CN102079806A - 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
- Publication number
- CN102079806A CN102079806A CN2010105890707A CN201010589070A CN102079806A CN 102079806 A CN102079806 A CN 102079806A CN 2010105890707 A CN2010105890707 A CN 2010105890707A CN 201010589070 A CN201010589070 A CN 201010589070A CN 102079806 A CN102079806 A CN 102079806A
- Authority
- CN
- China
- Prior art keywords
- organic silicon
- silicon modified
- polydimethylsiloxane
- modified polyurethane
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y02E10/722—
Landscapes
- Polyurethanes Or Polyureas (AREA)
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 the 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, formed by oligomer polyol, polyisocyanates and chainextender reaction usually.The Young's modulus of polyurethane elastomer is between rubber and plastics, and its biggest advantage is that existing high rigidity has snappiness again.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, generally can only anti--40 ℃ above low temperature; Polyether-type is softer, can anti--80 ℃～-70 ℃ low temperature.But two kinds polyurethane elastomer is ageing-resistant, hydrolysis is stable 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, for example 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 the wear-resisting property of synthetic urethane is relatively poor; It is that 1500～6000 liquid polybutadiene exists the method for preparing polyurethane elastomer down 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 the polyurethane elastomer and the polyurethane foam of high abrasion; CN 101486788 discloses a kind of low density, high hardness polyurethane micropore elastomer, is used to make 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 used in production 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, though the urethane of preparation has good thermotolerance and surface property, but its tensile strength is lower, have only 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) though the polyurethane elastomer wear resistance has improved, and moisture-proof thermal hydrolysis stability is also lower; Though 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, though use thermotolerance, weathering resistance and the surface hydrophobicity that the organic silicon modified polyurethane elastomerics has improved polyurethane elastomer in view of forefathers, is cost with the mechanical property of sacrificing polyurethane elastomer; Though 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.Contain the organic silicon modified polyurethane elastomerics of amino and/or hydroxyl as for application, in the thermotolerance, weathering resistance and the surface hydrophobicity that improve polyurethane elastomer, keep the mechanical property of polyurethane elastomer again, do not appear in the newspapers as yet.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, promptly, be main ingredient with ethers base polyurethane prepolymer for use as and ester class base polyurethane prepolymer for use as respectively, be aided with terminal hydroxy group liquid polybutadiene and terminal hydroxy group liquid nitrile rubber, under catalyst action, react synthetic a kind of organic-silicon-modified polyurethane elastomer 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, wearing and tearing (CC/1.61KM)≤0.01～0.08.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, wearing and tearing (CC/1.61KM)≤0.01～0.02.
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 0.5～3.5 pa.s) to viscosity.In one embodiment, its amino value is 0.4～0.8mmol/g, and (25 ℃ is 1.0～2.0 pa.s) to viscosity.Hydroxyl polydimethylsiloxane of the present invention can be a dialkyl polydimethylsiloxane, and (25 ℃ is 2～40 pa.s) to its viscosity, volatile matter (%)≤1.0～3.0, surperficial curing time (h)≤1.0～3.0.In one embodiment, dialkyl polydimethylsiloxane of the present invention, (25 ℃ is 2～5 pa.s) to its viscosity, volatile matter (%)≤1.5～2.0, surperficial curing time (h)≤1.5～2.0.
Catalyzer of the present invention is an 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 is a kind of solidifying agent in the reaction system of the present invention, triethylenediamine for example, 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 the elastomeric method of a kind of preparation organic silicon modified polyurethane, 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, vacuum removal solvent and other small molecules down at 80～120 ℃.Add solidifying agent then, the high-speed stirring mixing, injection molding, room temperature Procuring 1～2 day was solidified 4～7 days down at 55～65 ℃ again.
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 the nitrogen protection, under the speed of 2000rpm stirs, add following component (mass parts) successively: 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 under this temperature and the speed that remains on 1200rpm stirs reaction 5h down.Add 5 mass parts 3-[(2-amino-ethyls subsequently) amino] propyl group methylsiloxane and dimethyl siloxane multipolymer (900～1,200cSt, mp＜-60 ℃, 0.98g/Cm
3), under stirring, 85 ± 2 ℃ of speed with 1600rpm continue reaction 2h.Be cooled to 50 ℃, be evacuated to 50mmHg except that desolvating and micromolecular compound.Add 5 mass parts MOCA then, under the speed of 1600rpm, stir 20min.Injection molding in the teflon mould, room temperature Procuring 2 days was solidified 5 days down at 55～65 ℃ again.
Synthesizing of embodiment 2 organosilicon modified polyether type polyurethane elastomericss (II)
Prescription 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 are 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)
Prescription 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 are 85 ± 2, tensile yield (%)＞550, tear strength (KN/M)＞75, temperature limit of brittleness (℃)＜-30.
