CN115850642A - Preparation method of high-performance polyurethane elastomer - Google Patents
Preparation method of high-performance polyurethane elastomer Download PDFInfo
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- CN115850642A CN115850642A CN202211546196.5A CN202211546196A CN115850642A CN 115850642 A CN115850642 A CN 115850642A CN 202211546196 A CN202211546196 A CN 202211546196A CN 115850642 A CN115850642 A CN 115850642A
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- polyurethane elastomer
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- performance polyurethane
- chain extender
- reaction system
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 5
- 230000003014 reinforcing effect Effects 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- -1 polyethylene adipate Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a high-performance polyurethane elastomer. The preparation method of the high-performance polyurethane elastomer comprises the following steps: (1) Mixing and heating polymer polyol and polyisocyanate to carry out prepolymerization reaction; (2) Adding a catalyst and a chain extender into the reaction system in the step (1) for heating reaction; (3) Adding bridged siloxane into the reaction system in the step (2), and uniformly stirring to obtain a material to be mixed; (4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer. The polyurethane elastomer prepared by adding the reinforcing modifier bridging siloxane into a reaction system for synthesizing polyurethane has excellent mechanical property, hydrolysis resistance and oil resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a high-performance polyurethane elastomer.
Background
The polyurethane elastomer has excellent comprehensive properties such as high strength, high toughness, wear resistance, oil resistance and the like, has good processing performance, and is widely applied to various fields of national life such as cables, sealing elements, transmission belts, steel rolling rubber rollers and the like. With the development of science and technology, the application field of polyurethane elastomers is continuously expanded, and products in practical application have higher requirements on the performance of the polyurethane elastomers.
Currently, inorganic filler loading is the primary method of polyurethane elastomer reinforcement. The inorganic filler generally has the advantages of high strength, high rigidity, heat resistance, low price and the like, and when the inorganic filler is added into the polyurethane elastomer to prepare the composite material, the cost can be reduced, and the mechanical property, the heat resistance and the like of the material can be improved. Common inorganic fillers include: nano particles (Nano SiO) 2 Nano TiO 2 2 Nano CaCO, nano-grade CaCO 3 ) Layered silicate clay minerals (montmorillonite and attapulgite), short fibers (carbon fibers and glass fibers), carbon nanotubes and the like. However, the compatibility of the inorganic filler and polyurethane is poor, the inorganic filler is difficult to uniformly distribute in the system, and the surface modification needs to be carried out on the filler so as to improve the two-phase interface and improve the dispersion uniformity and stability. If the surface treatment cannot be performed efficiently, the material properties will be deteriorated.
Crosslinking technology is also an effective way to improve the performance of polyurethane elastomers. Chinese patent application document (publication No. CN 114369220A) discloses a thermoplastic polyurethane elastomer nano composite material and a preparation method thereof, and reactive nano silicon dioxide introduced in the polymerization process of a thermoplastic polyurethane elastomer is expected to solve the problem that the toughness of TPU cannot be maintained while the strength and the wear resistance of TPU are improved in the prior art. However, the reactive nano-silica is used as an inorganic particle, the number of active groups on the surface which can participate in the reaction is limited, the chemical bonding capability with the polyurethane elastomer is weak, and the mechanical property of the obtained composite material is poor.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a high-performance polyurethane elastomer which can provide a polyurethane elastomer having good mechanical properties and excellent hydrolysis resistance and oil resistance.
The preparation method of the high-performance polyurethane elastomer in the technical scheme of the invention comprises the following steps:
(1) Mixing and heating polymer polyol and polyisocyanate to carry out prepolymerization reaction;
(2) Adding a catalyst and a chain extender into the reaction system in the step (1) for heating reaction;
(3) Adding bridged siloxane into the reaction system in the step (2), and uniformly stirring to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer.
Adding a reinforcing modifier bridging siloxane into a reaction system for synthesizing polyurethane, pre-embedding the reinforcing modifier bridging siloxane in a polyurethane elastomer, and hydrolyzing the bridging siloxane embedded in the elastomer in a moist-heat environment and performing mutual polycondensation in the process of heating and forming the elastomer so as to form a cross-linked network structure in the process of forming the elastomer and improve the mechanical property of the polyurethane elastomer.
Further, the polymer polyol is one or two of polyester polyol and polyether polyol. Preferably, the polyester polyol includes, but is not limited to, any one of polyethylene adipate, polybutylene adipate, or polybutylene adipate, and the polyether polyol includes, but is not limited to, any one of polytetrahydrofuran glycol or polypropylene glycol.
Further, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI).
Further, the chain extender is one or two of diamine chain extender and alcohol chain extender, preferably, the diamine chain extender includes but is not limited to 3,3 '-dichloro-4,4' -diaminodiphenylmethane (MOCA), and any one of dimethylthiotoluenediamine (DMTDA), and the alcohol chain extender includes but is not limited to any one of 1,4-Butanediol (BDO), ethylene Glycol (EG), and Trimethylolpropane (TMP).
