CN103980697B - A kind of nano-silicon dioxide modified polyurethane elastomer and preparation method thereof - Google Patents
A kind of nano-silicon dioxide modified polyurethane elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nano-silicon dioxide modified polyurethane elastomer and preparation method thereof.Polyether glycol, isocyanic ester and small molecules dibasic alcohol are prepared base polyurethane prepolymer for use as through polyaddition reaction, as component A; Chainextender, tetraethyl silicate and silane coupling agent are mixed, nano-silicon dioxide particle is formed by tetraethyl silicate in-situ hydrolysis and by the modification of silane coupling agent surface hydrophobicity, by mixture desolvation, obtains B component.Component A and B component are mixed in proportion, degassed, cast, sulfidization molding, obtained nano modified urethane elastomer.Present invention achieves dispersed in urethane of silicon dioxide granule, give full play to the reinforcing effect of nanoparticle, obtained polyurethane elastomer is that nano-silicon dioxide particle is cross-linked, and significantly can improve thermotolerance and the chemical stability of polyurethane elastomer; The requirement of sealing member to physical strength, wear resisting property, snappiness and oil-proofness can be applicable to, there are wide market outlook.
Description
Technical field
The invention belongs to polyurethane elastomer material technical field, relate to a kind of method for preparing modified urethane elastomer, be specifically related to that a kind of rich surface generates containing the inorganic silicon dioxide nano particles in-situ of functional group, method for preparing modified urethane elastomer.
Background technology
Urethane is normally formed through addition polymerization by polyethers or polyester macromolecule polyvalent alcohol, polyisocyanates and small molecules polyamine or polyalcohols chainextender, the feature of the Soft hard segment structure in its macromolecular chain and the micron-scale phase separation of material makes urethane have excellent mechanical property, can make (foam) plastics, elastomerics, fiber, coating and tackiness agent etc.Wherein polyurethane elastomer is a kind of high molecular synthetic material between ordinary rubber and plastics, not only have the high strength of plastics, but also have the snappiness of rubber, outstanding performance is embodied in the characteristic of excellent wear resistance, oil-proofness, low temperature resistant, resistance to ozone, radiation hardness and adiabatic shock-absorbing.Thus, polyurethane elastomer is widely used in the fields such as solid tyre, adhesive tape, rubber roll lining, oil sealing, sealing-ring, die-cushion, electric elements embedding, tackiness agent and coating, is one of indispensable engineering materialss of each industrial sector such as building industry, automotive industry, aircraft industry.What require material over-all properties along with each Application Areas improves constantly, and the performance of conventional urethane can not meet the requirement of practical application, and people have carried out the performance that a large amount of research work improves polyurethane elastomer for this reason.
Because Nano filling has the character such as small-size effect, surface-interface effect, with polymeric matrix, strong interfacial interaction can occur, be that common fillers is incomparable to the modified effect of polyurethane material.Therefore, nano-filler modified urethane has become a very active research field.At present, in the research of inorganic nanoparticle modified polyurethane material, adopt maximum methods to be directly joined in urethane resin by nanoparticle, the shearing action by the external world forces inorganic component to disperse in polymeric system.But nanoparticle surface activity is high, very easily agglomeration occurs; Add the poor compatibility of polymeric constituent and inorganic component, high viscosity that polymeric matrix has, be difficult to obtain the homodisperse system of nanoparticle.And, even if scattered nanoparticle also can slowly self aggregation, mutually reunite.How realize dispersed in polyurethane matrix realizing inorganic nano-particle, play the reinforcing effect of inorganic component, improve the thermotolerance of polyurethane elastomer, solvent resistant and physical strength, still need research further.
Summary of the invention
The object of this invention is to provide a kind of nano-silicon dioxide modified polyurethane elastomer, another object is to provide nano-silicon dioxide modified method for preparing polyurethane elastic body.
