polyol can be a poly (ethylene oxide-propylene oxide) glycol having a molecular weight of 200 to 3,000 and a hydroxyl functionality of 2.0 to 8.0, wherein the molar ratio between the ethylene oxide repeating unit and the propylene oxide repeating unit can be from 5/95 to 95/5, such as from 10/90 to 90/10, or from 20/80 to 80/20, or from 40/60 to 60/40, or at about 50/50.
  • the polymer polyol is a composite particulate having a core-shell structure, wherein the core is a micro-sized or nano-sized core composed of any polymer or copolymer, such as SAN (styrene and acryl nitrile) , and the shell phase is composed of a polyether polyol, such as PO-EO polyol.
  • the polymer polyol has a shell phase based on the poly (C 2 -C 10 ) alkylene glycol or copolymer thereof.
  • the polymer polyol has a core phase and a shell phase based on the poly (C 2 -C 10 ) alkylene glycol or copolymer thereof, having a solid content of 1-50%, an OH value 10 ⁇ 149, and a hydroxyl functionality of 1.5-5.0, such as 2.0-5.0.
  • the shell phase may comprise at least one poly (C 2 -C 10 ) alkylene glycol or copolymer thereof, for example, the polyol may be selected from the group consisting of polyethylene, (methoxy) polyethylene glycol (MPEG) , polyethylene glycol (PEG) , poly (propylene glycol) , polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) or copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) with primary hydroxyl ended group or secondary hydroxyl ended group.
  • the core phase may be micro-sized and may comprise any polymers compatible with the shell phase.
  • the core phase may comprise polystyrene, polyacrylnitrile, polyester, polyolefin or polyether different (in either composition or polymerization degree) from those of the shell phase.
  • the polymer polyol is a composite particulate having a core-shell structure, wherein the core is a micro-sized core composed of SAN (styrene and acryl nitrile) and the shell phase is composed of PO-EO polyol.
  • SAN styrene and acryl nitrile
  • PO-EO polyol styrene and acryl nitrile
  • Such a polymer polyol can be prepared by radical copolymerization of styrene, acryl nitrile and poly (EO-PO) polyol comprising ethylenically unsaturated groups.
  • the polyether polyols can be prepared by polymerization of one or more linear or cyclic alkylene oxides selected from propylene oxide (PO) , ethylene oxide (EO) , butylene oxide, tetramethylene glycol, tetrahydrofuran, 2-methyl-1, 3-propane glycol and mixtures thereof, with proper starter molecules in the presence of a catalyst.
  • Typical starter molecules include compounds having at least 1, preferably from 1.5 to 3.0 hydroxyl groups or having one or more primary amine groups in the molecule.
  • Suitable starter molecules having at least 1 and preferably from 1.5 to 3.0 hydroxyl groups in the molecules are for example selected from the group comprising ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butenediol, 1, 4-butynediol, 1, 5-pentanediol, neopentyl glycol, 1, 4-bis (hydroxymethyl) -cyclohexane, 1, 2-bis (hydroxymethyl) cyclohexane, 1, 3-bis (hydroxymethyl) -cyclohexane, 2-methylpropane-1, 3-diol, methylpentanediols, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycols, trimethylolpropane, glycerol
  • Starter molecules having 1 or more primary amine groups in the molecules may be selected for example from the group consisting of aniline, EDA, TDA, MDA and PMDA, more preferably from the group comprising TDA and PMDA, an most preferably TDA.
  • TDA all isomers can be used alone or in any desired mixtures.
  • 2, 4-TDA, 2, 6-TDA, mixtures of 2, 4-TDA and 2, 6-TDA, 2, 3-TDA, 3, 4-TDA, mixtures of 3, 4-TDA and 2, 3-TDA, and also mixtures of all the above isomers can be used.
  • Catalysts for the preparation of polyether polyols may include alkaline catalysts, such as potassium hydroxide, for anionic polymerization or Lewis acid catalysts, such as boron trifluoride, for cationic polymerization.
  • Suitable polymerization catalysts may include potassium hydroxide, cesium hydroxide, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
  • DMC double cyanide complex
  • the starting material polyether polyol includes polyethylene, (methoxy) polyethylene glycol (MPEG) , polyethylene glycol (PEG) , poly (propylene glycol) , polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) or copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) with primary hydroxyl ended group or secondary hydroxyl ended group.
  • MPEG polyethylene glycol
  • PEG polyethylene glycol
  • PEG poly (propylene glycol)
  • polytetramethylene glycol poly (2-methyl-1, 3-propane glycol) or copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) with primary hydroxyl ended group or secondary hydroxyl ended group.
  • the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2 -C 12 aliphatic diol, and at least one additional polyol, wherein the at least one additional polyol is different from either one of the above diols and is more preferably one or more polyether polyol, a polymer polyol having a core phase and a shell phase based on polyether polyol, and any combinations thereof.
  • the content of the above said additional polyol (which is different from either one of the above diols) , is from 1%to 90%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 w
  • the isocyanate component (B) comprises at least one monomeric compound having at least two isocyanate groups, or at least one prepolymer having at least two isocyanate groups, or a mixture thereof.
  • the isocyanate component (B) has an average NCO functionality of at least about 1.5, preferably from about 2 to 10, more preferably from about 2 to about 8, more preferably from about 2 to about 6, and most preferably about 2.
  • the isocyanate component (B) has an average NCO functionality of 2.0.
  • prepolymer prepolymer of isocyanate
  • polyurethane prepolymer refers to a prepolymer prepared by reacting at least one isocyanate compound having at least two isocyanate groups with a polyol, wherein the prepolymer comprises at least two isocyanate groups and is used for further reacting with the isocyanate-reactive component (A) to form the polyurethane material such as polyurethane foam.
  • polyisocyanate compound in the context of the present disclosure, the terms “polyisocyanate compound” , “polyisocyanate” and “isocyanate compound comprising at least two isocyanate groups” are used interchangeably and refer to an isocyanate having at least two isocyanate groups, wherein the isocyanate is monomeric, dimeric, trimeric or oligomeric (such as having a polymerization degree of 2, 3, 4, 5 or 6) .
  • the monomeric compound having at least two isocyanate groups is selected from the group consisting of C 4 -C 12 aliphatic isocyanate comprising at least two isocyanate groups, C 6 -C 15 cycloaliphatic or aromatic isocyanate comprising at least two isocyanate groups, C 7 -C 15 araliphatic isocyanate comprising at least two isocyanate groups, a prepolymer comprising at least two isocyanate groups, and any combinations thereof.
  • the monomeric compound having at least two isocyanate groups may include m-phenylene diisocyanate, 2, 4-toluene diisocyanate and/or 2, 6-toluene diisocyanate (TDI) , the various isomers of diphenylmethanediisocyanate (MDI) , carbodiimide modified MDI products, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI) , isomers of naphthalene-dipolyisocyanate ( “NDI” ) such as 1, 5-NDI, isomers of hexamethylene dipolyisocyanate ( “HDI” )
  • the isocyanate compound can be a quasi-prepolymer fromed by reacting a monomeric MDI with one or more polyols.
  • the isocyanate compound is at least one aromatic isocyanate as stated above, having a NCO content between 12-32%and a viscosity below 1500 mPa ⁇ s at room temperature.
  • the amount of the isocyanate compound may vary based on the actual requirement of the foamed or non-foamed polyurethane products.
  • the content of the isocyanate compound can be from 15 wt%to 60 wt%, or from 20 wt%to 50 wt%, or from 23 wt%to 40 wt%, or from 25 wt%to 35 wt%, based on the total weight of the polyurethane composition.
  • the amount of the isocyanate compound is properly selected so that the isocyanate group is present at a stoichiometric molar amount relative to the total molar amount of the hydroxyl groups included in the first polyol component, the second polyol component, and any additional additives or modifiers.
  • the isocyanate component (B) comprises at least one prepolymer having at least two isocyanate groups.
  • prepolymer contained in the isocyanate component is a formed by the reaction of (i) one or more (monomeric) isocyanate compounds comprising at least two isocyanate groups, preferably comprising two isocyanate groups, with (ii) one or more isocyanate-reactive compounds having at least two isocyanate-reactive groups; wherein the prepolymer comprises at least two free isocyanate groups, preferably comprises two free isocyanate groups.
  • the isocyanate compound used for preparing the above stated prepolymer is selected from the group consisting of C 4 -C 12 aliphatic isocyanates comprising at least two isocyanate groups, C 6 -C 15 cycloaliphatic or aromatic isocyanates comprising at least two isocyanate groups, C 7 -C 15 araliphatic isocyanates comprising at least two isocyanate groups, and combinations thereof; and is more preferably selected from the group consisting of m-phenylene diisocyanate, 2, 4-toluene diisocyanate and/or 2, 6-toluene diisocyanate (TDI) , the various isomers of diphenylmethanediisocyanate (MDI) , carbodiimide modified MDI products, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyan
  • the isocyanate-reactive compound used for preparing the above stated prepolymer is selected from the group consisting of monomeric polyfunctional alcohols, such as C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxy groups; and polymeric polyols, such as polyester polyols, polyether polyols, polycarbonate polyols, a blend of said polyester polyols and polyether polyols, and a combination thereof.
  • monomeric polyfunctional alcohols such as C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxy
  • the isocyanate-reactive compound used for preparing the above stated prepolymer is one of the above stated monomeric polyol having a hydroxyl functionality of 2.0.
  • the isocyanate-reactive compound used for preparing the above stated prepolymer is one of the above stated monomeric polyol having a hydroxyl functionality of 2.0, and is more preferably a polyester polyol having a hydroxyl functionality of at least 2.0.
  • the polyester polyol may have a number average molecular weight of about 200 to 5,000 g/mol, such as 300 to 3,000 g/mol, or 400 to 2,000 g/mol.
  • the polyester polyol has two terminal hydroxyl groups attached to the main chain ends and does not comprise pendent hydroxyl group, more preferably does not comprise any pendent group.