Further, the catalyst is one or more of stannous octoate, dibutyltin dioctoate and dibutyltin laurate.
Further, the bridging siloxane is one or more of bis (3-triethoxysilylpropyl) amine (BTESPA), bis- (3- (triethoxysilyl) propyl) -disulfide (TSDS), 1,2-bis (triethoxysilyl) ethane (BTESE).
The structural formula of bis (3-triethoxysilylpropyl) amine is as follows:
the structural formula of bis- (3- (triethoxysilane) propyl) -disulfide is as follows:
1,2-bis (triethoxysilyl) ethane has the following structural formula:
further, the weight parts of the raw materials are as follows: 45-70 parts of polymer polyol, 15-30 parts of polyisocyanate, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.5-3.0 parts of reinforcing modifier bridging siloxane.
Further, adding a catalyst, a chain extender and a mineral filler into the reaction system of the step (1) and heating for reaction together.
Further, the mineral filler is one of calcium carbonate, talcum powder, titanium dioxide, silicon dioxide and montmorillonite.
Furthermore, the weight portion of the mineral filler is more than 0 portion and less than or equal to 10 portions.
Further, the temperature of the prepolymerization reaction in the step (1) is 20-80 ℃, and the time is 1-4 h.
Further, the heating reaction in the step (2) is carried out at the temperature of 20-80 ℃ for 1-4 h.
Further, in the step (3), the bridging siloxane is diluted by an organic solvent before being added into the reaction system, and the mass ratio of the bridging siloxane to the organic solvent is 1:5-10.
Further, the organic solvent is one or more of ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide.
A high-performance polyurethane elastomer is prepared by the preparation method of the high-performance polyurethane elastomer.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The reinforcing modifier bridged siloxane is added into a reaction system for synthesizing polyurethane, and the prepared polyurethane elastomer has excellent mechanical property, hydrolysis resistance and oil resistance;
(2) The bridged siloxane is hydrolyzed and mutually condensed in the elastomer heating and forming process to form a cross-linked network structure in the elastomer forming process, so that the mechanical property of the polyurethane elastomer is improved;
(3) The bridging siloxane adopted by the invention is further one or more of bis (3-triethoxysilylpropyl) amine, bis- (3- (triethoxysilylpropyl) -disulfide and 1,2-bis (triethoxysilyl) ethane, the siloxane with the structure has the advantages of mild polycondensation reaction conditions, stable product structure and good mechanical property, and can simultaneously improve the mechanical property, hydrolysis resistance and oil resistance of the polyurethane elastomer;
(4) The preparation method has the advantages of simple process, low cost, environmental friendliness and remarkable effect.
Detailed Description
The technical solutions of the present invention are further described and illustrated below by specific examples, it should be understood that the specific examples described herein are only for the purpose of facilitating understanding of the present invention, and are not intended to be specific limitations of the present invention. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1
The preparation method of the high-performance polyurethane elastomer comprises the following steps:
(1) Uniformly mixing 45 parts of polyethylene glycol adipate and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of catalyst stannous octoate, 3.0 parts of chain extender 3,3 '-dichloro-4,4' -diaminodiphenylmethane and 6.9 parts of calcium carbonate into the reaction system in the step (1), and uniformly stirring at 25 ℃ for reacting for 4 hours;
(3) Dissolving 2.0 parts of bis (3-triethoxysilylpropyl) amine in 13.0 parts of ethanol, adding into the reaction system in the step (2), and uniformly stirring to remove the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Example 2
The preparation method of the high-performance polyurethane elastomer of the embodiment comprises the following steps:
(1) Uniformly mixing 50 parts of polytetrahydrofuran diol and 30 parts of hexamethylene diisocyanate at 80 ℃ and reacting for 1 hour;
(2) Adding 0.05 part of catalyst dibutyltin laurate, 3.0 parts of chain extender glycol and 5.0 parts of silicon dioxide into the reaction system in the step (1), and uniformly stirring at 80 ℃ for reacting for 1h;
(3) Dissolving 1.5 parts of bis (3-triethoxysilylpropyl) amine in 10.5 parts of ethanol, adding into the reaction system in the step (2), uniformly stirring, and removing the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Example 3
The preparation method of the high-performance polyurethane elastomer comprises the following steps:
(1) Uniformly mixing 45 parts of polypropylene glycol and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of catalyst stannous octoate, 8.0 parts of chain extender trimethylolpropane and 5.0 parts of montmorillonite into the reaction system in the step (1), and uniformly stirring at 80 ℃ to react for 1 hour;
(3) Dissolving 1.0 part of bis (3-triethoxysilylpropyl) amine in 9.0 parts of ethanol, adding into the reaction system in the step (2), uniformly stirring, and removing the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Example 4
The preparation method of the high-performance polyurethane elastomer comprises the following steps:
(1) Uniformly mixing 70 parts of polybutylene adipate and 15 parts of diphenylmethane diisocyanate at 80 ℃, and reacting for 1 hour;
(2) Adding 0.05 part of catalyst stannous octoate, 8.0 parts of chain extender dimethylthiotoluenediamine and 1.95 parts of talcum powder into the reaction system in the step (1), and stirring uniformly at 80 ℃ for reacting for 1h;
(3) Dissolving 2.0 parts of bis- (3- (triethoxysilane) propyl) -disulfide in 13.0 parts of ethanol, adding into the reaction system in the step (2), uniformly stirring, and removing the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Example 5
The preparation method of the high-performance polyurethane elastomer comprises the following steps:
(1) Uniformly mixing 55 parts of polyethylene glycol adipate and 25 parts of isophorone diisocyanate at 60 ℃, and reacting for 2 hours;
(2) Adding 0.1 part of catalyst dibutyltin dioctoate, 5.0 parts of chain extender 1,4-butanediol and 5.0 parts of titanium dioxide into the reaction system in the step (1), and uniformly stirring at 60 ℃ for reacting for 2 hours;
(3) Dissolving 2.0 parts of 1,2-bis (triethoxysilyl) ethane in 13.0 parts of ethanol, adding into the reaction system in the step (2), uniformly stirring, and removing the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Example 6
This example differs from example 1 only in that bis (3-triethoxysilylpropyl) amine was added in an amount of 0.1 part in step (3).
