CN101486788A - Low density high hardness polyurethane micropore elastomer and preparation thereof - Google Patents
Low density high hardness polyurethane micropore elastomer and preparation thereofDownload PDFInfo
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- CN101486788A CN101486788ACNA2008101917239ACN200810191723ACN101486788ACN 101486788 ACN101486788 ACN 101486788ACN A2008101917239 ACNA2008101917239 ACN A2008101917239ACN 200810191723 ACN200810191723 ACN 200810191723ACN 101486788 ACN101486788 ACN 101486788A
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Abstract
Description
Technical field
The invention belongs to macromolecular material and make field, particularly a kind of low density high hardness polyurethane micropore elastomer and preparation method who is used to make sole.
Background technology
Urethane is a kind of novel high polymer material of excellent performance, two-fold advantage with plastics and rubber, be the fifth-largest plastics after polyethylene, polyvinyl chloride, polypropylene, polystyrene, being widely used in every field, especially shoe-making industries such as synthon, shoe-making industry, automotive industry, building materials has become an important consumption industry of polyurethane product.Because the material for sole of shoe of microporous polyurethane elastomer production has advantages such as light weight, anti-skidding, good springiness, intensity height, wear-resisting, oil resistant, it has obtained development at full speed in recent ten years.China is a shoemaking big country, and the output of its footwear accounts for 50% of Gross World Product; But use polyurethane elastomer only to account for about 6% of total material for sole of shoe as material for sole of shoe, the occupation rate of contrast American-European countries more than 25%, development is still very slowly.Therefore as seen, polyurethane elastomer material market at home has huge application potential.
Compare with traditional material for sole of shoe such as rubber, EVA (ethylene/vinyl acetate multipolymer) etc., an inferior position of microporous polyurethane elastomer is that cost is higher.In order to increase the competitive power of polyurethane elastomer in material for sole of shoe, be a kind of important approach keeping reducing Sole moulding density under the constant prerequisite of important physical index.But when using conventional urethane raw material production sole, density is crossed a series of problems such as can causing the decline of finished product hardness, sole shrinkage strain, the easy decortication in surface of hanging down.Make that material for sole of shoe has higher hardness under the low density, generally must improve the consumption of isocyanic ester in the polyurethane elastomer prescription, but, improve the cost of material for sole of shoe so on the contrary because the price of isocyanic ester is relatively costly.
A few thing attempts going to reduce the compact density of polyurethane sole materials, regrettably fails to make a breakthrough.CN1961016A discloses a kind of low-density polyurethane foam materials and preparation method thereof as patent, and its purposes in material for sole of shoe.Though can obtain density by this method is 0.12g/cm3To 0.30g/cm3Polyurethane foamed material, but it is mainly used in intermediate sole in sole, be not suitable as the mould material of sole outer bottom.And in raw material, used the butyleneglycol of a large amount of high prices, though the interpolation of butyleneglycol can work to improve mechanical property at the bottom of the polyurethane shoe, simultaneously also bigger raising the cost of product.Patent CN1590427A discloses the high foaming of a kind of low density polyurethane resin for shoes prescription, adopt this resin formula can reduce sole density effectively, but products obtained therefrom shrinks distortion easily, hardness can not satisfy the service requirements of some sole, and the pneumatogen M705b that uses in the prescription is unfavorable for environmental protection requirement.
Summary of the invention
The object of the present invention is to provide a kind of low density high hardness polyurethane micropore elastomer and preparation method thereof, solution polyurethane elastomer material for sole of shoe under case of low density case still can keep the technical barrier of high rigidity.
Purpose of the present invention can realize by the pre-polymerization method reaction by polyol component (A component) and isocyanate component (B component), wherein:
(1) A component, in parts by weight:
Polyester polyol A1 25～65
Polyester polyol A2 5～30
Polyester polyol A3 5～70
Dibasic alcohol chainextender 5～20
Linking agent 0.2～1
Tertiary amine or organo-metallic catalyst 0.5～3
Organosilicon foam stabilizer 0.2～1.5
Water 0.5～3
(2) B component, in parts by weight:
Polyisocyanates 65～75
Polyester polyol B1 15～30
Polyether glycol 0～15
Side reaction hold back agent 20～200ppm
Polyester polyol A1 be one or more and hexanodioic acid in ethylene glycol or the Diethylene Glycol by the transesterification reaction gained, be preferably 2 functionality, number-average molecular weight and be 1500～2500 polyester polyol.