The hardness of nano-silicon dioxide modified polyurethane elastomer of the present invention is greater than 80 Shao A, tensile strength is 30 ~ 44MPa, elongation rate of tensile failure is 260 ~ 550%, tear strength is 70 ~ 195KN/m, resilience 37 ~ 48%, density 1.17g/cm
3;
The present invention is first to hold the polyether glycol of OH, the polyaddition reaction successively between isocyanic ester and small molecules dibasic alcohol, and obtained end group is the base polyurethane prepolymer for use as of NCO group, as component A; Chainextender is joined in tetraethyl silicate and silane coupling agent, make tetraethyl silicate in-situ hydrolysis form nano-silicon dioxide particle simultaneously function modified by silane coupling agent in-situ surface, obtained chainextender B component; By above-mentioned base polyurethane prepolymer for use as component A and chainextender B component, mix according to a certain ratio, degassed, adopt cast spray method injection molding, obtained nano modified urethane elastomer after sulfidization molding.NCO group wherein in base polyurethane prepolymer for use as component A and the mol ratio of OH group are 1.1 ~ 2.0.
The concrete operation step preparing nano-silicon dioxide modified polyurethane elastomer is as follows:
(1) preparation of base polyurethane prepolymer for use as component A
Under nitrogen protection, in 100g polyether glycol, add 14 ~ 28g isocyanic ester, start mechanical stirring, slowly be warming up to 80 ~ 100 DEG C, insulation reaction 1 ~ 3h, adds 0.5 ~ 1.2g small molecules dibasic alcohol and continues reaction 2 ~ 4h, obtained base polyurethane prepolymer for use as component A;
(2) preparation of chainextender B component
Joined by 40g chainextender in 8 ~ 10g tetraethyl silicate and 1.2 ~ 2.4g silane coupling agent, under normal temperature, mechanical stirring 3 ~ 4h mixes, and removes the ethanol that tetraethyl silicate condensation reaction generates, obtained chainextender B component;
(3) described base polyurethane prepolymer for use as component A and chainextender B component are mixed by 100:10 ~ 15 mass ratio, degassed, add stannous octoate, rapid stirring is even, adopts cast spray method injection molding, sulfidization molding, obtained nano modified polyurethane material; The hardness of described nano-silicon dioxide modified polyurethane elastomer is greater than 80 Shao A, tensile strength is 30 ~ 44MPa, elongation rate of tensile failure is 260 ~ 550%, tear strength is 70 ~ 195KN/m, resilience 37 ~ 48%, density 1.17g/cm
3.
Described polyether glycol is the one in polytetrahydrofuran diol or polycaprolactone glycol or polyoxytrimethylene ether glycol, and its molecular weight is between 800 ~ 3000.
Described isocyanate-monomer is tolylene diisocyanate or diphenylmethanediisocyanate or hexamethylene-diisocyanate or isophorone diisocyanate.
Described small molecules dibasic alcohol is ethylene glycol or butyleneglycol or hexylene glycol.
The chainextender of described urethane B component is chloro-4, the 4'-diaminodiphenyl-methanes of 3,3'-bis-or two adjacent chlorodiphenyl amine methane (MOCA) or mphenylenediamine or sec.-propyl diamines or 4,4 '-diphenylmethanediamiand (MDA).
Described in step (2), tetraethyl silicate consumption is 10 ~ 80% of chainextender consumption.
In step (2), silane coupling agent is γ-aminopropyl triethoxysilane or γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane or gamma-mercaptopropyltriethoxysilane or N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane or N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, its consumption is 5 ~ 30% of tetraethyl silicate consumption.
Advantageous Effects of the present invention embodies in the following areas: inorganics presoma and silane coupling agent join in chainextender by (1), precursor in situ is hydrolyzed and generates inorganic nano silicon dioxide granule, silane coupling agent also take part in the condensation reaction of tetraethyl silicate, surface modification is carried out to nanoparticle, obtain hydrophobic inorganic silicon dioxide granule, improve the consistency between inorganic nano component and polymkeric substance; (2) rich surface of inorganic silicon dioxide nano particle is containing functional group, and can participate in the vulcanization reaction of base polyurethane prepolymer for use as, Nano particles of silicon dioxide act as the effect of solid linking agent, can significantly improve mechanical property and the thermotolerance of polymkeric substance; (3) due to the effect of the chemical bond between nano-silicon dioxide particle and polymer chain, the migration of inorganic nano component in polymeric matrix and agglomeration is avoided.Achieve nano-silicon dioxide particle in the present invention in the in-situ preparation of polyurethane elastomer, modification and dispersion, take part in vulcanization reaction at sulfurating stage, significantly improve thermotolerance and the mechanical property of polyurethane elastomer.Table 1 is that elastomer performance prepared by the nano-silicon dioxide modified polyurethane elastomer of the present invention and conventional mechanical hybrid system contrasts.
