CN102079806B - Preparation of organic silicon modified polyurethane elastic body and application thereof - Google Patents
Preparation of organic silicon modified polyurethane elastic body and application thereof Download PDFInfo
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Abstract
The invention relates to an organic silicon modified polyurethane elastic body composition which comprises the following components (in parts by weight): 100 parts of polyurethane prepolymers, 5-20 parts of HTPB (Hydroxyl-Terminated Polybutadiene), 5-25 parts of HTLN, 3-15 parts of poly-dimethyl siloxane, 0.1-1.0 part of catalyst, 3-10 parts of solidifying agents and 0-30 parts of solvents. The invention also relates to a method for preparing the organic silicon modified polyurethane elastic body, which comprises the following steps of: reacting the composition not containing the solidifying agents for 3-6h at 80-120 DEG C by stirring at a high speed (1000-5000rpm) in a nitrogen atmosphere, and removing the solvents and other micromolecules in a vacuum state; then adding the solidifying agents, uniformly stirring and mixing at the high speed, injection molding, pre-solidifying for 1-2 days at a room temperature, and then solidifying for 4-7 days at 55-65 DEG C. The synthesized organic silicon modified polyurethane elastic body has the advantages of favorable wear resistance, high elasticity and excellent weather-resistance and moist heat-resistance stability.
Description
Invention field
The present invention relates to a kind of organic silicon modified polyurethane elastomerics, more particularly, relate to the organic silicon modified polyurethane elastomerics that a kind of ageing-resistant, wear resistance has improved, its preparation method, and in the application aspect blade of wind-driven generator erosion resistant protective material.
Background of invention
Polyurethane elastomer is the serial elastomer material that contains carbamate groups and/or isocyanic ester on main polymer chain.Polymer chain also contains (carboxylic acid) ester group, ehter bond, urea groups, aryl and aliphatic chain etc. except containing above-mentioned group, usually formed by oligomer polyol, polyisocyanates and chainextender reaction.The Young's modulus of polyurethane elastomer is between rubber and plastics, and the advantage of its maximum is that existing high rigidity has again snappiness.Polyurethane elastomer has good intensity, hardness, anti-solvent, abrasion performance and anti-flexibility.Polyurethane elastomer roughly is divided into polyester type and polyether-type two classes, and wherein, polyester type is harder, above low temperature that generally can only anti--40 ℃; Polyether-type is softer, can anti--80 ℃～low temperature of-70 ℃.But two kinds polyurethane elastomer is ageing-resistant, stability to hydrolysis resistance is all relatively poor.
Organosilicon polymer high-low temperature resistant (60～300 ℃) excellent performance, UV resistant, resistance to oxidation degraded have low surface energy and good hydrophobicity, but wear resistance and chemical mediator-resitant property are relatively poor.The organic silicon modified polyurethane elastomerics is expected to obtain some special performances, such as good low temperature flexibility, thermostability, hydrophobicity, ageing-resistant and antioxidative stabilizer etc.
Some patent reports about the preparation of polyurethane elastomer, for example European patent EUP175733 and 235888; United States Patent (USP) 3591532,3901959,464759 and 4757095; Chinese patent CN 101134843 discloses a kind of high elasticity urethane elastomer composition, and the polyurethane elastomer of production is mainly used in the making of high-elastic wheel for roller skates or slide plate wheel; CN 101333280 discloses a kind of preparation method of carbon nano-tube modification polyurethane elastomer body, is intended to improve every mechanical property of polyurethane elastomer; USP (United States Patent (USP)) 4242468 discloses with the non-migrating softening agent of monohydroxylated polyhutadiene as urethane, and synthetic polyurethane wear resistant is relatively poor; It is that 1500～6000 liquid polybutadiene exists the lower method for preparing polyurethane elastomer that USP 5079270 discloses molecular weight, and this patent does not relate to wear resistance yet; CN 1192757 (former WO97/10590) discloses application liquid polybutadiene modified polyurethane elastomer, obtains polyurethane elastomer and the polyurethane foam of high abrasion; CN 101486788 discloses a kind of low density, high hardness polyurethane micropore elastomer, is used for making sole; CN 101039976 discloses a kind of highly-transparent polyurethane elastomerics, is mainly used in the manufacturing of sports goods.Other polyurethane elastomer report is mainly for the production of coating.