Polyester polyol A2 be one or more and hexanodioic acid in Diethylene Glycol or the TriMethylolPropane(TMP) by the transesterification reaction gained, be preferably 2 functionality, number-average molecular weight and be 1500～2000 polyester polyol.
Polyester polyol A3 is a polymer polyester polyol, usually prepare by radical polymerization in polyester polyol by vinyl monomers such as vinylbenzene, vinyl cyanide, acrylate and/or acrylamides, be preferably number-average molecular weight and be 2000～2500, viscosity is that 500～6000mPa.S (under 60 ℃), solid content are the styrene-grafted polymer polyester polyol of 15～35 quality %.
Chainextender is one or more small molecules dibasic alcohol, can be ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, glycol ether, dipropylene glycol, neopentyl glycol, 1, the mixture of one or more in the 6-hexylene glycol.
Linking agent is low-molecular-weight organic matters such as TriMethylolPropane(TMP), glycerol, trolamine, diethanolamine.
Catalyzer is tertiary amines and tin type organic, is preferably one or more mixtures in triethylene diamine, dibutyl tin laurate, the tetramethyl-diethylenetriamine.
Foam stabilizer is the organic silicon modified by polyether tensio-active agent, is preferably a kind of among DC193, DC3042, the DC3043 (U.S., air products company produces, and is commercially available).
Polyisocyanates is 4,4 '-diphenylmethanediisocyanate, carbodiimide modification 4,4 '-one or more mixture in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate, be preferably 4,4 '-diphenylmethanediisocyanate or carbodiimide modification 4,4 '-a kind of in the diphenylmethanediisocyanate or the mixture of the two.
Polyester polyol B1 be a kind of and ethylene glycol in hexanodioic acid or the terephthalic acid by the transesterification reaction gained, be preferably 2～3 functionality, number-average molecular weight and be 1800～2200 polyester polyol.
Polyether glycol can comprise in polyoxytrimethylene polyvalent alcohol, polyoxytrimethylene ethylene oxide copolyether polyvalent alcohol and the polytetrahydrofuran polyvalent alcohol one or more, is preferably the polyoxytrimethylene ethylene oxide copolyether polyvalent alcohol of 2～4 functionality, number-average molecular weight 500～6000.
The side reaction hold back agent can be preferably phosphoric acid for mineral acid, organic acid or Benzoyl chloride etc.
The present invention also provides a kind of preparation method of low density high hardness polyurethane micropore elastomer:
(1) A component preparation: in 20～50 ℃ reactor, polyester polyol A1, polyester polyol A2, polyester polyol A3, dibasic alcohol chainextender, linking agent, tertiary amine or organo-metallic catalyst, organosilicon foam stabilizer and water are carried out thorough mixing, discharging after 2～4 hours, sealing is preserved, and promptly gets the A component;
(2) B component preparation: in 60～80 ℃ reactor, diphenylmethanediisocyanate, polyester polyol B1, polyether glycol, side reaction hold back agent were reacted 2～3 hours, the vacuum removal bubble is cooled to 40～45 ℃, discharging, sealing is preserved, and promptly gets the B component;
(3) preparation of microporous polyurethane elastomer: the temperature of control A component and B component is in 40～45 ℃ of scopes, adjust the consumption of A component and B component, make the A component reactive hydrogen mole number and B component-ratio of the mole number of NCO is 100: 100, with two component thorough mixing, inject mould reaction moulding, the demoulding, slaking obtains goods.
The invention has the advantages that:
(1) product still has higher hardness under low density.
(2) complete processing is simple, and cost reduces.
(2) with water be whipping agent, environmental friendliness.