Synthesizing of comparative example's 1 unmodified polyurethane elastomer (IV)
Compare with embodiment 1, do not add HTPB, HTLN, organosilicon and dibutyl tin laurate.In 100 mass parts Polyether-Polyol Polyurethane Prepolymer, add 5 mass parts MOCA, under the speed of 1600rpm, stir 20min.Injection molding in the teflon mould solidifies 30min down at 90 ℃ earlier, solidifies 16h down at 100 ℃ again.
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 placed in 60 ℃ the constant water bath box, 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 the modification is changeed are respectively: I-174; II-118; III-92; IV-276.Contrast I and IV as seen, the wear resistance of polyurethane elastomer has greatly improved after the modification.
Changes of mechanical properties after 60 ℃ of wet heat treatment of polyurethane elastomer experience before and after table 1 modification
By table 1 as seen, by contrast, the elastomerics that unmodified polyurethane elastomer anti-(damp and hot) aging resistance is handled than organosilicon is very different.In addition, all than " Rhinoceros Hide " height, after 21 days wet heat treatment, II is still than " Rhinoceros Hide " intensity height 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 only is 3.5%.After 24 days, the intensity of II and III is lower than " Rhinoceros Hide " slightly.All in all, reach 24 days harsh wet heat treatment and cause that the tensile strength of II and III only descends 18%～19%; In addition, the time of wet heat treatment is long more, and the elongation of sample increases, and tensile strength descends." Rhinoceros Hide " tension set minimum of 3M.
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 to the hardness influence after 24 days.From shore a hardness, several elastomeric mechanical properties change very little, and the change of " Rhinoceros Hide " hardness is big slightly, is about 8%, secondly is I, change approximately 5%, and the hardness of II and III only changes 2.5%.
Claims (10)
1. organic silicon modified polyurethane elastic composition, it is characterized in that: it comprises (mass parts): base polyurethane prepolymer for use as 100, HTPB 5～20, HTLN 5～25, polydimethylsiloxane 3～15, catalyzer 0.1～1.0, solidifying agent 3～10, solvent 0～30;
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 terminal hydroxy group liquid polybutadiene (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 a preferred embodiment, the technical parameter of described HTPB 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 described terminal hydroxy group liquid nitrile rubber (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 a preferred embodiment, the technical parameter of described HTLN 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.
Described polydimethylsiloxane is the polydimethylsiloxane that contains amino and/or hydroxyl.
Described solidifying agent is a triethylenediamine, two (N, N-dimethylaminoethyl) amine, and dimethyl sulphide tolylene diamine (DADMT), 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA).
2. organic silicon modified polyurethane elastic composition according to claim 1, it is characterized in that, the technical parameter of described ethers base polyurethane prepolymer for use as 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 a preferred embodiment, the technical parameter of described ethers base polyurethane prepolymer for use as 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.
3. organic silicon modified polyurethane elastic composition according to claim 1, it is characterized in that, the technical parameter of described ester class base polyurethane prepolymer for use as 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, wearing and tearing (CC/1.61KM)≤0.01～0.08; In a preferred embodiment, the technical parameter of described ester class base polyurethane prepolymer for use as 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, wearing and tearing (CC/1.61KM)≤0.01～0.02.
4. organic silicon modified polyurethane elastic composition according to claim 1, it is characterized in that, the described polydimethylsiloxane that contains amino is the aminoalkyl group polydimethylsiloxane, amino-ethyl aminopropyl polydimethylsiloxane for example, 3-[(2-amino-ethyl) amino] multipolymer of propyl group methylsiloxane and dimethyl siloxane.
5. organic silicon modified polyurethane elastic composition according to claim 1 is characterized in that, the amino value of described aminoalkyl group polydimethylsiloxane is 0.2～1.0mmol/g, and (25 ℃ is 0.5～3.5 pa.s) to viscosity; In a preferred embodiment, the amino value of described aminoalkyl group polydimethylsiloxane is 0.4～0.8mmol/g, and (25 ℃ is 1.0～2.0 pa.s) to viscosity.
6. organic silicon modified polyurethane elastic composition according to claim 1 is characterized in that the polydimethylsiloxane of described hydroxyl is a dialkyl polydimethylsiloxane;
(25 ℃ is 2～40 pa.s) to the viscosity of described dialkyl polydimethylsiloxane, volatile matter (%)≤1.0～3.0, surperficial curing time (h)≤1.0～3.0; In a preferred embodiment, (25 ℃ is 2～5 pa.s) to the viscosity of described dialkyl polydimethylsiloxane, volatile matter (%)≤1.5～2.0, surperficial curing time (h)≤1.5～2.0.
7. organic silicon modified polyurethane elastic composition according to claim 1 is characterized in that described catalyzer is an 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.
8. organic silicon modified polyurethane elastic composition according to claim 1 is characterized in that described solvent is a butanone, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene etc., or its two or more combination.
