CN104231220A - Anti-yellowing transparent TPU (thermoplastic polyurethane) elastomer and preparation method thereof - Google Patents

Anti-yellowing transparent TPU (thermoplastic polyurethane) elastomer and preparation method thereof Download PDF

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Publication number
CN104231220A
CN104231220A CN201410479982.7A CN201410479982A CN104231220A CN 104231220 A CN104231220 A CN 104231220A CN 201410479982 A CN201410479982 A CN 201410479982A CN 104231220 A CN104231220 A CN 104231220A
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Prior art keywords
elastomer
preparation
polyurethane
polyurethane elastomer
butyleneglycol
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CN201410479982.7A
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Chinese (zh)
Inventor
王一良
何健雄
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Suzhou Xionglin New Material Technology Co Ltd
Dongguan City Ji Xin Macromolecule Science And Technology Ltd
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Suzhou Xionglin New Material Technology Co Ltd
Dongguan City Ji Xin Macromolecule Science And Technology Ltd
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Priority to CN201410479982.7A priority Critical patent/CN104231220A/en
Publication of CN104231220A publication Critical patent/CN104231220A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472Five-membered rings
    • C08K5/3475Five-membered rings condensed with carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3

Abstract

Anti-yellowing transparent TPU (thermoplastic polyurethane) elastomer comprises components in percentage by mass as follows: 20%-35% of polyethylene glycol, 5%-25% of polyphosphazene, 10%-25% of toluene diisocynate, 10%-30% of butanediol, 1%-5% of phosphite without a benzene ring, 1%-5% of an ultraviolet light absorber and 1%-5% of hydrosilicone oil. The TPU elastomer can be prepared with the method comprising the following steps: (1) dehydration is performed on polyethylene glycol; (2) dehydration is performed on butanediol, and toluene diisocynate is molten; (3) a mixture obtained in step (1) and butanediol after dehydration are mixed and heated; and (4) the molten toluene diisocynate in step (2) and a mixture obtained in the step (3) are mixed with other components, then a mixture is heated, stirred and cured, and a product is subjected to granulation and injection molding to obtain the TPU elastomer. The elastomer is transparent and has better anti-yellowing performance, larger tensile elongation and higher tensile strength.