Elastomer performance prepared by the nano-silicon dioxide modified polyurethane elastomer of table 1 the present invention and conventional mechanical hybrid system contrasts
From table 1, mix with conventional mechanical and add compared with modified polyurethane elastomer prepared by nano-powder, the performance boost of the present invention's nano-silicon dioxide modified polyurethane elastomer is obvious.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
the technical performance index of the nano modified urethane elastomer prepared by embodiment 1-6 is as shown in table 2:
。
embodiment 1
Component A comprises following raw materials according:
Polytetrahydrofuran ethoxylated polyhydric alcohol (molecular weight is 2000) 100g,
Butyleneglycol 0.9g,
Tolylene diisocyanate 19.0g,
B component comprises following raw materials according:
Tetraethyl silicate 8g,
γ-aminopropyl triethoxysilane 2.4g,
MOCA40g。
The concrete preparation manipulation step of nano-silicon dioxide modified polyurethane elastomer is as follows:
(1) preparation of base polyurethane prepolymer for use as component A: take 100g PTMG join have agitator, thermometer, by the four-hole boiling flask of filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 19g tolylene diisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add 1.2g butyleneglycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
(2) preparation of chainextender B component: 40gMOCA is joined in 8g tetraethyl silicate and 2.4g γ-aminopropyl triethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, tetraethyl silicate in-situ hydrolysis forms nano-silicon dioxide particle, silane coupling agent also participates in hydrolysis-condensation reaction simultaneously, and nano-silicon dioxide particle, by silane coupling agent in-situ-surface modifying, obtains chainextender B component;
(3) by component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and component A, B component mix by 100:10 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, obtains nano-silicon dioxide modified polyurethane elastomer; The hardness of nano-silicon dioxide modified polyurethane elastomer is 80 Shao A, tensile strength is 30MPa, elongation rate of tensile failure is 550%, tear strength is 70KN/m, resilience 48%, density 1.17g/cm
3.
embodiment 2
Component A comprises following raw materials according:
Polytetrahydrofuran ethoxylated polyhydric alcohol 100g,
Butyleneglycol 1.2g,
Diphenylmethanediisocyanate 27.5g;
B component comprises following raw materials according:
N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 1.2g,
Tetraethyl silicate 8g,
MOCA40g。
The concrete preparation manipulation step of nano-silicon dioxide modified polyurethane elastomer is as follows:
(1) preparation of base polyurethane prepolymer for use as component A: take 100g PTMG join have agitator, thermometer, by the four-hole boiling flask of filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 27.5g diphenylmethanediisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add 0.5g butyleneglycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
(2) preparation of chainextender B component: 40gMOCA is joined in 8g tetraethyl silicate and 2.4gN-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, obtained chainextender B component;
(3) by component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and A, B component mix by 100:12 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, obtains nano-silicon dioxide modified polyurethane elastomer; The hardness of nano-silicon dioxide modified polyurethane elastomer is 90 Shao A, tensile strength is 35MPa, elongation rate of tensile failure is 500%, tear strength is 80KN/m, resilience 44%, density 1.17g/cm
3.
embodiment 3
Component A comprises following raw materials according:
Polycaprolactone glycol (molecular weight is 2000) 100g,
Butyleneglycol 0.5g,
Diphenylmethanediisocyanate 27.5g;
B component comprises following raw materials according:
γ-aminopropyl triethoxysilane 2.4g,
Tetraethyl silicate 8.0g,
MDA40g。
Concrete preparation method is as follows:
The preparation of base polyurethane prepolymer for use as component A: take 100g polycaprolactone glycol join have agitator, thermometer, by the four-hole boiling flask of filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 27.5g diphenylmethanediisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add 0.5g butyleneglycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
B: the preparation of chainextender B component: 40gMDA is joined in 8g tetraethyl silicate and 2.4g γ-aminopropyl triethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, obtained chainextender B component;
By component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and A, B component mix by 100:12 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, is met the polyurethane elastomer that physical and mechanical properties requires.