  • the isocyanate-reactive compounds used for preparing the prepolymer may comprise one or more of the diol represented by Formula I and the saturated linear C 2 -C 12 aliphatic diol.
  • the amount of the above said monomeric isocyanate compound and/or prepolymer may vary based on the actual requirement of the polyurethane foam and the polyurethane tire.
  • the content of the monomeric isocyanate compound and/or prepolymer can be from 10 wt%to 70 wt%, or from 15 wt%to 60 wt%, or from 20 wt%to 50 wt%, or from 23 wt%to 40 wt%, or from 25 wt%to 35 wt%, based on the total weight of the polyurethane composition.
  • the amount of the monomeric isocyanate compound/prepolymer is properly selected so that the isocyanate group is present at a stoichiometric molar amount relative to the total molar amount of the hydroxyl groups included in the isocyanate component, the isocyanate-reactive component, and any additional additives or modifiers.
  • the prepolymer has a NCO group content of from 5 to 60 wt%, preferably from 6 to 49 wt%, based on the total weight of the prepolymer.
  • the reaction for preparing the prepolymer and the reaction between the isocyanate-reactive component (A) and the isocyanate component (B) may occur in the presence of one or more catalysts that can promote the reaction between the isocyanate group and the hydroxyl group.
  • the catalysts can include, for example, glycine salts; tertiary amines; tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; morpholine derivatives; piperazine derivatives; chelates of various metals, such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate and the like with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; acidic metal salts of strong acids such as ferric chloride and stannic chloride; salts of organic acids with variety of metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu; organotin compounds, such as tin (II
  • Tertiary amine catalysts include organic compounds that contain at least one tertiary nitrogen atom and are capable of catalyzing the hydroxyl/isocyanate reaction.
  • the tertiary amine, morpholine derivative and piperazine derivative catalysts can include, by way of example and not limitation, triethylenediamine, tetramethylethylenediamine, pentamethyl-diethylene triamine, bis (2-dimethylaminoethyl) ether, triethylamine, tripropylamine, tributyl-amine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethylenediamine, 2, 4, 6-tridimethylamino-methyl) phenol, N, N’ , N” -tris (dimethyl amino-propyl) sym-hexahydro triazine, or mixtures thereof.
  • the content of the catalyst used herein is larger than zero and is at most 3.0 wt%, preferably at most 2.5 wt%, more preferably at most 2.0 wt%, based on the total weight of the polyurethane composition.
  • the diol represented by Formula II is the only one monomer which will introduce ethylenically unsaturated functionality (especially, carbon-carbon double bond) in the backbone of the resultant polyurethane product.
  • the polyurethane composition comprises one or more additives selected from the group consisting of chain extenders, crosslinkers, blowing agents, foam stabilizers, tackifiers, plasticizers, rheology modifiers, antioxidants, fillers, colorants, pigments, water scavengers, surfactants, solvents, diluents, flame retardants, slippery-resistance agents, antistatic agents, preservatives, biocides, antioxidants and combinations of two or more thereof.
  • additives can be transmitted and stored as independent components and incorporated into the polyurethane composition shortly or immediately before the combination of components (A) and (B) .
  • these additives may be contained in either of components (A) and (B) when they are chemically inert to the isocyanate group or the isocyanate-reactive group.
  • a chain extender may be present in the reactants that form the foamed or non-foamed polyurethane products.
  • a chain extender is a chemical having two or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300, preferably less than 200 and especially from 31 to 125.
  • the isocyanate reactive groups are preferably hydroxyl, primary aliphatic or aromatic amino or secondary aliphatic or aromatic amino groups.
  • chain extenders include monoethylene glycol (MEG) , diethylene glycol, triethylene glycol, 1, 2-propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, cyclohexane dimethanol, ethylene diamine, phenylene diamine, bis (3-chloro-4-aminophenyl) methane, dimethylthio-toluenediamine and diethyltoluenediamine.
  • the chain extender is a short chain (such as C 2 to C 4 ) polyol exclusively comprising hydroxyl group as the isocyanate-reactive group, and is preferably monoethylene glycol.
  • the chain extender is an aliphatic or cyclo-aliphatic C 2 -C 12 polyol having a hydroxyl functionality of 2.0 to 8.0, such as 3.0 to 7.0, or from 4.0 to 6.0, or from 5.0 to 5.5, and can be selected from the group consisting of ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, 1, 4-cyclohexane dimethanol, and their isomers.
  • the chain extender is contained as part of the component (B) .
  • crosslinkers are materials having three or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300.
  • Crosslinkers preferably contain from 3 to 8, especially from 3 to 4 hydroxyl (including primary hydroxyl, secondary hydroxyl and tertiary hydroxyl) , primary amine, secondary amine, or tertiary amine groups per molecule and have an equivalent weight of from 30 to about 200, especially from 50 to 125.
  • the crosslinker has an isocyanate-reactive hydrogen functionality (i.e.
  • the crosslinker can be selected from the group consisting of diisopropanolamine, triisopropanolamine, N, N, N', N” , N” -pentakis (2-hydroxypropyl) diethylenetriamine, and any combinations thereof.
  • examples of suitable crosslinkers include diethanol amine, monoethanol amine, triethanol amine, mono-, di-or tri (isopropanol) amine, glycerine, trimethylol propane, pentaerythritol, and the like.
  • Chain extenders and crosslinkers are suitably used in small amounts, as hardness increases as the amount of either of these materials increases. From 0 to 25 parts by weight of a chain extender is suitably used per 100 parts by weight of the second polyol component (B) . A preferred amount is from 1 to 20, or from 0.1 to 10, or from 1 to 6, or from 1 to 15 parts per 100 parts by weight of the second polyol component (B) . From 0 to 10 parts by weight of a crosslinker is suitably used per 100 parts by weight of the second polyol component (B) . A preferred amount is from 0 to 5 parts per 100 parts by weight of the second polyol component (B) .
  • a filler may be present in the polyurethane composition. Fillers are mainly included to reduce cost. Particulate rubbery materials are especially useful fillers. Such a filler may constitute from 1 to 50%or more of the weight of the polyurethane composition.
  • Suitable blowing agents include water, air, nitrogen, argon, carbon dioxide, hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons and other volatile chemicals with low boiling points of from -30 °C to 75°C.
  • a surfactant may be present in the reaction mixture. It can be used, for example, if a cellular tire filling is desired, as the surfactant stabilizes a foaming reaction mixture until it can harden to form a cellular polymer.
  • a surfactant also may be useful to wet filler particles and thereby help disperse them into the reactive composition and the elastomer. Silicone surfactants are widely used for this purpose and can be used here as well. The amount of surfactant used will in general be between 0.02 and 1 part by weight per 100 parts by weight polyol component.
  • one or more foam stabilizer such as silicone-based foam stabilizers; anti-foam agents, such as silicone-based anti-foam agents; functional additives, such as anti-static electricity agents, flame-retardant agents, slippery resistance agents, and etc. may be further included in the polyurethane composition.
  • foam stabilizer such as silicone-based foam stabilizers
  • anti-foam agents such as silicone-based anti-foam agents
  • functional additives such as anti-static electricity agents, flame-retardant agents, slippery resistance agents, and etc.
  • the polyurethane composition comprises one or more antioxidants.
  • the antioxidant is preferably included in component B but not in component A.
  • the antioxidant is a substituted phenol type antioxidant, and is more preferably of sterically hindered phenol type antioxidant.
  • the amount of the antioxidant is from 0.3 to 2%by weight, such as from 0.5 to 1%by weight, based on the total weight of the component B.
  • the polyurethane composition comprises one or more UV absorbers.
  • the UV absorber is preferably included in component B but not in component A.
  • the absorber is a benzotriaole type UV absorber, and is more preferably 2- (2H-benzotriazo-2-yl) -6-dodecyl-4-methyl-phennol.
  • the amount of the UV absorber is from 0.5 to 2.5%by weight, such as from 1.0 to 1.8%by weight, based on the total weight of the component B.
  • the polyurethane composition comprises one or more light stabilizers.
  • the light stabilizer is preferably included in component B but not in component A.
  • the light stabilizer is a hindered aliphatic light stabilizer (HALS) , preferably a substituted alicyclic-amine HALS, and more preferably and bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate.
  • HALS hindered aliphatic light stabilizer
  • the amount of the light stabilizer is from 0.5 to 2.5%by weight, such as from 1.0 to 1.8%by weight, based on the total weight of the component B.
  • the polyurethane composition comprises at least one of colorant, pigment and dye.
  • the colorant, pigment and dye can be included in either component A or component B, and are preferably included in component B but not in component A.
  • the colorant, pigment and dye include carbon black, titanium dioxide or isoindolinon.
  • the amount of each of the colorant, pigment and dye is from 0.3 to 3.0%by weight, based on the total weight of the component B.
  • the colorant, pigment or dye can be added as a dispersion in polyol, such as a dispersion in the polyol component.
  • the polyurethane composition of the present disclosure can be used for preparing foamed polyurethane product, or polyurethane foam.
  • the polyurethane foam is applicable to prepare a wide range of tires that can be used in many applications.
  • the tires can be, for example, for a bicycle, a cart such as a golf cart or shopping cart, a motorized or unmotorized wheelchair, an automobile or truck, any other type of transportation vehicles including an aircraft, as well as various types of agriculture, industrial and construction equipment. Large tires that have an internal volume of 0.1 cubic meter or more are of particular interest.
  • the polyurethane foam has a density of at least 100 kg/m 3 , such as from 100 to 950 kg/m 3 , from 200 to 850 kg/m 3 , from 300 to 800 kg/m 3 , from 400 to 750 kg/m 3 , from 500 to 700 kg/m 3 , from 550 to 650 kg/m 3 , or from 580 to 620 kg/m 3 , or about 600 kg/m 3 .
  • the polyurethane composition is substantially free of water or moisture intentionally added therein.