Embodiment
Preparation technology's unanimity of following 6 embodiment that exemplify, the proportioning raw materials of A and B component changes.
Proportionally weighing configuration A component material double centner drops in the reactor, and in the discharging after 2～4 hours of 20～50 ℃ of following thorough mixing, sealing is preserved with standby; Proportionally weighing configuration B component double centner places reactor, reacts 2～3 hours under 60～80 ℃ of conditions, and the vacuum removal bubble is cooled to 40～45 ℃, sampling analysis free-NCO content, and sealing is preserved with standby; The temperature of control A component and B component is 40～45 ℃, adjusts the consumption of A component and B component, the reactive hydrogen mole number that makes the A component and B component-ratio of the mole number of NCO is 100: 100, with two component thorough mixing, inject mould reaction moulding, the demoulding, slaking obtains goods.
Raw materials used being specially among the embodiment:
Polyester polyol A1 is that ethylene glycol, Diethylene Glycol and hexanodioic acid pass through the transesterification reaction gained, and wherein the mass ratio of ethylene glycol and Diethylene Glycol is 0.583:1, and the number-average molecular weight of polyester polyol is 1500;
Polyester polyol A2 is that Diethylene Glycol, TriMethylolPropane(TMP) and hexanodioic acid pass through the transesterification reaction gained, and wherein the mass ratio of Diethylene Glycol and TriMethylolPropane(TMP) is 11.307:1, and the number-average molecular weight of polyester polyol is 1850;
Polyester polyol A3 is that styrene monomer prepares gained by radical polymerization in polyester polyol, and polymer content is 25 quality %, and 60 ℃ of following viscosity are 1800mPa.S;
Polyester polyol B1 is that ethylene glycol and hexanodioic acid, terephthalic acid pass through the transesterification reaction gained, and wherein the mass ratio of hexanodioic acid and terephthalic acid is 7.992:1, and the number-average molecular weight of polyester polyol is 2040;
(above raw material is self-control)
Polyether glycol is the polyether glycol product available from Tianjin the 3rd petroleum chemical plant, and the trade mark is ZS-T280, and molecular weight is 4000;
The organosilicon foam stabilizer is that the trade mark is DC-3043 available from U.S. aerification chemical product company product.
The raw materials used concrete ratio of A component and B component sees the following form among the embodiment:
Result to each group embodiment narrates respectively below:
Embodiment 1: product molding density is 0.318g/cm3, hardness Shao Shi A is 71, smooth in appearance is smooth, shrinkage strain do not occur, but material flowability is relatively poor, and the goods part is easy to generate defective;
Embodiment 2: product molding density is 0.321g/cm3, hardness Shao Shi A is 70, smooth in appearance is smooth, shrinkage strain do not occur;
Embodiment 3: product molding density is 0.309g/cm3, hardness Shao Shi A is 68, smooth in appearance is smooth, shrinkage strain do not occur;
Embodiment 4: product molding density is 0.325g/cm3, hardness Shao Shi A is 72, shrinkage strain do not occur, but outward appearance smooth finish is relatively poor;
Embodiment 5: product molding density is 0.314g/cm3, hardness Shao Shi A is 69, smooth in appearance is smooth, but shrinkage strain occurs easily;
Embodiment 6: product molding density is 0.323g/cm3, hardness Shao Shi A is 68, outward appearance smooth finish is relatively poor, and occurs shrinkage strain easily.