Description

A kind of high Yellowing-resistant transparent Polyurethane Thermoplastic Elastomer and preparation method thereof
Technical field
The present invention relates to a kind of polyurethane elastomer and preparation method thereof, particularly relate to a kind of high Yellowing-resistant transparent Polyurethane Thermoplastic Elastomer and preparation method thereof.
Background technology
Thermoplastic polyurethane (Thermoplastic polyyrethane, TPU) be a kind of novel organic polymer synthetic materials, belong to compound, English trade(brand)name: Flexible polyurethane, that a kind of properties is excellent, rubber rubber can be replaced, soft polyvinyl chloride material PVC.Such as it has excellent physicals, such as wear resistance, and screen resilience is all better than conventional polyurethanes, PVC, and ageing resistance is better than rubber, can be described as the optimal material of alternative PVC and PU, is called novel polymer material in the world.
Thermoplastic polyurethane has many uses general, such as, can be used for footwear as sports shoes Logo, sports shoes air cushion, climbing boot, snowshoe, golf shoes, ice skate, fabric and laminated material inside, become clothing as snow clothing, raincoat, wind coat, cold-proof jacket, field jacket, paper diaper, physiological brief, in fabric matrix material (Waterproof Breathable), pharmaceutical is as operating coat, cap, footwear, hospital's mattress, ice bag, bandage, plasma bags, surgery wrapping cloth, mouth mask, Deng fabric and material inside, operation table air bag, national defence articles for use are as fuel tanker, and overlay film sealed up for safekeeping by weapon, camp window, military water bag, vestlifejacket, fills fabric and the fabric inside of motorboat etc., air bag, and sporting goods is as football surface and inner bag, air mattress, lister bag, ski glove (waterproof bag), submarine armor, snow clothing, swimsuit, ski, trade mark, air bag, sweater, the fabrics such as weight reducing clothing and inside material, industrial goods is as loudspeaker drum paper rubber edge, water-proof strip, sound insulation material, fire proofing wood, fire-protection suit, bunker clothing, the fabrics such as asbeston and inside matrix material, electric wire jacket material, other purposes are as mobile phone key, plastic inflatable toy, sheet, tablecloth, shower curtain, furniture cloth, apron, piano, computor-keyboard, the fabrics such as overlay film and inside material.
Polyurethane termoplastic elastomer has polyester type and polyether-type two class, and the random spherical or cylindrical particle of white, relative density 1.10-1.25, polyether-type relative density is less than polyester type.The outstanding feature of polyurethane termoplastic elastomer is excellent in abrasion resistance, ozone resistance is fabulous, hardness is large, intensity is high, good springiness, low temperature resistant, have good oil resistant, chemical-resistant resistance and environmental resistance, in wet environment, polyether-type Ester hydrolysis stability far exceedes polyester type.Polyether-type thermoplastic polyurethane elastomer is the large class of one in Polyurethane Thermoplastic Elastomer, is generally synthesized by polytetramethylene ether diol (PTMGE), MDI and small molecule chain extender.Compared with polyester type Polyurethane Thermoplastic Elastomer, Polyether-type thermoplastic polyurethane elastomer has excellent low-temperature performance, anti-hydrolytic performance and elasticity, obtain in film, electric wire, spandex fibre etc. and apply widely, also more and more deep to its research.
As CN103193950A discloses a kind of Polyether-type thermoplastic polyurethane elastomer and preparation method thereof, described Polyether-type thermoplastic polyurethane elastomer is made up of 40 ~ 55% oligopolymer dibasic alcohol, 30 ~ 45% isocyanic ester, 5 ~ 20% chainextenders and 0.05 ~ 0.2% oxidation inhibitor, namely its preparation method adds oxidation inhibitor in oligopolymer dibasic alcohol, vacuumizes the oligopolymer dibasic alcohol containing oxidation inhibitor that dewaters to obtain; By chainextender vacuum hydro-extraction process; Isocyanic ester constant temperature oil bath is dissolved; The chainextender of the oligopolymer dibasic alcohol containing oxidation inhibitor and vacuum hydro-extraction process is mixed and heat regulation mixes to 90-100 DEG C with the isocyanic ester that oil bath has been dissolved, obtain when being stirred to 150 DEG C block elements in 80 DEG C of baking oven slakings, pulverize, be placed in that twin-screw extrusion unit is extruded, Qie La, dry up rear injection moulding machine injection moulding, flatness modulus must be had, longer elongation at break, the Polyether-type thermoplastic polyurethane elastomer that tensile strength scope is adjustable.
But, more and more wider along with polyurethane elastomer application, also more and more higher to its requirement, if the transparent polyurethane of yellowing resistance is also referred to as one of demand.
Summary of the invention
One of the object of the invention is to provide a kind of high Yellowing-resistant transparent Polyurethane Thermoplastic Elastomer.Described elastomerics is transparent and has excellent anti-yellowing property, also has longer elongation at break and stronger tensile strength.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A kind of high Yellowing-resistant transparent Polyurethane Thermoplastic Elastomer, by mass percentage, containing following component:
Polyoxyethylene glycol 20-35% is such as 22%, 26%, 32%, 34% etc.
Poly phosphazene 5-25% is such as 7%, 10%, 14%, 18%, 23% etc.
Tolylene diisocyanate 10-25% is such as 13%, 18%, 24% etc.
Butyleneglycol 10-30% is such as 13%, 18%, 24%, 29% etc.
Without the phosphorous acid ester 1-5% of phenyl ring, such as, be 1.4%, 2.2%, 2.9%, 3.5%, 4.6% etc.
UV light absorber 1-5% is such as 1.4%, 2.2%, 2.9%, 3.5%, 4.6% etc.
Containing hydrogen silicone oil 1-5% is such as 1.4%, 2.2%, 2.9%, 3.5%, 4.6% etc.
According to polyurethane elastomer of the present invention, by mass percentage, containing following component:
Polyoxyethylene glycol 20-30%
Poly phosphazene 10-15%
Tolylene diisocyanate 10-15%
Butyleneglycol 15-20%
Without the phosphorous acid ester 2-4% of phenyl ring
UV light absorber 2-4%
Containing hydrogen silicone oil 2-4%.
According to polyurethane elastomer of the present invention, described polyoxyethylene glycol is Polyethylene Glycol-600.
According to polyurethane elastomer of the present invention, described UV light absorber is 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole.
An object of the present invention is also to provide according to method for preparing polyurethane elastic body of the present invention, comprises the steps:
(1) by polyoxyethylene glycol 70-80 DEG C under vacuo, such as, be vacuumize dehydration under 72 DEG C, 76 DEG C, 79 DEG C etc.;
(2) by 85-95 DEG C under butyleneglycol vacuum, such as, be the lower dehydrations such as 88 DEG C, 94 DEG C; Melt at tolylene diisocyanate 57-68 DEG C;
(3) butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80-90 DEG C, and being such as lower heating more than the 0.5h such as 82 DEG C, 86 DEG C, 89 DEG C, such as, is 0.8h, 1.5h, 3h, 5h etc.;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, 145-155 DEG C, be such as 148 DEG C, 153 DEG C etc. and stir more than 0.5h down, be such as 0.8h, 1.5h, 3h, 5h etc., then at 85-95 DEG C, being such as lower more than the slaking 12h such as 87 DEG C, 90 DEG C, 94 DEG C, such as, is 14h, 20h, 30h etc.;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
According to preparation method of the present invention, the vacuum tightness of described vacuum is 0.2-0.5kPa.
According to preparation method of the present invention, the time of step (3) described heating is 1-3h.
According to preparation method of the present invention, the time of step (4) described stirring is 1-2h, and the time of slaking is 15-20h.。
The Polyurethane Thermoplastic Elastomer that the present invention obtains is transparent and has higher elongation at break, tensile strength, has excellent anti-yellowing property simultaneously.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
A kind of high resistance to yellow type transparent thermoplastic polyurethane elastomerics, by mass percentage, containing following component:
Polyoxyethylene glycol 20-35%
Poly phosphazene 5-25%
Tolylene diisocyanate 10-25%
Butyleneglycol 10-30%
Without the phosphorous acid ester 1-5% of phenyl ring
UV light absorber 1-5%
Containing hydrogen silicone oil 1-5%; Prepared by employing following methods:
(polyoxyethylene glycol is vacuumized dehydration at 70-80 DEG C by 1 under 0.2-0.5kPa vacuum;
(2) dewater under butyleneglycol 0.2-0.5kPa vacuum 85-95 DEG C; Melt at tolylene diisocyanate 57-68 DEG C;
(3) more than 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80-90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs more than 0.5h, then more than slaking 12h at 85-95 DEG C at 145-155 DEG C;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
Embodiment 1
A kind of high resistance to yellow type transparent thermoplastic polyurethane elastomerics, by mass percentage, containing following component:
Polyoxyethylene glycol 35%
Poly phosphazene 5%
Tolylene diisocyanate 19%
Butyleneglycol 30%
Without the phosphorous acid ester 1% of phenyl ring
UV light absorber 5%
Containing hydrogen silicone oil 5%; Prepared by employing following methods:
(1) polyoxyethylene glycol is vacuumized dehydration at 70 DEG C under 0.5kPa vacuum;
(2) dewater at lower for butyleneglycol 0.2kPa vacuum 95 DEG C; Melt at tolylene diisocyanate 68 DEG C;
(3) 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 3h, then slaking 12h at 90 DEG C at 150 DEG C;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
Embodiment 2
A kind of high resistance to yellow type transparent thermoplastic polyurethane elastomerics, by mass percentage, containing following component:
Polyoxyethylene glycol 24%
Poly phosphazene 25%
Tolylene diisocyanate 25%
Butyleneglycol 15%
Without the phosphorous acid ester 5% of phenyl ring
UV light absorber 3%
Containing hydrogen silicone oil 3%; Prepared by employing following methods:
(1) polyoxyethylene glycol is vacuumized dehydration at 80 DEG C under 0.2kPa vacuum;
(2) dewater at lower for butyleneglycol 0.5kPa vacuum 85 DEG C; Melt at tolylene diisocyanate 57 DEG C;
(3) 1h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 0.5h, then slaking 20h at 85 DEG C at 155 DEG C;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
Embodiment 3
A kind of high resistance to yellow type transparent thermoplastic polyurethane elastomerics, by mass percentage, containing following component:
Polyoxyethylene glycol 30%
Poly phosphazene 20%
Tolylene diisocyanate 20%
Butyleneglycol 10%
Without the phosphorous acid ester 3% of phenyl ring
UV light absorber 1%
Containing hydrogen silicone oil 2% and talcum powder 14%; Prepared by employing following methods:
(1) polyoxyethylene glycol is vacuumized dehydration at 75 DEG C under 0.4kPa vacuum;
(2) dewater at lower for butyleneglycol 0.3kPa vacuum 90 DEG C; Melt at tolylene diisocyanate 60 DEG C;
(3) 2h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 85 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs 3h, then slaking 30h at 95 DEG C at 145 DEG C;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
Respectively by the Polyurethane Thermoplastic Elastomer particle of gained in above-described embodiment 1-3 injection moulding growth 25mm in plastic-injection moulding machine, wide 6.1mm, the dumb-bell shape Polyether-type thermoplastic polyurethane elastomer of thick 2mm, then respectively the dumb-bell shape Polyether-type thermoplastic polyurethane elastomer of gained is pressed GB/T528-1998 (ISO37:2005) on electronic universal tension testing machine, in temperature (23 ± 2) DEG C, humidity (50 ± 2%), draw speed is measure its mechanics performance determining under the condition of 200mm/min, and measure the yellowness index change of transparency and UV illumination 24h, the results are shown in following table 1.
Table 1
As can be seen from the table, the elastomerics that the present invention obtains not only length of fracture, tensile strength is high, and anti-yellowing property is excellent.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (8)