Patent report about organic silicon modified polyurethane is less, for example, CN 1470544 discloses a kind of preparation method of amino-modified silicone urethane, although the urethane of preparation has good thermotolerance and surface property, but its tensile strength is lower, only have 2.2～4.2MPa, be not suitable for Application Areas of the present invention; CN 101516949 (former US 2007/020390 and WO2008/036365) discloses the polyurethane foam composition with organic silicon surfactant, it has the katalysis that improves foam materials hardness of delay and the foam materials perforate of improvement, also is not suitable for Application Areas of the present invention; CN 101348554 discloses a kind of preparation of organic silicon modified aqueous polyurethane, is mainly used in top coat; CN 1854165 discloses a kind of organic silicon modified aqueous polyurethane, is mainly used in coating, finishing agent and tackiness agent.Some papers have been reported organic silicon modified polyurethane, generally use silanol (Eur.Polym.J.1999,35 (11): 1959; Polyurethane industrial, 18) or amido silicon oil (Nanjing University's journal (natural science edition), 2002,38 (2): 205) 2000,15 (4):; Also have report to use KH-560 (γ-glycidoxypropyltrime,hoxysilane) modified polyurethane, synthesized a kind of modified polyurethane elastomer (China Synthetic Rubber Industry, 2005,28 (1): 26), but, this mechanics of elastic bodies poor-performing, stress at definite elongation is lower than 5.5MPa.
In a word, (unmodified) of aforementioned patent or paper report do not relate to ageing-resistant performance (based on analysis of the molecular structure, their ageing-resistant performance is relatively poor) although the polyurethane elastomer wear resistance has improved, and the wet-heat resisting stability to hydrolysis is also lower; Although and utilize organic-silicon-modified polyurethane elastomer ageing-resistant performance to increase, mechanical property is relatively poor.
Summary of the invention
The present invention relates to a kind of ageing-resistant, wear resistance and improved, and the good organic silicon modified polyurethane elastomerics of solidity to corrosion and preparation method thereof, also relate to this elastomerics in the application aspect blade of wind-driven generator erosion resistant protective material.
The present invention is based on this imagination, that is, although use thermotolerance, weathering resistance and the surface hydrophobicity that the organic silicon modified polyurethane elastomerics has improved polyurethane elastomer in view of forefathers, take the mechanical property of sacrificing polyurethane elastomer as cost; Although and application of active liquid polybutadiene modified polyurethane elastomer reaches the improvement of resistance to low temperature, the wear resistance improvement is limited, even decreases.The organic silicon modified polyurethane elastomerics that contains amino and/or hydroxyl as for application keeps again the mechanical property of polyurethane elastomer when improving thermotolerance, weathering resistance and the surface hydrophobicity of polyurethane elastomer, there is not yet report.So, inventor's application end hydroxyl liquid polybutadiene, terminal hydroxy group hydroxyl liquid nitrile rubber and aminoalkylpolysiloxanes carry out modification to polyurethane elastomer simultaneously, on the one hand, improve thermotolerance, weathering resistance and the surface hydrophobicity of polyurethane elastomer by organosilicon, on the other hand, the polyhutadiene molecule segment guarantees the snappiness of polymer molecule, and by wear resistance and all well paracril and elastic polyurethane volume recombinations of snappiness, reaches collaborative wear resistance synergism.
Therefore, the present invention synthesizes a kind of organic silicon modified polyurethane elastomerics, namely, respectively take ethers base polyurethane prepolymer for use as and ester class base polyurethane prepolymer for use as main ingredient, be aided with terminal hydroxy group liquid polybutadiene and terminal hydroxy group liquid nitrile rubber, react synthetic a kind of organic-silicon-modified polyurethane elastomer under catalyst action together with the polysiloxane that contains amino and/or hydroxyl.