  • “free of water” or “water free” means that the mixture of all the raw materials used for preparing the polyurethane composition comprise less than 3%by weight, preferably less than 2%by weight, preferably less than 1%by weight, more preferably less than 0.5%by weight, more preferably less than 0.2%by weight, more preferably less than 0.1%by weight, more preferably less than 100 ppm by weight, more preferably less than 50 ppm by weight, more preferably less than 10 ppm by weight, more preferably less than 1ppm by weight of water, based on the total weight of the mixture of raw materials.
  • the polyurethane material is prepared under an isocyanate index between 90 and 120, wherein index 100 means the molar ratio between isocyanate group and isocyanate-reactive groups is 1.00.
  • Suitable conditions for promoting the curing of the polyurethane polymer include a temperature of from about 20°C to about 150°C. In some embodiments, the curing is performed at a temperature of from about 30°C to about 120°C, such as from 80 °C to 100 °C. In other embodiments, the curing is performed at a temperature of from about 35 °C to about 110°C. In various embodiments, the temperature for curing may be selected at least in part based on the time duration required for the polyurethane polymer to gel and/or cure at that temperature. Cure time will also depend on other factors, including, for example, the particular components (e.g., catalysts and quantities thereof) , and the size and shape of the article being manufactured, and can be from 0.1 to 60 hours, such as from 0.5 to 24 hours.
  • polyurethane foams especially, polyurethane foams
  • linear saturated polyols e.g. 1, 4-butanediol, BDO
  • said technical progresses may include one or more of improved cost competitiveness, good processibility, improved tear-resistance and heat resistance, hence the polyurethane foams prepared in the present disclosure is suitable for many applications like footwear, tires, seals, cushioning parts, bumpers, etc.
  • the polyurethane foam prepared by using 1-20 wt% (based on the total amount of component A) of diol represented by Formula I can achieve an improvement of at least 10%in the tear strength and at least 30%in the heat resistance (measured by delta storage modulus at low-high temperature) when compared with polyurethane prepared by using linear saturated polyols.
  • the technology of the present disclosure will not result in significantly increased cost.
  • Tear strength were determined on a Gotech AI-7000S1 universal testing machine according to the testing method DIN 53543, and the general industrial requirement on tear strength is higher than 180 N/cm.
  • the storage modulus was characterized via Dynamic mechanical analysis (DMA) , wherein DMA was performed on a TA RSA G2 analyzer under strain-control mode at a frequency of 1 Hz and 0.1%strain, in a temperature range from -80 °C to 200 °C with a ramp rate of 3 °C/min.
  • DMA Dynamic mechanical analysis
  • DSC Differential scanning calorimeter
  • the polyol components were made by mixing the polyols, catalysts, blowing agents and silicon compounds as shown in Table 2 &3. Then the polyol components were mixed with the isocyanate prepolymer (NE569) at room temperature with a high speed stirrer (at a stirring rate of 2500 RPM) for 7 seconds. The mixture was poured into a metal mold (which is lined with PTFE film to aid the demolding at a later stage) at 50 °C and then the mold was sealed immediately. The reaction between the polyol components and prepolymer occurred instantly after the mixing, the reaction content was cured at 50°C to produce a foam sample. The mold was opened and the foam sample was demolded. The foam samples were stored overnight at room temperature, subject to another post-curing treatment in an oven at 50°C for 24 hours, and then characterized.
  • inventive examples which comprise residual moieties of unsaturated linear diol in the polyurethane backbone exhibit significant improvement in the tear strength and thermal resistance over the polyurethane prepared by using saturated linear diols.
  • Comparative Examples 2 and 3 illustrate that the attachment of ethylenically unsaturated side chains to the polyurethane backbone will substantially deteriorate the tear strength and thermal resistance.
  • the comparison among results of inventive examples 2-5 also show that the highest tear strength and thermal resistance can be achieved at an optimized ratio of unsaturated diol and saturated diol.

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Abstract

A polyurethane composition comprising (A) an isocyanate-reactive component comprising at least one unsaturated linear diol represented by Formula I, and at least one second polyol; and (B) an isocyanate component is disclosed, wherein the polyurethane composition does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into a polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component. The foamed polyurethane product prepared by using the polyurethane composition can achieve inhibited internal heat buildup and superior mechanical strength. A method for preparing the polyurethane foam is also provided. HO-R 1-C (R 2) =C (R 3) -R 4-OH Formula I

Description

POLYURETHANE COMPOSITIONS, FOAMS PREPARED WITH SAME AND PREPARATION METHODS THEREOF FIELD OF THE INVENTION
The present disclosure relates to a polyurethane composition, a polyurethane material, preferably a polyurethane foam prepared by using the composition, and a method for preparing the polyurethane material. The polyurethane composition has a particularly designed formulation so as to produce a polyurethane foam exhibiting excellent properties such as inhibited internal heat buildup, enhanced thermal resistance, tear strength, among others.
BACKGROUND TECHNOLOGY
Microcellular polyurethane foams are foamed polyurethane materials with a density of about 100-900 kg/m 3 and are usually fabricated via a two-component process of reacting Component A (polyols, chain extenders, foaming agents, catalysts, surfactants, etc. ) and Component B (monomeric isocyanate, prepolymer of polyols and isocyanates, or blend thereof) . The two components are usually blended at high speed and then transferred into varied molds with desired shapes. Over the past decades, microcellular polyurethane foams have been employed in a wide range of end use applications like shoemaking (e.g., soles) and automotive industries (e.g., bumpers and arm rests of integral skin foams) . Recently, microcellular polyurethane foams have been explored in solid tire applications. These microcellular polyurethane solid tires have been attractive due to the possibility of eliminating deflation risk that all the pneumatic rubber tires inherently possess and may bring about potential safety issues and increased maintenance costs.
The uses of polyurethane in tire applications have been challenging due to inherent attributes of polyurethanes to generate “internal heat” . The internal heat buildup originates from transition of mechanical energy into heat inside polyurethanes and is characterized by significant augmentation of the tire temperature during rolling especially under high speed and load. With increasing temperature, material failures including fatigue cracking and/or melting are usually observed. Thus the upper limits of speed and load under which a polyurethane tire can operate are determined by internal heat buildup, and of course, thermal stability of the polyurethane tire. Significant efforts have been made to increase the thermal stability of  polyurethanes by introduction of functional moieties e.g. isocyanurate, oxazolidone, oxamide or borate groups or to reduce the “internal heat buildup” in polyurethanes by using special isocyanates like 1, 5-naphthylene diisocyanate. However, the above indicated modification by using the chemicals with special groups or special isocyanates are usually too expensive to be commercialized. Besides, it was found that when compared with polyether polyols, polyester polyols can impart polyurethanes with higher tear strength due to higher cohesive energy thereof, but their processing and durability are poor due to their high viscosity and insufficient resistance to hydrolytic attack, respectively. There were also reports about using specific isocyanates like 1, 5-Naphthalene diisocyanate (NDI) and specific chain extender (e.g. amines) to improve the tear strength and thermal stability of polyurethane material, but all of raw materials exhibit unacceptable disadvantages such as excessively high cost, poor storage stability, poor processing properties, etc.
For the above reasons, there is still a need in the polyurethane manufacture industry to develop a polyurethane composition whose performance properties as stated above can be improved with an economical way. After persistent exploration, the inventors have surprisingly developed a polyurethane composition which can achieve one or more of the above targets.
SUMMARY OF THE INVENTION
The present disclosure provides a unique polyurethane composition, a polyurethane material, preferably a polyurethane foam, prepared by using the composition, a method for preparing the polyurethane material and a method for improving the performance properties of the polyurethane material.
In a first aspect of the present disclosure, the present disclosure provides a polyurethane composition, comprising
(A) an isocyanate-reactive component comprising at least one unsaturated linear diol represented by Formula I,
HO-R 1-C (R 2) =C (R 3) -R 4-OH Formula I
wherein each of R 1 and R 4 is independently selected from the group consisting of covalent bond, C 1 to C 6 alkylene group, C 2-C 6 alkenylene group, C 6-C 12 cycloalkylene group, and C 6-C 12 arylene group; and each of R 2 and R 3 is independently selected from the group  consisting of hydrogen and C 1-C 6 alkyl group;
and at least one second polyol other than the unsaturated linear diol; and
(B) an isocyanate component comprising at least one first isocyanate compound comprising at least two isocyanate groups,
wherein the polyurethane composition does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into a polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component.
According to a preferable embodiment of the present disclosure, the polyurethane composition can be used for preparing a polyurethane material comprising a plurality of polyurethane backbones, wherein the unsaturated linear diol of formula I forms at least part of the repeating units in the polyurethane backbones, and there is no ethylenically unsaturated side chain linked to the polyurethane backbones.