1. a high resistance to yellow type transparent thermoplastic polyurethane elastomerics, is characterized in that, by mass percentage, containing following component:
2. polyurethane elastomer according to claim 1, is characterized in that, by mass percentage, containing following component:
3. polyurethane elastomer according to claim 1 and 2, is characterized in that, described polyoxyethylene glycol is Polyethylene Glycol-600.
4. the polyurethane elastomer according to any one of claim 1-3, is characterized in that, described UV light absorber is 2-(2 ˊ-hydroxyl-5 ˊ-aminomethyl phenyl) benzotriazole.
5. the method for preparing polyurethane elastic body described in any one of claim 1-4, comprises the steps:
(1) dehydration is vacuumized by polyoxyethylene glycol under vacuo 70-80 DEG C;
(2) dewater under butyleneglycol vacuum 85-95 DEG C; Melt at tolylene diisocyanate 57-68 DEG C;
(3) more than 0.5h is heated at the butyleneglycol after step (1) gained mixture and step (2) being dewatered is blended in 80-90 DEG C;
(4) tolylene diisocyanate after step (2) being melted mixes with step (3) gained mixture and other components, stirs more than 0.5h, then more than slaking 12h at 85-95 DEG C at 145-155 DEG C;
(5) namely step (4) products therefrom granulation, injection moulding are obtained described polyurethane elastomer.
6. preparation method according to claim 5, is characterized in that, the vacuum tightness of described vacuum is 0.2-0.5kPa.
7. preparation method according to claim 5, is characterized in that, the time of step (3) described heating is 1-3h.
8. preparation method according to claim 5, is characterized in that, the time of step (4) described stirring is 1-2h, and the time of slaking is 15-20h.
CN201410479982.7A 2014-09-18 2014-09-18 Anti-yellowing transparent TPU (thermoplastic polyurethane) elastomer and preparation method thereof Pending CN104231220A (en)