The technical parameter of ethers base polyurethane prepolymer for use as of the present invention is: tensile strength (MPa)＞15～40, shore a hardness is 75 ± 5～95 ± 2, tensile yield (%)＞300～500,300% tensile modulus (MPa)＞6～18, tension set (%)＜10～30, shock elasticity (%)＞15～50, tear strength (KN/M)＞40～100, temperature limit of brittleness (℃)＜-50～-40.In one embodiment, the technical parameter of ethers base polyurethane prepolymer for use as of the present invention is: tensile strength (MPa)＞25～30, shore a hardness is 75 ± 5～85 ± 5, tensile yield (%)＞350～400,300% tensile modulus (MPa)＞8～15, tension set (%)＜10～15, shock elasticity (%)＞20～40, tear strength (KN/M)＞45～60, temperature limit of brittleness (℃)＜-50～-45.
The technical parameter of ester class base polyurethane prepolymer for use as of the present invention is: tensile strength (MPa)＞35～55, shore a hardness is 70 ± 3～96 ± 2, tensile yield (%)＞400～600,300% tensile modulus (MPa)＞5～17, tension set (%)＜10, shock elasticity (%)＞20, tear strength (KN/M)＞40～120, temperature limit of brittleness (℃)＜-35～-30, (CC/1.61KM)≤0.01～0.08 of wearing and tearing.In one embodiment, the technical parameter of ethers base polyurethane prepolymer for use as of the present invention is: tensile strength (MPa)＞40～45, shore a hardness is 80 ± 3～85 ± 2, tensile yield (%)＞500～550,300% tensile modulus (MPa)＞10～12, tension set (%)＜10, shock elasticity (%)＞20, tear strength (KN/M)＞75～90, temperature limit of brittleness (℃)＜-35～-30, (CC/1.61KM)≤0.01～0.02 of wearing and tearing.
The technical parameter of terminal hydroxy group liquid polybutadiene of the present invention (HTPB) is: hydroxyl value 〉=0.5～1.0mmol/g, and Mn≤2300～4500, viscosity (40 ℃, pa.s)≤1.5～9.0, moisture % (m/m)≤0.1, superoxide is (with H
2O
2Meter) %≤0.05.In one embodiment, the technical parameter of HTPB of the present invention is: hydroxyl value 〉=1.0mmol/g, and Mn≤2300～2500, viscosity (40 ℃, pa.s)≤1.5～2.5, moisture % (m/m)≤0.1, superoxide is (with H
2O
2Meter) %≤0.05.
The technical parameter of terminal hydroxy group liquid nitrile rubber of the present invention (HTLN) is: itrile group massfraction (%) is 5.0 ± 1.5～15 ± 2.0, hydroxyl value (mmol/g) 〉=0.4～0.7, viscosity (40 ℃, pa.s)≤8～20, Mn 〉=2300～3000.In one embodiment, the technical parameter of HTLN of the present invention is: itrile group massfraction (%) is 10.0 ± 1.5～15 ± 2.0, hydroxyl value (mmol/g) 〉=0.55～0.7, viscosity (40 ℃, pa.s)≤12～15, Mn 〉=2500～2700.
Organosilicon of the present invention is the polydimethylsiloxane that contains amino and/or hydroxyl, in one embodiment, it is of the present invention that to contain amino polydimethylsiloxane can be the aminoalkyl group polydimethylsiloxane, amino-ethyl aminopropyl polydimethylsiloxane for example, 3-[(2-amino-ethyl) amino] multipolymer of propyl group methylsiloxane and dimethyl siloxane.Its amino value is 0.2～1.0mmol/g, and (25 ℃ is pa.s) 0.5～3.5 to viscosity.In one embodiment, its amino value is 0.4～0.8mmol/g, and (25 ℃ is pa.s) 1.0～2.0 to viscosity.Hydroxyl polydimethylsiloxane of the present invention can be dialkyl polydimethylsiloxane, and (25 ℃ is pa.s) 2～40 to its viscosity, volatile matter (%)≤1.0～3.0, surface sulfide time (h)≤1.0～3.0.In one embodiment, dialkyl polydimethylsiloxane of the present invention, (25 ℃ is pa.s) 2～5 to its viscosity, volatile matter (%)≤1.5～2.0, surface sulfide time (h)≤1.5～2.0.
Catalyzer of the present invention is organotin catalysts, stannous octoate for example, dibutyl tin laurate, dibutyltin diacetate, toxilic acid dibutyl tin, oxalic acid dilauryl tin, the oxalic acid dioctyl tin, two (4-methylamino phenylformic acid) dibutyl tin, dilauryl dibutyl tin thiolate, two (6-methylamino caproic acid) dibutyl tin etc., or its two or more combination.