According to another embodiment, the unsaturated linear diol represented by Formula I is selected from a group consisting of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, 2, 4-hexadiene-1, 6-diol, 2-heptene-1, 7-diol, 3-heptene-1, 7-diol, 2, 4-heptadiene-1, 7-diol, 2, 5-heptadiene-1, 7-diol, 2-octene-1, 8-diol, 3-octene-1, 8-diol, 4-octene-1, 8-diol, 2, 4-octadiene-1, 8-diol, 2, 5-octadiene-1, 8-diol, 2, 6-octadiene-1, 8-diol, 1, 2-bis (4-hydroxylcyclohexyl) ethylene, 1, 2-bis (3-hydroxylcyclohexyl) ethylene, 1, 2-bis (4-methylolcyclohexyl) ethylene, 1, 2-bis (3-methylolcyclohexyl) ethylene, 1, 2-bis (4-hydroxyl-phenyl) ethylene, 1, 2-bis (4-methylol-phenyl) ethylene, 1, 2-bis (4-hydroxyl-benzyl) -ethylene, 1, 2-bis (4-methylol-benzyl) ethylene, and any combinations thereof. According to another embodiment, the content of the unsaturated linear diol represented by Formula I is from 1%to 20%by weight, based on the total weight of the isocyanate-reactive component (A) . According to another embodiment, the second polyol is selected from the group consisting of C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7-C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof. According to another embodiment,  the second polyol optionally includes at least one saturated linear C 2-C 12 aliphatic diol, and the weight ratio between the saturated linear C 2-C 12 aliphatic diol and the unsaturated linear diol is from 0: 20 to 10: 1. According to another embodiment, the weight ratio between the saturated linear C 2-C 12 aliphatic diol and the unsaturated linear diol is from 1: 1 to 1: 3. According to another embodiment, the first isocyanate compound is selected from the group consisting of C 4-C 12 aliphatic isocyanate comprising at least two isocyanate groups, C 6-C 15 cycloaliphatic or aromatic isocyanate comprising at least two isocyanate groups, C 7-C 15 araliphatic isocyanate comprising at least two isocyanate groups, a prepolymer comprising at least two isocyanate groups, and any combinations thereof. According to another embodiment, the polyurethane composition further comprises at least one additive selected from the group consisting of chain extender, crosslinker, blowing agent, foam stabilizer, tackifier, plasticizer, rheology modifier, antioxidant, UV-absorbent, light-stabilizer, catalyst, cocatalyst, filler, colorant, pigment, water scavenger, surfactant, solvent, diluent, flame retardant, slippery-resistance agent, antistatic agent, preservative, biocide and any combinations thereof.
In a second aspect of the present disclosure, the present disclosure provides a polyurethane material prepared with the polyurethane composition as stated above, wherein the polyurethane material comprises polyurethane main chains derived from the reaction of
(A) an isocyanate-reactive component comprising at least one unsaturated linear diol represented by Formula I,
HO-R 1-C (R 2) =C (R 3) -R 4-OH Formula I
wherein each of R 1 and R 4 is independently selected from the group consisting of direct bond, C 1 to C 6 alkylene group, C 2-C 6 alkenylene group, C 6-C 12 cycloalkylene group, and C 6-C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1-C 6 alkyl group;
and at least one second polyol other than the unsaturated linear diol; and
(B) an isocyanate component comprising at least one first isocyanate compound comprising at least two isocyanate groups,
wherein repeating units derived from the unsaturated linear diol constitute at least part of the polyurethane backbone, and none of the polyurethane backbone in the polyurethane material comprises an ethylenically unsaturated side chain.
According to a preferable embodiment of the present disclosure, the polyurethane  material is a microcellular polyurethane foam.
In a third aspect of the present disclosure, the present disclosure provides a method for preparing said polyurethane material (foam) , comprising a step of reacting the isocyanate-reactive component (A) with the (B) isocyanate component to form the polyurethane material (foam) .
In a fourth aspect of the present disclosure, the present disclosure provides a method for improving the performance property of said polyurethane material, comprising the step of introducing repeating units derived from an unsaturated linear diol represented by Formula I into at least part of polyurethane main chains in the polyurethane material,
and excluding ethylenically unsaturated side chain from all the polyurethane backbones in the polyurethane material,
wherein the performance property includes at least one of internal heat buildup, thermal stability, tear strength, viscosity, abrasion resistance and hydrolysis resistance.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
DETAILED DESCRIPTION OF THE INVENTION
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Also, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.
As disclosed herein, "and/or" means "and, or as an alternative" . All ranges include endpoints unless otherwise indicated. Unless indicated otherwise, all the percentages and ratios are calculated based on weight, and all the molecular weights are number average molecular weights.
According to an embodiment of the present disclosure, the polyurethane composition is a "two-component" , "two-part" or "two-package" composition comprising an isocyanate-reactive component (A) and an isocyanate component (B) . The isocyanate-reactive component (A) and the isocyanate component (B) are transported and stored separately, combined shortly or immediately before being applied during the manufacture of the polyurethane foam, such as  solid tire. Once combined, the isocyanate groups in component (B) reacts with the isocyanate-reactive groups (particularly, hydroxyl group) in component (A) to form polyurethane.
One of the most important technical breakthrough of the present disclosure is to incorporate residual moiety of linear unsaturated diols having carbon-carbon double bond (which is also known as “ethylenically unsaturated linear diol” or “linear diol having ethylenically unsaturated functionality” ) into the backbones of the polyurethane material and as constitution units of the polyurethane material by particularly designing the formulation of the raw materials, especially the polyol compounds contained in the isocyanate-reactive component (A) and the isocyanate component (B) , e.g. those used for preparing the prepolymer.
According to various embodiment of the present disclosure, the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I,
HO-R 1-C (R 2) =C (R 3) -R 4-OH Formula I
wherein each of R 1 and R 4 is independently selected from the group consisting of covalent bond, C 1 to C 6 alkylene group, C 2-C 6 alkenylene group, C 6-C 12 cycloalkylene group, and C 6-C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1-C 6 alkyl group. Preferably, the unsaturated linear diol represented by Formula I can be selected from the group consisting of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, 2, 4-hexadiene-1, 6-diol, 2-heptene-1, 7-diol, 3-heptene-1, 7-diol, 2, 4-heptadiene-1, 7-diol, 2, 5-heptadiene-1, 7-diol, 2-octene-1, 8-diol, 3-octene-1, 8-diol, 4-octene-1, 8-diol, 2, 4-octadiene-1, 8-diol, 2, 5-octadiene-1, 8-diol, 2, 6-octadiene-1, 8-diol, 1, 2-bis (4-hydroxylcyclohexyl) ethylene, 1, 2-bis (3-hydroxylcyclohexyl) ethylene, 1, 2-bis (4-methylolcyclohexyl) ethylene, 1, 2-bis (3-methylolcyclohexyl) ethylene, 1, 2-bis (4-hydroxyl-phenyl) ethylene, 1, 2-bis (4-methylol-phenyl) ethylene, 1, 2-bis (4-hydroxyl-benzyl) -ethylene, 1, 2-bis (4-methylol-benzyl) ethylene, and any combinations thereof. More preferably, the unsaturated linear diol represented by Formula I is 2-butene-1, 4-diol, which is also known as butenediol (BEDO) in the context of the present disclosure. According to a preferable embodiment of the present disclosure, the content of the above said unsaturated linear diol represented by Formula I is from 1%to 20%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%,  4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%and 20 wt%.
According to various embodiment of the present disclosure, the isocyanate-reactive component (A) , more preferably the whole polyurethane composition, does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into the polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component, thus none of the polyurethane backbones in the polyurethane material comprises an ethylenically unsaturated side chain.
In the context of the present disclosure, the term “polyurethane backbone” refers to the main chain or the longest linear polymeric chain contained in the polyurethane material or polyurethane foam prepared by reacting component (A) with component (B) of the present disclosure. The polyurethane backbone is formed with repeating units (residual moieties) derived from the isocyanate compounds contained in the isocyanate component (B) , various polyols, such as the unsaturated linear diol represented by Formula I, the saturated linear C 2-C 12 aliphatic diol, and any other polyols contained in the isocyanate-reactive component (A) , and any other additive which comprises at least two isocyanate-reactive groups and may be included in the polyurethane backbone. The residual moiety derived from the isocyanate compound and the residual moiety derived from the isocyanate-reactive compounds (polyol, chain extender, crosslinker, etc. ) are linked via urethane bond to form a linear polyurethane backbone, and the ethylenically unsaturated functionality (the carbon-carbon double bond) is preferably retained intact in the linear polyurethane backbone of the resultant polyurethane foam product.
In the context of the present disclosure, the term “an unsaturated compound which will introduce an ethylenically unsaturated side chain into the polyurethane backbone” refers to a compound whose molecular chain containing one or more ethylenically unsaturated functionalities (carbon-carbon double bond) is not terminated at both ends with a isocyanate-reactive (such as hydroxyl group, amine group, carboxyl group, etc. ) , and thus the ethylenically unsaturated functionality will be linked to the polyurethane backbone in the form of a side chain rather than as part of the linear polyurethane backbone. For example, 3-  (allyloxy) propane-1, 2-diol, whose molecular structure is shown in Formula II, is a typical unsaturated compound which “will form an ethylenically unsaturated side chain” attached to the polyurethane backbone, hence such a compound and any analogs shall be particularly excluded from the polyurethane composition of the present disclosure.
Figure PCTCN2020108790-appb-000001
According to an embodiment of the present disclosure, one or more of the isocyanate compound, the unsaturated linear diol represented by Formula I, the second polyol, and the additives (chain extender, crosslinker, etc. ) may introduce at least one side chain to the polyurethane backbone, but none of the said chain comprises an ethylenically unsaturated functionality.
According to an embodiment of the present disclosure, the isocyanate-reactive component (A) further comprises at least one second polyol other than the unsaturated linear diol represented by Formula I. For example, the second polyol can be selected from the group consisting of C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7-C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof.
According to a preferable embodiment of the present disclosure, the second polyol includes at least one saturated linear C 2-C 12 aliphatic diol and at least one additional polyol, i.e. the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2-C 12 aliphatic diol, and at least one additional polyol which is different from either one of the above diols. According to this preferable embodiment of the present disclosure, the saturated linear C 2-C 12 aliphatic diol can be selected from the group consisting of ethylene glycol (ethane diol) , propylene glycol (propane diol) , tetramethylene glycol (1, 4-butane diol) , and 2-methyl-1, 3-propane glycol (1, 3-butane diol) , and is more preferably 1, 4-butane diol. According to an embodiment of the present disclosure, the content of the above said saturated linear C 2-C 12 aliphatic diol is from  0.5%to 40%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%. According to another embodiment of the present disclosure, the weight ratio between the saturated linear C 2-C 12 aliphatic diol and the unsaturated linear diol represented by Formula I is from 0: 20 to 20: 1, such as from 1: 10 to 10: 1, or from 1: 1 to 1: 3, such as in the numerical range obtained by combining any two of the following ratios: 0: 20, 1: 20, 1: 18, 1: 15, 1: 10, 1: 8, 1: 7, 1: 6, 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 3: 2, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, 12: 1, 13: 1, 14: 1, 15: 1, 16: 1, 17: 1, 18: 1, 19: 1, and 20: 1.