embodiment 4:
Component A comprises following raw materials according:
Polycaprolactone glycol (molecular weight is 2000) 100g,
Tolylene diisocyanate 14.8g,
Hexylene glycol 0.8g;
B component comprises following raw materials according:
γ-aminopropyl triethoxysilane 2.4g,
Tetraethyl silicate 8.0g,
MOCA40g。
Concrete preparation method is as follows:
The preparation of base polyurethane prepolymer for use as component A: take 100g polycaprolactone glycol and join in the four-hole boiling flask having agitator, thermometer, filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 14.8g tolylene diisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add 0.8g hexylene glycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
B: the preparation of chainextender B component: 40gMOCA is joined in 8g tetraethyl silicate and 2.4g γ-aminopropyl triethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, obtained chainextender B component;
By component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and A, B component mix by 100:15 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, is met the polyurethane elastomer that physical and mechanical properties requires.
embodiment 5:
Component A comprises following raw materials according:
Polytetrahydrofuran ethoxylated polyhydric alcohol (molecular weight is 2000) 100g,
Hexylene glycol 0.8g,
Tolylene diisocyanate 15.6g;
B component comprises following raw materials according:
γ-aminopropyl triethoxysilane 2.4g,
Tetraethyl silicate 8.0g,
MOCA40g。
Concrete preparation method is as follows:
The preparation of base polyurethane prepolymer for use as component A: take 100g PTMG join have agitator, thermometer, by the four-hole boiling flask of filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 15.6g tolylene diisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add 0.8g hexylene glycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
B: the preparation of chainextender B component: 40gMOCA is joined in 8g tetraethyl silicate and 2.4g γ-aminopropyl triethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, obtained chainextender B component;
By component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and A, B component mix by 100:12 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, is met the polyurethane elastomer that physical and mechanical properties requires.
embodiment 6:
Component A comprises following raw materials according:
Polytetrahydrofuran ethoxylated polyhydric alcohol (molecular weight is 2000) 100g,
Ethylene glycol 0.6g,
Tolylene diisocyanate 16.8g;
B component comprises following raw materials according:
γ-aminopropyl triethoxysilane 2.4g,
Tetraethyl silicate 10.0g,
MOCA40g。
Concrete preparation method is as follows:
The preparation of base polyurethane prepolymer for use as component A: take 100g PTMG join have agitator, thermometer, by the four-hole boiling flask of filling tube, nitrogen adapter, vacuum adapter and dried chimney filter, removed under reduced pressure micro-moisture, add 16.8g tolylene diisocyanate, after being warming up to 85 DEG C of insulation reaction 1.5h, add ethylene glycol and continue reaction 3h, prepare base polyurethane prepolymer for use as component A;
B: the preparation of chainextender B component: 40gMOCA is joined in 8g tetraethyl silicate and 2.4g γ-aminopropyl triethoxysilane, mix under normal temperature, mechanical stirring 3h, the ethanol that the condensation reaction of removed under reduced pressure tetraethyl silicate generates, obtained chainextender B component;
By component A degassed 30min at 85 DEG C, inflated with nitrogen removes vacuum, and A, B component mix by 100:12 mass ratio, add 0.15g stannous octoate, rapid stirring number minute, injects the mould of 100 DEG C immediately, sulfuration 3h at 85 DEG C.After solidification, cooling and demolding, is met the polyurethane elastomer that physical and mechanical properties requires.
Claims (9)
1. a nano-silicon dioxide modified polyurethane elastomer, is characterized in that: the hardness of described nano-silicon dioxide modified polyurethane elastomer is greater than 80 Shao A, tensile strength is 30 ~ 44MPa, elongation rate of tensile failure is 260 ~ 550%, tear strength is 70 ~ 195KN/m, resilience 37 ~ 48%, density 1.17g/cm
3;
First to hold the polyether glycol of OH, the polyaddition reaction successively between isocyanic ester and small molecules dibasic alcohol, obtained end group is the base polyurethane prepolymer for use as of NCO group, as component A; Chainextender is joined in tetraethyl silicate and silane coupling agent, make tetraethyl silicate in-situ hydrolysis form nano-silicon dioxide particle simultaneously function modified by silane coupling agent in-situ surface, obtained chainextender B component; By above-mentioned base polyurethane prepolymer for use as component A and chainextender B component, mix according to a certain ratio, degassed, adopt cast spray method injection molding, obtained nano modified urethane elastomer after sulfidization molding.
2. the nano-silicon dioxide modified polyurethane elastomer of one according to claim 1, is characterized in that: the NCO group in described base polyurethane prepolymer for use as component A and the mol ratio of OH group are 1.1 ~ 2.0.