9. one kind prepares the elastomeric method of organic silicon modified polyurethane, it comprises: in nitrogen atmosphere, (under 1000～5000rpm) stirrings, will not contain composition reaction 3～6h under 80～120 ℃ of the claim 1 of solidifying agent, vacuum removal solvent and other small molecules at a high speed; Add solidifying agent then, the high-speed stirring mixing, injection molding, room temperature Procuring 1～2 day was solidified 4～7 days down at 55～65 ℃ again.
10. the application of the organic silicon modified polyurethane elastomerics of claim 14 aspect the wind blade reinforcement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105890707A CN102079806B (en) | 2010-12-15 | 2010-12-15 | Preparation of organic silicon modified polyurethane elastic body and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105890707A CN102079806B (en) | 2010-12-15 | 2010-12-15 | Preparation of organic silicon modified polyurethane elastic body and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102079806A true CN102079806A (en) | 2011-06-01 |
| CN102079806B CN102079806B (en) | 2013-05-15 |
Family
ID=44086023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105890707A Expired - Fee Related CN102079806B (en) | 2010-12-15 | 2010-12-15 | Preparation of organic silicon modified polyurethane elastic body and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102079806B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532478A (en) * | 2012-02-17 | 2012-07-04 | 北京光华纺织集团有限公司 | Method for synthesizing organosilicon modified polyurethane |
| CN104894992A (en) * | 2015-05-27 | 2015-09-09 | 安徽博昌电子科技股份有限公司 | 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN117164810A (en) * | 2023-10-07 | 2023-12-05 | 东莞市森宏新材料科技有限公司 | Environment-friendly TPU shoe material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2008036365A1 (en) * | 2006-09-21 | 2008-03-27 | Momentive Performance Materials Inc. | Polyurethane foam composition possessing modified silicone surfactants |
-
2010
- 2010-12-15 CN CN2010105890707A patent/CN102079806B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2008036365A1 (en) * | 2006-09-21 | 2008-03-27 | Momentive Performance Materials Inc. | Polyurethane foam composition possessing modified silicone surfactants |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532478A (en) * | 2012-02-17 | 2012-07-04 | 北京光华纺织集团有限公司 | Method for synthesizing organosilicon modified polyurethane |
| 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 |
| CN104894992A (en) * | 2015-05-27 | 2015-09-09 | 安徽博昌电子科技股份有限公司 | 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 |
| 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 |
| 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 |
| 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 |
| CN117164810A (en) * | 2023-10-07 | 2023-12-05 | 东莞市森宏新材料科技有限公司 | Environment-friendly TPU shoe material 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102079806B (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102079806B (en) | Preparation of organic silicon modified polyurethane elastic body and application thereof | |
| Lee et al. | Green polyurethane from lignin and soybean oil through non-isocyanate reactions | |
| CN101050223B (en) | Tripolymer in isocyanic ester class modified by silicane or functional polusiloxane, preparation method | |
| CN101020738B (en) | Water-base polyurethane material and its preparation process and application | |
| EP2042542B1 (en) | Application of linear siloxanes and method for their manufacture | |
| CN103172823B (en) | For the preparation method of water lubricating compound polyurethane material | |
| CN104448183A (en) | Plant oil-based polyurethane composite material and preparation method thereof | |
| CN1208365C (en) | Method for preparing amino silicone oil modified polyurethane | |
| CN107216845A (en) | A kind of environment-friendly type end siloxy group polyurethane sealant and preparation method thereof | |
| CN103998500B (en) | Comprise the single-layer flexible foams of polyurethane gle | |
| CN102757728A (en) | Moisture-solidified antifouling paint composition | |
| CN108219096B (en) | Surface-hydrophobic buffer material and preparation method and application thereof | |
| CN111040113A (en) | Hydrophilic sponge material and preparation method thereof | |
| CN109517125A (en) | A kind of microporous polyurethane material and preparation method thereof with nonslip properties | |
| CN107522864A (en) | A kind of silane modified polymer and preparation method thereof | |
| CN110527059A (en) | A kind of low temperature perception memory foam and preparation method based on air and structural support | |
| CN103012725A (en) | Polyurethane raw liquid for rubber rolls available for mould-free casting | |
| CN103820019A (en) | Water-based polyurethane-containing stripping coating and preparation method thereof | |
| CN115028797A (en) | Organic silicon modified polyurethane elastomer and preparation method thereof | |
| Vaidya et al. | Recent developments in waterborne polyurethane dispersions (WPUDs): a mini-review on thermal and mechanical properties improvement | |
| Ren et al. | Triethoxysilane end-functional branched waterborne polyurethane adhesives for leather substrates | |
| CN105732935B (en) | A kind of preparation method of microporous polyurethane elastomer | |
| CN102532475A (en) | Polyurea resin compound and hardener | |
| CN103608374A (en) | High-value polyurethane elastomers and production thereof | |
| CN107936216A (en) | A kind of organic-silicon-modified Isocyanate prepolymers body of no-solvent type use for synthetic leather and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130515 Termination date: 20131215 |