According to a preferable embodiment of the present disclosure, the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2-C 12 aliphatic diol, and at least one additional polyol, wherein the at least one additional polyol is different from either one of the above diols and is selected from the group consisting of C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7-C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof. More preferably, the at least one additional polyol is different from either one of the above diols and is selected from the group consisting of C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, dimer of the C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, trimer of the C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C 7-C 15 araliphatic polyhydric alcohols comprising at  least two hydroxy groups, polyester polyols having a molecular weight from 500 to 5,000, polycarbonate polyols having an average functionality of 2 to 5 and a molecular weight from 200 to 5,000, polyether polyols having an average functionality of 2 to 5 and an average molecular weight of 200 to 12,000, C 2-C 10 alkanolamine comprising at least one hydroxyl group and at least one amino group, vegetable oil having at least two hydroxyl groups, and a combination thereof.
In an embodiment of the present disclosure, the polyether polyol used for component (A) has a molecular weight of 100 to 10,000 g/mol, and may have a molecular weight in the numerical range obtained by combining any two of the following end point values: 120, 150, 180, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, 8000, 8200, 8500, 8800, 9000, 9200, 9500, 9800, and 10000 g/mol. In an embodiment of the present disclosure, the polyether polyol used for component (A) has an average hydroxyl functionality of 1.0 to 8.0, or from 1.5 to 5.0, and may have an average hydroxyl functionality in the numerical range obtained by combining any two of the following end point values: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 and 7.9. According to a preferable embodiment of the present disclosure, the polyether polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) and any copolymers thereof, such as poly (ethylene oxide-propylene oxide) glycol. According to another embodiment of the present application, the polyether polyol can be polytetramethylene glycol (PTMEG) having a molecular weight of 200 to 3,000 and a hydroxyl functionality of 1.0 to 3.0. According to another embodiment of the present application, starting material polyether polyol can be a poly (ethylene oxide-propylene oxide) glycol having a molecular weight of 200 to 3,000 and a hydroxyl functionality of 2.0 to 8.0, wherein the molar ratio between the ethylene oxide repeating unit and the propylene oxide repeating unit can be from 5/95 to 95/5, such as from 10/90 to 90/10, or from 20/80 to 80/20, or from 40/60 to 60/40, or at  about 50/50.
According to a preferable embodiment of the present application, the polymer polyol is a composite particulate having a core-shell structure, wherein the core is a micro-sized or nano-sized core composed of any polymer or copolymer, such as SAN (styrene and acryl nitrile) , and the shell phase is composed of a polyether polyol, such as PO-EO polyol. According to another embodiment of the present application, the polymer polyol has a shell phase based on the poly (C 2-C 10) alkylene glycol or copolymer thereof. Preferably, the polymer polyol has a core phase and a shell phase based on the poly (C 2-C 10) alkylene glycol or copolymer thereof, having a solid content of 1-50%, an OH value 10 ～ 149, and a hydroxyl functionality of 1.5-5.0, such as 2.0-5.0. The shell phase may comprise at least one poly (C 2-C 10) alkylene glycol or copolymer thereof, for example, the polyol may be selected from the group consisting of polyethylene, (methoxy) polyethylene glycol (MPEG) , polyethylene glycol (PEG) , poly (propylene glycol) , polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) or copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) with primary hydroxyl ended group or secondary hydroxyl ended group. The core phase may be micro-sized and may comprise any polymers compatible with the shell phase. For example, the core phase may comprise polystyrene, polyacrylnitrile, polyester, polyolefin or polyether different (in either composition or polymerization degree) from those of the shell phase. According to a preferable embodiment of the present application, the polymer polyol is a composite particulate having a core-shell structure, wherein the core is a micro-sized core composed of SAN (styrene and acryl nitrile) and the shell phase is composed of PO-EO polyol. Such a polymer polyol can be prepared by radical copolymerization of styrene, acryl nitrile and poly (EO-PO) polyol comprising ethylenically unsaturated groups.
According to an embodiment of the present disclosure, the polyether polyols can be prepared by polymerization of one or more linear or cyclic alkylene oxides selected from propylene oxide (PO) , ethylene oxide (EO) , butylene oxide, tetramethylene glycol, tetrahydrofuran, 2-methyl-1, 3-propane glycol and mixtures thereof, with proper starter molecules in the presence of a catalyst. Typical starter molecules include compounds having at least 1, preferably from 1.5 to 3.0 hydroxyl groups or having one or more primary amine groups in the molecule. Suitable starter molecules having at least 1 and preferably from 1.5 to 3.0 hydroxyl groups in the molecules are for example selected from the group comprising  ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butenediol, 1, 4-butynediol, 1, 5-pentanediol, neopentyl glycol, 1, 4-bis (hydroxymethyl) -cyclohexane, 1, 2-bis (hydroxymethyl) cyclohexane, 1, 3-bis (hydroxymethyl) -cyclohexane, 2-methylpropane-1, 3-diol, methylpentanediols, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycols, trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as, for example, glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines, and also melamine. Starter molecules having 1 or more primary amine groups in the molecules may be selected for example from the group consisting of aniline, EDA, TDA, MDA and PMDA, more preferably from the group comprising TDA and PMDA, an most preferably TDA. When TDA is used, all isomers can be used alone or in any desired mixtures. For example, 2, 4-TDA, 2, 6-TDA, mixtures of 2, 4-TDA and 2, 6-TDA, 2, 3-TDA, 3, 4-TDA, mixtures of 3, 4-TDA and 2, 3-TDA, and also mixtures of all the above isomers can be used. Catalysts for the preparation of polyether polyols may include alkaline catalysts, such as potassium hydroxide, for anionic polymerization or Lewis acid catalysts, such as boron trifluoride, for cationic polymerization. Suitable polymerization catalysts may include potassium hydroxide, cesium hydroxide, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound. In a preferable embodiment of the present disclosure, the starting material polyether polyol includes polyethylene, (methoxy) polyethylene glycol (MPEG) , polyethylene glycol (PEG) , poly (propylene glycol) , polytetramethylene glycol, poly (2-methyl-1, 3-propane glycol) or copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) with primary hydroxyl ended group or secondary hydroxyl ended group.
According to an embodiment of the present disclosure, the isocyanate-reactive component (A) comprises at least one unsaturated linear diol represented by Formula I, at least one saturated linear C 2-C 12 aliphatic diol, and at least one additional polyol, wherein the at least one additional polyol is different from either one of the above diols and is more preferably one or more polyether polyol, a polymer polyol having a core phase and a shell phase based on polyether polyol, and any combinations thereof. According to an embodiment  of the present disclosure, the content of the above said additional polyol (which is different from either one of the above diols) , is from 1%to 90%by weight, based on the total weight of the isocyanate-reactive component (A) , such as in the numerical range obtained by combining any two of the following end point values: 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6wtt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 20 wt%, 22 wt%, 24 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 85 wt%, 88 wt%, and 90 wt%.
In various embodiments, the isocyanate component (B) comprises at least one monomeric compound having at least two isocyanate groups, or at least one prepolymer having at least two isocyanate groups, or a mixture thereof. According to an embodiment of the present disclosure, the isocyanate component (B) has an average NCO functionality of at least about 1.5, preferably from about 2 to 10, more preferably from about 2 to about 8, more preferably from about 2 to about 6, and most preferably about 2. Preferably, the isocyanate component (B) has an average NCO functionality of 2.0.
In the context of the present disclosure, the terms “prepolymer” , “prepolymer of isocyanate” and “polyurethane prepolymer” are used interchangeably and refer to a prepolymer prepared by reacting at least one isocyanate compound having at least two isocyanate groups with a polyol, wherein the prepolymer comprises at least two isocyanate groups and is used for further reacting with the isocyanate-reactive component (A) to form the polyurethane material such as polyurethane foam. In the context of the present disclosure, the terms “polyisocyanate compound” , “polyisocyanate” and “isocyanate compound comprising at least two isocyanate groups” are used interchangeably and refer to an isocyanate having at least two isocyanate groups, wherein the isocyanate is monomeric, dimeric, trimeric or oligomeric (such as having a polymerization degree of 2, 3, 4, 5 or 6) .
According to an embodiment of the present disclosure, the monomeric compound having at least two isocyanate groups is selected from the group consisting of C 4-C 12 aliphatic isocyanate comprising at least two isocyanate groups, C 6-C 15 cycloaliphatic or aromatic  isocyanate comprising at least two isocyanate groups, C 7-C 15 araliphatic isocyanate comprising at least two isocyanate groups, a prepolymer comprising at least two isocyanate groups, and any combinations thereof. For example, the monomeric compound having at least two isocyanate groups may include m-phenylene diisocyanate, 2, 4-toluene diisocyanate and/or 2, 6-toluene diisocyanate (TDI) , the various isomers of diphenylmethanediisocyanate (MDI) , carbodiimide modified MDI products, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI) , isomers of naphthalene-dipolyisocyanate ( “NDI” ) such as 1, 5-NDI, isomers of hexamethylene dipolyisocyanate ( “HDI” ) , isomers of isophorone dipolyisocyanate ( “IPDI” ) , isomers of xylene dipolyisocyanate ( “XDI” ) , or mixtures thereof. According to a preferable embodiment of the present disclosure, the isocyanate compound can be a quasi-prepolymer fromed by reacting a monomeric MDI with one or more polyols. According to a preferable embodiment of the present disclosure, the isocyanate compound is at least one aromatic isocyanate as stated above, having a NCO content between 12-32%and a viscosity below 1500 mPa·s at room temperature. Generally, the amount of the isocyanate compound may vary based on the actual requirement of the foamed or non-foamed polyurethane products. For example, as one illustrative embodiment, the content of the isocyanate compound can be from 15 wt%to 60 wt%, or from 20 wt%to 50 wt%, or from 23 wt%to 40 wt%, or from 25 wt%to 35 wt%, based on the total weight of the polyurethane composition. According to a preferable embodiment of the present disclosure, the amount of the isocyanate compound is properly selected so that the isocyanate group is present at a stoichiometric molar amount relative to the total molar amount of the hydroxyl groups included in the first polyol component, the second polyol component, and any additional additives or modifiers.