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Publication number Priority date Publication date Assignee Title
CN106957404A (en) * 2017-03-14 2017-07-18 浙江环龙新材料科技有限公司 A kind of color inhibition TPU film and its manufacture method
CN110712355A (en) * 2019-10-12 2020-01-21 东莞市米儿塑胶原料有限公司 Dynamic manufacturing method of high-light-transmittance yellowing-resistant TPU
WO2021155715A1 (en) * 2020-02-07 2021-08-12 山东理工大学 Reactive polyurethane flame retardant, preparation method therefor and use thereof

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CN101599314A (en) * 2008-06-05 2009-12-09 上海斯瑞聚合体科技有限公司 A kind of environmentally-friendly flame retardant thermoplastic polyurethane elastomer cable material
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CN101599314A (en) * 2008-06-05 2009-12-09 上海斯瑞聚合体科技有限公司 A kind of environmentally-friendly flame retardant thermoplastic polyurethane elastomer cable material
CN103804628A (en) * 2014-02-25 2014-05-21 偲众新材料科技(上海)有限公司 Polyphosphazene-modified cellular polyurethane elastomer and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106957404A (en) * 2017-03-14 2017-07-18 浙江环龙新材料科技有限公司 A kind of color inhibition TPU film and its manufacture method
CN110712355A (en) * 2019-10-12 2020-01-21 东莞市米儿塑胶原料有限公司 Dynamic manufacturing method of high-light-transmittance yellowing-resistant TPU
WO2021155715A1 (en) * 2020-02-07 2021-08-12 山东理工大学 Reactive polyurethane flame retardant, preparation method therefor and use thereof

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Application publication date: 20141224