Claims (10)
1, a kind of low density high hardness polyurethane micropore elastomer is characterized in that being generated by A component and B component reaction, wherein:
(1) A component, in parts by weight:
Polyester polyol A1 25～65
Polyester polyol A2 5～30
Polyester polyol A3 5～70
Dibasic alcohol chainextender 5～20
Linking agent 0.2～1
Tertiary amine or organo-metallic catalyst 0.5～3
Organosilicon foam stabilizer 0.2～1.5
Water 0.5～3
Described polyester polyol A1 is that one or more and the hexanodioic acid in ethylene glycol or the Diethylene Glycol is 1500～2500 polyester polyol by transesterification reaction gained, number-average molecular weight; Described polyester polyol A2 is that one or more and the hexanodioic acid in Diethylene Glycol or the TriMethylolPropane(TMP) is 1500～2000 polyester polyol by transesterification reaction gained, number-average molecular weight; Described dibasic alcohol chainextender is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, glycol ether, dipropylene glycol, neopentyl glycol, 1, the mixture of one or more in 6-hexylene glycol, the cyclohexanedimethanol; Described linking agent is a kind of in TriMethylolPropane(TMP), glycerine, trolamine, the diethanolamine; Described organosilicon foam stabilizer is the organic silicon modified by polyether tensio-active agent; Described tertiary amine or organo-metallic catalyst are one or more mixtures in dibutyl tin laurate, triethylene diamine, the tetramethyl-diethylenetriamine;
(2) B component, in parts by weight:
Polyisocyanates 65～75
Polyester polyol B1 15～30
Polyether glycol 0～15
Side reaction hold back agent 20～200ppm
Described polyisocyanates is 4,4 '-diphenylmethanediisocyanate, carbodiimide modification 4,4 '-one or more mixture in diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate; Described polyester polyol B1 is that a kind of and ethylene glycol in hexanodioic acid or the terephthalic acid is 1800～2200 polyester polyol by transesterification reaction gained, number-average molecular weight; Described side reaction hold back agent is mineral acid, organic acid or Benzoyl chloride.
2, microporous polyurethane elastomer according to claim 1 is characterized in that described polyester polyol A3 is 2000～2500 polyester polyol for the number-average molecular weight that is prepared by radical polymerization by vinyl monomer in polyester polyol;
3, microporous polyurethane elastomer according to claim 2 is characterized in that described vinyl monomer is a kind of or its mixture of vinylbenzene, vinyl cyanide, acrylate, acrylamide.
4, microporous polyurethane elastomer according to claim 2 is characterized in that the viscosity of polyester polyol A3 under 60 ℃ is 500～6000mPa.S.
5, microporous polyurethane elastomer according to claim 2, it is characterized in that being that the quality percentage composition of the monomeric unit of vinyl monomer formation among the described polyester polyol A3 is 5～50% of polyester polyol A3, be preferably 10～40%, be preferably 15～35% especially.
6, microporous polyurethane elastomer according to claim 1, the hardness that it is characterized in that described microporous polyurethane elastomer are 50～85 Shao Shi A.
7, microporous polyurethane elastomer according to claim 1, the compact density that it is characterized in that described microporous polyurethane elastomer is 0.2～0.50g/cm3
8, microporous polyurethane elastomer according to claim 1, it is characterized in that polyisocyanates be 4,4 '-diphenylmethanediisocyanate or carbodiimide modification 4,4 '-a kind of in the diphenylmethanediisocyanate or the mixture of the two.
9, the preparation method of each described microporous polyurethane elastomer of claim 1～8 is characterized in that:
(1) A component preparation: in 20～50 ℃ reactor, polyester polyol A1, polyester polyol A2, polyester polyol A3, dibasic alcohol chainextender, linking agent, tertiary amine or organo-metallic catalyst, organosilicon foam stabilizer and water are carried out thorough mixing, discharging after 2～4 hours, sealing is preserved, and promptly gets the A component;
(2) B component preparation: in 60～80 ℃ reactor, diphenylmethanediisocyanate, polyester polyol B1, polyether glycol, side reaction hold back agent were reacted 2～3 hours, the vacuum removal bubble is cooled to 40～45 ℃, discharging, sealing is preserved, and promptly gets the B component;
(3) preparation of microporous polyurethane elastomer: the temperature of control A component and B component is in 40～45 ℃ of scopes, adjust the consumption of A component and B component, make the A component reactive hydrogen mole number and B component-ratio of the mole number of NCO is 100: 100, with two component thorough mixing, inject mould reaction moulding, the demoulding, slaking obtains goods.
10, the application of the described microporous polyurethane elastomer of claim 1 in material for sole of shoe is produced.
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