According to another embodiment of the present disclosure, the isocyanate component (B) comprises at least one prepolymer having at least two isocyanate groups. prepolymer contained in the isocyanate component is a formed by the reaction of (i) one or more (monomeric) isocyanate compounds comprising at least two isocyanate groups, preferably comprising two isocyanate groups, with (ii) one or more isocyanate-reactive compounds having at least two isocyanate-reactive groups; wherein the prepolymer comprises at least two free isocyanate groups, preferably comprises two free isocyanate groups. According to a  preferable embodiment, the isocyanate compound used for preparing the above stated prepolymer is selected from the group consisting of C 4-C 12 aliphatic isocyanates comprising at least two isocyanate groups, C 6-C 15 cycloaliphatic or aromatic isocyanates comprising at least two isocyanate groups, C 7-C 15 araliphatic isocyanates comprising at least two isocyanate groups, and combinations thereof; and is more preferably selected from the group consisting of m-phenylene diisocyanate, 2, 4-toluene diisocyanate and/or 2, 6-toluene diisocyanate (TDI) , the various isomers of diphenylmethanediisocyanate (MDI) , carbodiimide modified MDI products, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate, cyclohexane-1, 4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1, 5-diisocyanate, isophorone diisocyanate (IPDI) , isomers of naphthalene-dipolyisocyanate ( “NDI” ) such as 1, 5-NDI, isomers of hexamethylene dipolyisocyanate ( “HDI” ) , isomers of isophorone dipolyisocyanate ( “IPDI” ) , isomers of xylene dipolyisocyanate ( “XDI” ) , or mixtures thereof. According to another preferable embodiment of the present disclosure, the isocyanate-reactive compound used for preparing the above stated prepolymer is selected from the group consisting of monomeric polyfunctional alcohols, such as C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C 7-C 15 araliphatic polyhydric alcohols comprising at least two hydroxy groups; and polymeric polyols, such as polyester polyols, polyether polyols, polycarbonate polyols, a blend of said polyester polyols and polyether polyols, and a combination thereof. According to a preferable embodiment of the present application, the isocyanate-reactive compound used for preparing the above stated prepolymer is one of the above stated monomeric polyol having a hydroxyl functionality of 2.0. According to another preferable embodiment of the present application, the isocyanate-reactive compound used for preparing the above stated prepolymer is one of the above stated monomeric polyol having a hydroxyl functionality of 2.0, and is more preferably a polyester polyol having a hydroxyl functionality of at least 2.0. According to an embodiment of the present disclosure, the polyester polyol may have a number average molecular weight of about 200 to 5,000 g/mol, such as 300 to 3,000 g/mol, or 400 to 2,000 g/mol. According to a preferable embodiment of the present disclosure, the polyester polyol has two terminal hydroxyl groups attached to the main chain ends and does not comprise pendent hydroxyl group, more preferably does not comprise any pendent group. According to another  embodiment of the present disclosure, the isocyanate-reactive compounds used for preparing the prepolymer may comprise one or more of the diol represented by Formula I and the saturated linear C 2-C 12 aliphatic diol.
Generally, the amount of the above said monomeric isocyanate compound and/or prepolymer may vary based on the actual requirement of the polyurethane foam and the polyurethane tire. For example, as one illustrative embodiment, the content of the monomeric isocyanate compound and/or prepolymer can be from 10 wt%to 70 wt%, or from 15 wt%to 60 wt%, or from 20 wt%to 50 wt%, or from 23 wt%to 40 wt%, or from 25 wt%to 35 wt%, based on the total weight of the polyurethane composition. According to a preferable embodiment of the present disclosure, the amount of the monomeric isocyanate compound/prepolymer is properly selected so that the isocyanate group is present at a stoichiometric molar amount relative to the total molar amount of the hydroxyl groups included in the isocyanate component, the isocyanate-reactive component, and any additional additives or modifiers. According to another embodiment of the present disclosure, the prepolymer has a NCO group content of from 5 to 60 wt%, preferably from 6 to 49 wt%, based on the total weight of the prepolymer.
The reaction for preparing the prepolymer and the reaction between the isocyanate-reactive component (A) and the isocyanate component (B) may occur in the presence of one or more catalysts that can promote the reaction between the isocyanate group and the hydroxyl group. Without being limited to theory, the catalysts can include, for example, glycine salts; tertiary amines; tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; morpholine derivatives; piperazine derivatives; chelates of various metals, such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate and the like with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; acidic metal salts of strong acids such as ferric chloride and stannic chloride; salts of organic acids with variety of metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu; organotin compounds, such as tin (II) salts of organic carboxylic acids, e.g., tin (II) diacetate, tin (II) dioctanoate, tin (II) diethylhexanoate, and tin (II) dilaurate, and dialkyltin (IV) salts of organic carboxylic acids, e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate; bismuth salts of organic carboxylic acids, e.g., bismuth octanoate; organometallic derivatives of trivalent and pentavalent As, Sb and Bi and  metal carbonyls of iron and cobalt; or mixtures thereof.
Tertiary amine catalysts include organic compounds that contain at least one tertiary nitrogen atom and are capable of catalyzing the hydroxyl/isocyanate reaction. The tertiary amine, morpholine derivative and piperazine derivative catalysts can include, by way of example and not limitation, triethylenediamine, tetramethylethylenediamine, pentamethyl-diethylene triamine, bis (2-dimethylaminoethyl) ether, triethylamine, tripropylamine, tributyl-amine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethylenediamine, 2, 4, 6-tridimethylamino-methyl) phenol, N, N’ , N” -tris (dimethyl amino-propyl) sym-hexahydro triazine, or mixtures thereof.
In general, the content of the catalyst used herein is larger than zero and is at most 3.0 wt%, preferably at most 2.5 wt%, more preferably at most 2.0 wt%, based on the total weight of the polyurethane composition.
In an embodiment of the present disclosure, the diol represented by Formula II is the only one monomer which will introduce ethylenically unsaturated functionality (especially, carbon-carbon double bond) in the backbone of the resultant polyurethane product.
In various embodiments of the present disclosure, the polyurethane composition comprises one or more additives selected from the group consisting of chain extenders, crosslinkers, blowing agents, foam stabilizers, tackifiers, plasticizers, rheology modifiers, antioxidants, fillers, colorants, pigments, water scavengers, surfactants, solvents, diluents, flame retardants, slippery-resistance agents, antistatic agents, preservatives, biocides, antioxidants and combinations of two or more thereof. These additives can be transmitted and stored as independent components and incorporated into the polyurethane composition shortly or immediately before the combination of components (A) and (B) . Alternatively, these additives may be contained in either of components (A) and (B) when they are chemically inert to the isocyanate group or the isocyanate-reactive group.
A chain extender may be present in the reactants that form the foamed or non-foamed polyurethane products. A chain extender is a chemical having two or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300, preferably less than 200 and especially from 31 to 125. The isocyanate reactive groups are preferably hydroxyl, primary aliphatic or aromatic amino or secondary aliphatic or aromatic amino groups. Representative chain extenders include monoethylene glycol (MEG) ,  diethylene glycol, triethylene glycol, 1, 2-propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, cyclohexane dimethanol, ethylene diamine, phenylene diamine, bis (3-chloro-4-aminophenyl) methane, dimethylthio-toluenediamine and diethyltoluenediamine. According to a preferable embodiment of the present disclosure, the chain extender is a short chain (such as C 2 to C 4) polyol exclusively comprising hydroxyl group as the isocyanate-reactive group, and is preferably monoethylene glycol. According to another preferable embodiment of the present disclosure, the chain extender is an aliphatic or cyclo-aliphatic C 2-C 12 polyol having a hydroxyl functionality of 2.0 to 8.0, such as 3.0 to 7.0, or from 4.0 to 6.0, or from 5.0 to 5.5, and can be selected from the group consisting of ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, 1, 4-cyclohexane dimethanol, and their isomers. According to a preferable embodiment of the present disclosure, the chain extender is contained as part of the component (B) .
One or more crosslinkers also may be present in the reactants that form the foamed or non-foamed polyurethane product. For purposes of this invention, "crosslinkers" are materials having three or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300. Crosslinkers preferably contain from 3 to 8, especially from 3 to 4 hydroxyl (including primary hydroxyl, secondary hydroxyl and tertiary hydroxyl) , primary amine, secondary amine, or tertiary amine groups per molecule and have an equivalent weight of from 30 to about 200, especially from 50 to 125. According to a preferable embodiment of the present disclosure, the crosslinker has an isocyanate-reactive hydrogen functionality (i.e. the sum of hydroxyl and amine groups) of 3 to 6, such as 3 to 4, and more preferably comprises at least one amine group (such as primary amine, secondary amine, or tertiary amine group, and more preferably a tertiary amine group) and at least one, more preferably at least two or at least three secondary and/or tertiary hydroxyl groups. According to a more preferable embodiment of the present disclosure, the crosslinker can be selected from the group consisting of diisopropanolamine, triisopropanolamine, N, N, N', N” , N” -pentakis (2-hydroxypropyl) diethylenetriamine, and any combinations thereof. According to another embodiment of the present disclosure, examples of suitable crosslinkers include diethanol amine, monoethanol amine, triethanol amine, mono-, di-or tri (isopropanol) amine, glycerine, trimethylol propane, pentaerythritol, and the like.