Reaction of the present invention is generally carried out in organic solvent, butanone for example, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene etc., or its two or more combination.Necessary, also there are a kind of solidifying agent, for example triethylenediamine in reaction system of the present invention, two (N, N-dimethylaminoethyl) amine, dimethyl sulphide tolylene diamine (DADMT), 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA).
On the one hand, the invention provides a kind of organic silicon modified polyurethane elastic composition, it comprises (mass parts): base polyurethane prepolymer for use as 100, HTPB 10, and HTLN 15, polydimethylsiloxane 3～15, catalyzer 0.1～1.0, solidifying agent 3～10, solvent 0～30.On the other hand, the invention provides a kind of elastomeric method of organic silicon modified polyurethane for preparing, it comprises: in nitrogen atmosphere, at a high speed (under 1000～5000rpm) stirrings, the above-mentioned composition that does not contain solidifying agent is reacted 3～6h under 80～120 ℃, vacuum removal solvent and other small molecules.Then add solidifying agent, the high-speed stirring mixing, injection molding, room temperature Procuring 1～2 day, then solidified under 55～65 ℃ 4～7 days.
Hereinafter will the present invention be described in more detail by embodiment, but those skilled in the art should understand, the invention is not restricted to following embodiment, but limit scope of the present invention by attached claim.
Synthesizing of embodiment 1 organosilicon modified polyether type polyurethane elastomerics (I)
In the closed reactor under nitrogen protection, under the speed of 2000rpm stirs, add successively following component (mass parts): Polyether-Polyol Polyurethane Prepolymer [tensile strength (MPa)＞25, shore a hardness is 90 ± 2, tensile yield (%)＞350, tear strength (KN/M)＞50, temperature limit of brittleness (℃)＜-40] 100; HTPB (hydroxyl value 〉=1mmol/g, Mn≤2300, viscosity (40 ℃, pa.s)≤2.0) 10; HTLN (itrile group massfraction 15%, hydroxyl value 0.5mmol/g, viscosity (70 ℃, pa.s)≤15) 15; Dibutyl tin laurate 0.3, butanone 20.Be warming up to 85 ± 2 ℃, remain at this temperature and the speed that remains on 1200rpm stirs lower reaction 5h.Add subsequently 5 mass parts 3-[(2-amino-ethyls) amino] multipolymer (900～1,200cSt, mp＜-60 ℃, the 0.98g/Cm of propyl group methylsiloxane and dimethyl siloxane
3), under stirring, 85 ± 2 ℃ of speed with 1600rpm continue reaction 2h.Be cooled to 50 ℃, be evacuated to 50mmHg desolventizing and micromolecular compound.Then add 5 mass parts MOCA, stir 20min under the speed of 1600rpm.Injection molding in the teflon mould, room temperature Procuring 2 days, then solidified 5 days under 55～65 ℃.
Synthesizing of embodiment 2 organosilicon modified polyether type polyurethane elastomericss (II)
Formula and experimental implementation are with embodiment 1, different is the Polyether-Polyol Polyurethane Prepolymer of using following technical parameter: tensile strength (MPa)＞38, shore a hardness is 92 ± 1, tensile yield (%)＞430, tear strength (KN/M)＞90, temperature limit of brittleness (℃)＜-50.
Synthesizing of embodiment 3 organosilicon modified polyester type polyurethane elastomericss (III)
Formula and experimental implementation are with embodiment 1, different is the Polyether-Polyol Polyurethane Prepolymer of using following technical parameter: tensile strength (MPa)＞45, shore a hardness is 85 ± 2, tensile yield (%)＞550, tear strength (KN/M)＞75, temperature limit of brittleness (℃)＜-30.
Synthesizing of the unmodified polyurethane elastomer of comparative example 1 (IV)
Compare with embodiment 1, do not add HTPB, HTLN, organosilicon and dibutyl tin laurate.Add 5 mass parts MOCA in 100 mass parts Polyether-Polyol Polyurethane Prepolymer, stir 20min under the speed of 1600rpm.Injection molding in the teflon mould first solidifies 30min, then solidify 16h under 100 ℃ under 90 ℃.