3. prepare the method for a kind of nano-silicon dioxide modified polyurethane elastomer according to claim 1, it is characterized in that concrete preparation manipulation step is as follows:
(1) preparation of base polyurethane prepolymer for use as component A
Under nitrogen protection, in 100g polyether glycol, add 14 ~ 28g isocyanic ester, start mechanical stirring, slowly be warming up to 80 ~ 100 DEG C, insulation reaction 1 ~ 3h, adds 0.5 ~ 1.2g small molecules dibasic alcohol and continues reaction 2 ~ 4h, obtained base polyurethane prepolymer for use as component A;
(2) preparation of chainextender B component
Joined by 40g chainextender in 8 ~ 10g tetraethyl silicate and 1.2 ~ 2.4g silane coupling agent, under normal temperature, mechanical stirring 3 ~ 4h mixes; Remove the ethanol that tetraethyl silicate condensation reaction generates, obtained chainextender B component;
(3) described base polyurethane prepolymer for use as component A and chainextender B component are mixed by 100:10 ~ 15 mass ratio, degassed, add stannous octoate, rapid stirring is even, adopts cast spray method injection molding, sulfidization molding, obtained nano modified polyurethane material; The hardness of described nano-silicon dioxide modified polyurethane elastomer is greater than 80 Shao A, tensile strength is 30 ~ 44MPa, elongation rate of tensile failure is 260 ~ 550%, tear strength is 70 ~ 195KN/m, resilience 37 ~ 48%, density 1.17g/cm
3.
4. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, it is characterized in that: polyether glycol described in step (1) is the one in polytetrahydrofuran diol or polycaprolactone glycol or polyoxytrimethylene ether glycol, and its molecular weight is between 800 ~ 3000.
5. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, is characterized in that: isocyanate-monomer described in step (1) is tolylene diisocyanate or diphenylmethanediisocyanate or hexamethylene-diisocyanate or isophorone diisocyanate.
6. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, is characterized in that: small molecules dibasic alcohol described in step (1) is ethylene glycol or butyleneglycol or hexylene glycol.
7. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, it is characterized in that: the chainextender of described urethane B component is 3,3'-bis-chloro-4,4'-diaminodiphenyl-methane or two adjacent chlorodiphenyl amine methane (MOCA) or mphenylenediamine or sec.-propyl diamines or 4,4 '-diphenylmethanediamiand (MDA).
8. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, is characterized in that: described in step (2), tetraethyl silicate consumption is 10 ~ 80% of chainextender consumption.
9. the nano-silicon dioxide modified method for preparing polyurethane elastic body of one according to claim 3, it is characterized in that: in step (2), silane coupling agent is γ-aminopropyl triethoxysilane or γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane or gamma-mercaptopropyltriethoxysilane or N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane or N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, its consumption is 5 ~ 30% of tetraethyl silicate consumption.
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| CN112095230B (en) * | 2020-08-15 | 2022-09-13 | 福建冠泓工业有限公司 | Super-soft super-fluffy spun-bonded non-woven fabric and preparation method thereof |
| CN111961186A (en) * | 2020-08-27 | 2020-11-20 | 栖霞市兴邦新材料科技有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN112169724A (en) * | 2020-09-24 | 2021-01-05 | 苏州复之恒新材料科技有限公司 | Mesoporous silica modified polyurethane elastomer and production device thereof |
| CN112646360A (en) * | 2020-12-24 | 2021-04-13 | 淮北五星铝业有限公司 | Preparation method of functional waterborne polyurethane-based nano composite protective film |
| CN114774061B (en) * | 2022-06-07 | 2023-09-22 | 广州市盛邦康体场地材料有限公司 | Adhesive for bonding prefabricated rubber runway |
| CN115010893B (en) * | 2022-06-30 | 2023-01-10 | 盛鼎高新材料有限公司 | Thermoplastic polyurethane elastomer and processing technology thereof |
| CN115287034B (en) * | 2022-09-29 | 2022-12-09 | 铁科腾跃科技有限公司 | Interfacial agent-free polyurethane elastomer for railway concrete expansion joints and preparation method thereof |
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| CN102010486B (en) * | 2010-10-14 | 2012-11-14 | 安徽大学 | Method for preparing nano SiO2/polyurethane/acrylic ester composite emulsion and miniemulsion polymerization |
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