Chain extenders and crosslinkers are suitably used in small amounts, as hardness  increases as the amount of either of these materials increases. From 0 to 25 parts by weight of a chain extender is suitably used per 100 parts by weight of the second polyol component (B) . A preferred amount is from 1 to 20, or from 0.1 to 10, or from 1 to 6, or from 1 to 15 parts per 100 parts by weight of the second polyol component (B) . From 0 to 10 parts by weight of a crosslinker is suitably used per 100 parts by weight of the second polyol component (B) . A preferred amount is from 0 to 5 parts per 100 parts by weight of the second polyol component (B) .
A filler may be present in the polyurethane composition. Fillers are mainly included to reduce cost. Particulate rubbery materials are especially useful fillers. Such a filler may constitute from 1 to 50%or more of the weight of the polyurethane composition.
Suitable blowing agents include water, air, nitrogen, argon, carbon dioxide, hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons and other volatile chemicals with low boiling points of from -30 ℃ to 75℃.
A surfactant may be present in the reaction mixture. It can be used, for example, if a cellular tire filling is desired, as the surfactant stabilizes a foaming reaction mixture until it can harden to form a cellular polymer. A surfactant also may be useful to wet filler particles and thereby help disperse them into the reactive composition and the elastomer. Silicone surfactants are widely used for this purpose and can be used here as well. The amount of surfactant used will in general be between 0.02 and 1 part by weight per 100 parts by weight polyol component.
According to a preferable embodiment of the present disclosure, one or more foam stabilizer, such as silicone-based foam stabilizers; anti-foam agents, such as silicone-based anti-foam agents; functional additives, such as anti-static electricity agents, flame-retardant agents, slippery resistance agents, and etc. may be further included in the polyurethane composition.
According to a preferable embodiment of the present disclosure, the polyurethane composition comprises one or more antioxidants. Preferably, the antioxidant is preferably included in component B but not in component A. According to a preferable embodiment of the present disclosure, the antioxidant is a substituted phenol type antioxidant, and is more preferably of sterically hindered phenol type antioxidant. According to a preferable embodiment of the present disclosure, the amount of the antioxidant is from 0.3 to 2%by  weight, such as from 0.5 to 1%by weight, based on the total weight of the component B.
According to a preferable embodiment of the present disclosure, the polyurethane composition comprises one or more UV absorbers. The UV absorber is preferably included in component B but not in component A. According to a preferable embodiment of the present disclosure, the absorber is a benzotriaole type UV absorber, and is more preferably 2- (2H-benzotriazo-2-yl) -6-dodecyl-4-methyl-phennol. According to a more preferable embodiment of the present disclosure, the amount of the UV absorber is from 0.5 to 2.5%by weight, such as from 1.0 to 1.8%by weight, based on the total weight of the component B.
According to a preferable embodiment of the present disclosure, the polyurethane composition comprises one or more light stabilizers. The light stabilizer is preferably included in component B but not in component A. According to a preferable embodiment of the present disclosure, the light stabilizer is a hindered aliphatic light stabilizer (HALS) , preferably a substituted alicyclic-amine HALS, and more preferably and bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate. According to a more preferable embodiment of the present disclosure, the amount of the light stabilizer is from 0.5 to 2.5%by weight, such as from 1.0 to 1.8%by weight, based on the total weight of the component B.
According to a preferable embodiment of the present disclosure, the polyurethane composition comprises at least one of colorant, pigment and dye. The colorant, pigment and dye can be included in either component A or component B, and are preferably included in component B but not in component A. According to a preferable embodiment of the present disclosure, the colorant, pigment and dye include carbon black, titanium dioxide or isoindolinon. According to a preferable embodiment of the present disclosure, the amount of each of the colorant, pigment and dye is from 0.3 to 3.0%by weight, based on the total weight of the component B. For example, the colorant, pigment or dye can be added as a dispersion in polyol, such as a dispersion in the polyol component.
According to another embodiment of the present application, the polyurethane composition of the present disclosure can be used for preparing foamed polyurethane product, or polyurethane foam. For example, the polyurethane foam is applicable to prepare a wide range of tires that can be used in many applications. The tires can be, for example, for a bicycle, a cart such as a golf cart or shopping cart, a motorized or unmotorized wheelchair, an automobile or truck, any other type of transportation vehicles including an aircraft, as well as  various types of agriculture, industrial and construction equipment. Large tires that have an internal volume of 0.1 cubic meter or more are of particular interest.
According to various embodiments of the present disclosure, the polyurethane foam has a density of at least 100 kg/m 3, such as from 100 to 950 kg/m 3, from 200 to 850 kg/m 3, from 300 to 800 kg/m 3, from 400 to 750 kg/m 3, from 500 to 700 kg/m 3, from 550 to 650 kg/m 3, or from 580 to 620 kg/m 3, or about 600 kg/m 3.
According a preferable embodiment of the present disclosure, the polyurethane composition is substantially free of water or moisture intentionally added therein. For example, “free of water” or “water free” means that the mixture of all the raw materials used for preparing the polyurethane composition comprise less than 3%by weight, preferably less than 2%by weight, preferably less than 1%by weight, more preferably less than 0.5%by weight, more preferably less than 0.2%by weight, more preferably less than 0.1%by weight, more preferably less than 100 ppm by weight, more preferably less than 50 ppm by weight, more preferably less than 10 ppm by weight, more preferably less than 1ppm by weight of water, based on the total weight of the mixture of raw materials. According to a preferable embodiment of the present disclosure, the polyurethane material is prepared under an isocyanate index between 90 and 120, wherein index 100 means the molar ratio between isocyanate group and isocyanate-reactive groups is 1.00.
Upon reacting, the mixture takes the shape of the mold or adheres to the substrate to produce polyurethane material which is then allowed to cure, either partially or fully. Suitable conditions for promoting the curing of the polyurethane polymer include a temperature of from about 20℃ to about 150℃. In some embodiments, the curing is performed at a temperature of from about 30℃ to about 120℃, such as from 80 ℃ to 100 ℃. In other embodiments, the curing is performed at a temperature of from about 35 ℃ to about 110℃. In various embodiments, the temperature for curing may be selected at least in part based on the time duration required for the polyurethane polymer to gel and/or cure at that temperature. Cure time will also depend on other factors, including, for example, the particular components (e.g., catalysts and quantities thereof) , and the size and shape of the article being manufactured, and can be from 0.1 to 60 hours, such as from 0.5 to 24 hours.
According to an embodiment of the present disclosure, it is surprisingly found that the introduction of repeating units derived from linear unsaturated diols with double bond into the  backbone of polyurethane material (especially, polyurethane foams) can bring about notable technical progresses over a polyurethane material prepared by using linear saturated polyols (e.g. 1, 4-butanediol, BDO) , wherein said technical progresses may include one or more of improved cost competitiveness, good processibility, improved tear-resistance and heat resistance, hence the polyurethane foams prepared in the present disclosure is suitable for many applications like footwear, tires, seals, cushioning parts, bumpers, etc. According to a preferable embodiment of the present disclosure, the polyurethane foam prepared by using 1-20 wt% (based on the total amount of component A) of diol represented by Formula I can achieve an improvement of at least 10%in the tear strength and at least 30%in the heat resistance (measured by delta storage modulus at low-high temperature) when compared with polyurethane prepared by using linear saturated polyols. Besides, the technology of the present disclosure will not result in significantly increased cost.
The description hereinabove is intended to be general and is not intended to be inclusive of all possible embodiments of the invention. Similarly, the examples hereinbelow are provided to be illustrative only and are not intended to define or limit the invention in any way. Those skilled in the art will be fully aware that other embodiments, within the scope of the claims, will be apparent from consideration of the specification and/or practice of the invention as disclosed herein. Such other embodiments may include selections of specific components and constituents and proportions thereof; mixing and reaction conditions, vessels, deployment apparatuses, and protocols; performance and selectivity; identification of products and by-products; subsequent processing and use thereof; and the like; and that those skilled in the art will recognize that such may be varied within the scope of the claims appended hereto.
EXAMPLES
Some embodiments of the invention will now be described in the following Examples. However, the scope of the present disclosure is not, of course, limited to the formulations set forth in these examples. Rather, the Examples are merely inventive of the disclosure.
The information of the raw materials used in the examples is listed in the following table 1:
Table 1. Raw materials used in the examples
Figure PCTCN2020108790-appb-000002
Figure PCTCN2020108790-appb-000003
In the following Inventive Examples 1-5 and Comparative Examples 1-4, polyurethane foam samples were synthesized and characterized.
Characterization Technologies for the Inventive Examples 1-5 and Comparative  Examples 1-4:
Tear strength were determined on a Gotech AI-7000S1 universal testing machine according to the testing method DIN 53543, and the general industrial requirement on tear strength is higher than 180 N/cm.
The storage modulus was characterized via Dynamic mechanical analysis (DMA) , wherein DMA was performed on a TA RSA G2 analyzer under strain-control mode at a frequency of 1 Hz and 0.1%strain, in a temperature range from -80 ℃ to 200 ℃ with a ramp rate of 3 ℃/min.
Differential scanning calorimeter (DSC) was performed on a TA Q1500 analyzer with a cooling speed of 10 ℃/min and heating speed of 20 ℃/min under N 2 atmosphere.
Table 2. Formulations of polyurethane foams prepared in Comparative Examples (Com. Ex.) 1-3 and Inventive Example 1 (Inv. Ex. ) (PTMEG-based) .
Component Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Inv. Ex. 1
PTMEG2000 57 57 57 57
DNC 701 30 30 30 30
BDO 11.9
BEDO 8.9 11.9
GEDO 11.9 3
Niax A-1 0.05 0.05 0.05 0.05
B8408 0.1 0.1 0.1 0.1
Dabco 33s 1 1 1 1
Fomrez UL 38 0.02 0.02 0.02 0.02
Water 0.3 0.3 0.3 0.3
Total 100.37 100.37 100.37 100.37
Average OHV 217.11 170.10 207.78 220.48
Iso/OH ratio 1 1 1 1
NE569 85.42 66.92 81.74 86.74
Table 3. Formulations of polyurethane foams prepared in Comparative Example (Com. Ex. ) 4 and Inventive Examples (Inv. Ex. ) 2-5 (CP6001-based) .