Performance test:
Polishing is weightless, presses GB 1768-79 test; Shore a hardness is pressed GB/T 531-1999 test; Tensile strength is pressed GB/T 529-1999 test.
Anti-aging test:
The sample of according to the rules size cutting is placed in the constant water bath box of 60 ℃, experience thermostat(t)ed water steam is stifling, and sampling and testing mechanical property at set intervals compares with " Rhinoceros Hide " of Minnesota Mining and Manufacturing Company.
Abrasion (mg) after polyurethane elastomer polishing 1000 before and after modification turns are respectively: I-174; II-118; III-92; IV-276.Contrast I and IV as seen, after modification, the wear resistance of polyurethane elastomer has greatly improved.
The variation of mechanical property after 60 ℃ of wet heat treatment of polyurethane elastomer experience before and after table 1 modification
By as seen from Table 1, by contrast, the elastomerics that unmodified polyurethane elastomer anti-(damp and hot) aging resistance is processed than organosilicon is very different.In addition, all than " Rhinoceros Hide " height, after the wet heat treatment of 21 days, II is still high than " Rhinoceros Hide " intensity through the tensile strength of the polyurethane elastomer II of liquid polybutadiene and paracril modification simultaneously and III, the strength degradation of III is about 17%, and the strength degradation of II is only 3.5%.After 24 days, the intensity of II and III is slightly lower than " Rhinoceros Hide ".All in all, reach the harsh wet heat treatment of 24 days and cause that the tensile strength of II and III only descends 18%～19%; In addition, the time of wet heat treatment is longer, and the elongation of sample increases, and tensile strength descends." Rhinoceros Hide " tension set of 3M is minimum.
The variation of hardness after 60 ℃ of wet heat treatment of polyurethane elastomer experience before and after table 2 modification
| Time (my god) | Ⅳ | " Rhinoceros Hide " | Ⅲ | Ⅱ | Ⅰ |
| Be untreated | 87 | 88 | 86 | 89 | 90 |
| 6 | 87 | 82 | 85 | 87 | 88 |
| 9 | 88 | 84 | 85 | 86 | 87 |
| 12 | 86 | 85 | 86 | 86 | 85 |
| 18 | 85 | 81 | 86 | 86 | 86 |
| 21 | 84 | 83 | 85 | 86 | 86 |
| 24 | 83 | 81 | 84 | 83 | 85 |
As seen, 60 ℃ of wet heat treatment are very little on the hardness impact after 24 days.From shore a hardness, several elastomeric mechanical properties change very little, and the change of " Rhinoceros Hide " hardness is slightly large, is about 8%, is secondly I, change approximately 5%, and the hardness of II and III only change 2.5%.
Claims (10)
1. organic silicon modified polyurethane elastic composition, it is characterized in that: it comprises base polyurethane prepolymer for use as 100 mass parts, HTPB5～20 mass parts, HTLN5～25 mass parts, polydimethylsiloxane 3～15 mass parts, catalyzer 0.1～1.0 mass parts, solidifying agent 3～10 mass parts, solvent 0～30 mass parts;
Described base polyurethane prepolymer for use as is ethers base polyurethane prepolymer for use as and/or ester class base polyurethane prepolymer for use as;
The technical parameter of described HTPB is: hydroxyl value is 0.5～1.0mmol/g, and Mn is 2300～4500, is 1.5～9.0pa.s 40 ℃ of lower viscosity, moisture≤0.1%, and superoxide is with H
2O
2Meter≤0.05%;
The technical parameter of described HTLN is: the itrile group massfraction is 5.0 ± 1.5～15 ± 2.0%, and hydroxyl value is 0.4～0.7mmol/g, is 8～20pa.s 40 ℃ of lower viscosity, and Mn is 2300～3000;
Described polydimethylsiloxane is the polydimethylsiloxane that contains amino and/or hydroxyl;
Described solidifying agent is triethylenediamine, two (N, N-dimethylaminoethyl) amine, and the dimethyl sulphide tolylene diamine, 3,3 '-two chloro-4,4 '-diamino-ditan.
2. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, the technical parameter of described HTPB is: hydroxyl value is 1.0mmol/g, Mn is 2300～2500, be 1.5～2.5pa.s 40 ℃ of lower viscosity, moisture≤0.1%, superoxide is with H
2O
2Meter≤0.05%.
3. organic silicon modified polyurethane elastic composition according to claim 1, it is characterized in that, the technical parameter of described HTLN is: the itrile group massfraction is 10.0 ± 1.5～15 ± 2.0%, hydroxyl value is 0.55～0.7mmol/g, be 12～15pa.s 40 ℃ of lower viscosity, Mn is 2500～2700.
4. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, the described polydimethylsiloxane that contains amino is the aminoalkyl group polydimethylsiloxane.
5. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, the polydimethylsiloxane of described hydroxyl is dialkyl polydimethylsiloxane;
Described dialkyl polydimethylsiloxane are 2～40pa.s 25 ℃ of lower viscosity, the volatilization be divided into 1.0～3.0%, the surface sulfide time is 1.0～3.0h.
6. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, described catalyzer is organotin catalysts.
7. organic silicon modified polyurethane elastic composition according to claim 6, it is characterized in that, described organotin catalysts is stannous octoate, dibutyl tin laurate, dibutyltin diacetate, the toxilic acid dibutyl tin, oxalic acid dilauryl tin, oxalic acid dioctyl tin, two (4-methylamino phenylformic acid) dibutyl tin, dilauryl dibutyl tin thiolate, two (6-methylamino caproic acid) dibutyl tin, or its two or more combination.
8. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, described solvent is butanone, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene, or its two or more combination.
9. method for preparing organic silicon modified polyurethane elastic composition as claimed in claim 1, it comprises: in nitrogen atmosphere, under 1000～5000rpm stirs at a high speed, the composition that does not contain solidifying agent is reacted 3～6h under 80～120 ℃, vacuum removal solvent and other small molecules; Then add solidifying agent, the high-speed stirring mixing, injection molding, room temperature Procuring 1～2 day, then solidified under 55～65 ℃ 4～7 days.
10. organic silicon modified polyurethane elastic composition according to claim 1, is characterized in that, described organic silicon modified polyurethane elastic composition is applied in wind blade reinforcement aspect.
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| CN102532478B (en) * | 2012-02-17 | 2014-04-16 | 北京光华纺织集团有限公司 | Method for synthesizing organosilicon modified polyurethane |
| CN104894992B (en) * | 2015-05-27 | 2017-05-17 | 明光泰源安防科技有限公司 | Wireless alarm road cone |
| CN105131380A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | High-performance modified carboxylated acrylonitrile butadiene rubber composite material |
| CN105860501A (en) * | 2016-04-19 | 2016-08-17 | 滁州环球聚氨酯科技有限公司 | Heat-resistant and water-resistant polyurethane composite material |
| CN105820551A (en) * | 2016-04-19 | 2016-08-03 | 滁州环球聚氨酯科技有限公司 | Antiaging polyurethane composite material |
| CN105885006A (en) * | 2016-04-19 | 2016-08-24 | 滁州环球聚氨酯科技有限公司 | Preparation method of heat-resisting modified polyurethane composite |
| CN105778475A (en) * | 2016-04-19 | 2016-07-20 | 滁州环球聚氨酯科技有限公司 | Waterproof anti-bacterial polyurethane composite material |
| CN110105535A (en) * | 2019-05-21 | 2019-08-09 | 华侨大学 | A kind of preparation method of silane coupling agent graft modified aqueous polyurethane |
| CN110105745A (en) * | 2019-05-23 | 2019-08-09 | 厦门扬丰塑胶科技有限公司 | A kind of plastic products rubber material and preparation method thereof |
| CN112979962A (en) * | 2021-02-04 | 2021-06-18 | 成都思立可科技有限公司 | Branched-chain type organic silicon modified polyurethane elastomer and preparation method thereof |
| CN117164810B (en) * | 2023-10-07 | 2024-03-15 | 东莞市森宏新材料科技有限公司 | Environment-friendly TPU shoe material and preparation method thereof |
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| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
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| CN1470544A (en) * | 2003-06-24 | 2004-01-28 | 中国科学院广州化学研究所 | Method for preparing amino silicone oil modified polyurethane |
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