Components Com. Ex. 4 Inv. Ex. 2 Inv. Ex. 3 Inv. Ex. 4 Inv. Ex. 5
CP6001 57 57 57 57 57
DNC 701 30 30 30 30 30
BDO 11.9 8.93 5.95 2.98 0
BEDO 0 2.98 5.95 8.93 11.9
Niax A-1 0.05 0.05 0.05 0.05 0.05
B8408 0.1 0.1 0.1 0.1 0.1
Dabco 33s 1 1 1 1 1
Fomrez UL 38 0.02 0.02 0.02 0.02 0.02
Water 0.3 0.3 0.3 0.3 0.3
Total 100.37 100.37 100.37 100.37 100.37
Average OHV 201.19 202.03 202.87 203.72 204.56
Iso/OH ratio 1 1 1 1 1
NE569 79.15 79.48 79.81 80.15 80.48
In the Inventive Examples 1-5 and Comparative Examples 1-4, the polyol components were made by mixing the polyols, catalysts, blowing agents and silicon compounds as shown in Table 2 &3. Then the polyol components were mixed with the isocyanate prepolymer (NE569) at room temperature with a high speed stirrer (at a stirring rate of 2500 RPM) for 7 seconds. The mixture was poured into a metal mold (which is lined with PTFE film to aid the demolding at a later stage) at 50 ℃ and then the mold was sealed immediately. The reaction between the polyol components and prepolymer occurred instantly after the mixing, the reaction content was cured at 50℃ to produce a foam sample. The mold was opened and the foam sample was demolded. The foam samples were stored overnight at room temperature, subject to another post-curing treatment in an oven at 50℃ for 24 hours, and then characterized.
All the characterization results were summarized in Table 4.
Table 4 Characterization results of Comparative Examples 1-4 and Inventive Examples 1-5
Categories of Diols Tear Strength (N)  G’ (MPa, 25 ℃)  G’ (MPa, 160 ℃)  Delta G’ (MPa)
Com. Ex. 1 BDO 160 3.71 0.91 2.8
Com. Ex. 2 GEDO Fail to demold Fail to demold Fail to demold Fail to demold
Com. Ex. 3 BEDO+GEDO 150 3.62 1.01 2.61
Inv. Ex. 1 BEDO 220 3.72 1.76 1.96
Com. Ex. 4 BDO 205 4.41 1.45 2.96
Inv. Ex. 2 BEDO: BDO 25: 75 207 2.70 1.08 1.62
Inv. Ex. 3 BEDO: BDO 50: 50 210 2.71 1.07 1.64
Inv. Ex. 4 BEDO: BDO 75: 25 264 3.78 1.04 2.74
Inv. Ex. 5 BEDO 220 3.27 1.42 1.85
As shown in Table 4, the inventive examples which comprise residual moieties of unsaturated linear diol in the polyurethane backbone exhibit significant improvement in the tear strength and thermal resistance over the polyurethane prepared by using saturated linear diols. Comparative Examples 2 and 3 illustrate that the attachment of ethylenically unsaturated side chains to the polyurethane backbone will substantially deteriorate the tear strength and thermal resistance. Furthermore, the comparison among results of inventive examples 2-5 also show that the highest tear strength and thermal resistance can be achieved at an optimized ratio of unsaturated diol and saturated diol.

Claims (11)

  1. A polyurethane composition, comprising
    (A) an isocyanate-reactive component comprising at least one unsaturated linear diol represented by Formula I,
    HO-R 1-C (R 2) =C (R 3) -R 4-OH  Formula I
    wherein each of R 1 and R 4 is independently selected from the group consisting of covalent bond, C 1 to C 6 alkylene group, C 2-C 6 alkenylene group, C 6-C 12 cycloalkylene group, and C 6-C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1-C 6 alkyl group;
    and at least one second polyol other than the unsaturated linear diol; and
    (B) an isocyanate component comprising at least one first isocyanate compound comprising at least two isocyanate groups,
    wherein the polyurethane composition does not comprise an unsaturated compound which will introduce an ethylenically unsaturated side chain into a polyurethane backbone formed by reacting the (A) isocyanate-reactive component with the (B) isocyanate component.
  2. The polyurethane composition according to claim 1, wherein the unsaturated linear diol represented by Formula I is selected from a group consisting of 2-butene-1, 4-diol, 2-pentene-1, 5-diol, 2-hexene-1, 6-diol, 3-hexene-1, 6-diol, 2, 4-hexadiene-1, 6-diol, 2-heptene-1, 7-diol, 3-heptene-1, 7-diol, 2, 4-heptadiene-1, 7-diol, 2, 5-heptadiene-1, 7-diol, 2-octene-1, 8-diol, 3-octene-1, 8-diol, 4-octene-1, 8-diol, 2, 4-octadiene-1, 8-diol, 2, 5-octadiene-1, 8-diol, 2, 6-octadiene-1, 8-diol, 1, 2-bis (4-hydroxylcyclohexyl) ethylene, 1, 2-bis (3-hydroxylcyclohexyl) ethylene, 1, 2-bis (4-methylolcyclohexyl) ethylene, 1, 2-bis (3-methylolcyclohexyl) ethylene, 1, 2-bis (4-hydroxyl-phenyl) ethylene, 1, 2-bis (4-methylol-phenyl) ethylene, 1, 2-bis (4-hydroxyl-benzyl) -ethylene, 1, 2-bis (4-methylol-benzyl) ethylene, and any combinations thereof.
  3. The polyurethane composition according to claim 1, wherein the content of the unsaturated linear diol represented by Formula I is from 1%to 20%by weight, based on the total weight of the isocyanate-reactive component (A) .
  4. The polyurethane composition according to claim 1, wherein the second polyol is selected from the group consisting of C 2-C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6-C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7-C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polyether polyol having a molecular weight from 100 to 12,000 and an average hydroxyl functionality of 1.1 to 8.0, a polymer polyol having a core phase and a shell phase based on polyether/polyester polyol, and any combinations thereof.
  5. The polyurethane composition according to claim 4, wherein the second polyol optionally includes at least one saturated linear C 2-C 12 aliphatic diol, and the weight ratio between the saturated linear C 2-C 12 aliphatic diol and the unsaturated linear diol is from 0: 20 to 10: 1.
  6. The polyurethane composition according to claim 5, wherein the weight ratio between the saturated linear C 2-C 12 aliphatic diol and the unsaturated linear diol is from 1: 1 to 1: 3.
  7. The polyurethane composition according to claim 1, wherein the first isocyanate compound is selected from the group consisting of C 4-C 12 aliphatic isocyanate comprising at least two isocyanate groups, C 6-C 15 cycloaliphatic or aromatic isocyanate comprising at least two isocyanate groups, C 7-C 15 araliphatic isocyanate comprising at least two isocyanate groups, a prepolymer comprising at least two isocyanate groups, and any combinations thereof.
  8. The polyurethane composition according to claim 1, wherein the polyurethane composition further comprises at least one additive selected from the group consisting of chain extender, crosslinker, blowing agent, foam stabilizer, tackifier, plasticizer, rheology modifier, antioxidant, UV-absorbent, light-stabilizer, catalyst, cocatalyst, filler, colorant, pigment, water scavenger, surfactant, solvent, diluent, flame retardant, slippery-resistance agent, antistatic agent, preservative, biocide and any combinations thereof.
  9. A polyurethane material formed by using the polyurethane composition according to any of claim 1 to 8, wherein the polyurethane material comprises polyurethane main chains derived from the reaction of
    (A) an isocyanate-reactive component comprising at least one unsaturated linear diol represented by Formula I,
    HO-R 1-C (R 2) =C (R 3) -R 4-OH  Formula I
    wherein each of R 1 and R 4 is independently selected from the group consisting of direct bond, C 1 to C 6 alkylene group, C 2-C 6 alkenylene group, C 6-C 12 cycloalkylene group, and C 6-C 12 arylene group; and each of R 2 and R 3 is independently selected from the group consisting of hydrogen and C 1-C 6 alkyl group;
    and at least one second polyol other than the unsaturated linear diol; and
    (B) an isocyanate component comprising at least one first isocyanate compound comprising at least two isocyanate groups,
    wherein repeating units derived from the unsaturated linear diol constitute at least part of the polyurethane main chains, and none of the polyurethane backbone in the polyurethane material comprises an ethylenically unsaturated side chain.
  10. The polyurethane material according to claim 9, wherein the polyurethane material is a microcellular polyurethane foam.
  11. A method for preparing the polyurethane material according to claim 9, comprising a step of reacting the isocyanate-reactive component (A) with the (B) isocyanate component to form the polyurethane material.
PCT/CN2020/108790 2020-08-13 2020-08-13 Polyurethane compositions, foams prepared with same and preparation methods thereof WO2022032552A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093844A1 (en) * 2008-02-25 2009-08-26 Corning Cable Systems LLC Sealant gel for a telecommunication enclosure
CN109354668A (en) * 2018-09-11 2019-02-19 东莞市吉鑫高分子科技有限公司 A kind of high fire-retardance thermoplastic polyurethane elastomer and preparation method thereof
WO2020142887A1 (en) * 2019-01-08 2020-07-16 Dow Global Technologies Llc Rigid polyisocyanurate and polyurethane foams and methods for preparing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093844A1 (en) * 2008-02-25 2009-08-26 Corning Cable Systems LLC Sealant gel for a telecommunication enclosure
CN109354668A (en) * 2018-09-11 2019-02-19 东莞市吉鑫高分子科技有限公司 A kind of high fire-retardance thermoplastic polyurethane elastomer and preparation method thereof
WO2020142887A1 (en) * 2019-01-08 2020-07-16 Dow Global Technologies Llc Rigid polyisocyanurate and polyurethane foams and methods for preparing the same

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