Example 7
This example differs from example 1 only in that bis (3-triethoxysilylpropyl) amine was added in an amount of 5.0 parts in step (3).
Comparative example 1
The preparation method of the comparative example polyurethane elastomer comprises the following steps:
(1) Uniformly mixing 45 parts of polyethylene glycol adipate and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of catalyst stannous octoate, 3.0 parts of chain extender 3,3 '-dichloro-4,4' -diaminodiphenylmethane and 6.9 parts of calcium carbonate into the reaction system in the step (1), and uniformly stirring at 25 ℃ for reacting for 4 hours;
(3) Dissolving 2.0 parts of reactive silica in 13.0 parts of ethanol, adding the mixture into the reaction system in the step (2), and uniformly stirring to remove the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Comparative example 2
The preparation method of the polyurethane elastomer of the comparative example comprises the following steps:
(1) Uniformly mixing 45 parts of polyethylene glycol adipate and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of catalyst stannous octoate, 3.0 parts of chain extender 3,3 '-dichloro-4,4' -diaminodiphenylmethane and 6.9 parts of calcium carbonate into the reaction system in the step (1), and uniformly stirring at 25 ℃ for reacting for 4 hours;
(3) Dissolving 2.0 parts of silane coupling agent KH-550 in 13.0 parts of ethanol, adding into the reaction system in the step (2), uniformly stirring, and removing the solvent to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Comparative example 3
The preparation method of the polyurethane elastomer of the comparative example comprises the following steps:
(1) Uniformly mixing 45 parts of polyethylene glycol adipate and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of catalyst stannous octoate, 3.0 parts of chain extender 3,3 '-dichloro-4,4' -diaminodiphenylmethane and 6.9 parts of calcium carbonate into the reaction system in the step (1), and uniformly stirring at 25 ℃ for reacting for 4 hours;
(3) Dissolving 2.0 parts of tetraethoxysilane in 40 parts of ammonia water (27%), adding into the reaction system in the step (2), and heating and stirring at 40 ℃ for 1h to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
Comparative example 4
The preparation method of the polyurethane elastomer of the comparative example comprises the following steps:
(1) Uniformly mixing 45 parts of polyethylene glycol adipate and 30 parts of toluene diisocyanate at 25 ℃, and reacting for 4 hours;
(2) Adding 0.1 part of stannous octoate catalyst, 3.0 parts of chain extender 3,3 '-dichloro-4,4' -diaminodiphenylmethane and 6.9 parts of calcium carbonate into the reaction system in the step (1), uniformly stirring at 25 ℃ for reacting for 4 hours, and removing the solvent to obtain a material to be mixed;
(3) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer, wherein the temperature range of each section of the extruder is 160-220 ℃.
The polyurethane elastomers obtained in the above examples and comparative examples were tested for mechanical properties, water resistance and oil resistance, the water resistance was determined by testing the tensile strength and the elongation at break after being left at 80 ℃ for 168 hours, the oil resistance was determined by testing the tensile strength and the elongation at break after being left at 100 ℃ for 168 hours, and the property data are shown in table 1.
TABLE 1 polyurethane elastomer Properties data Table
As can be seen from the data in table 1, the polyurethane elastomer obtained in the present application has excellent mechanical properties, hydrolysis resistance and oil resistance. Example 6 when the amount of the bridged siloxane used is too small, the cross-linked network structure formed in the elastomer molding process is small, and the mechanical strength of the obtained polyurethane elastomer is poor; example 7 when the amount of the bridged siloxane is too large, a crosslinked network structure is formed in the elastomer molding process, and the obtained polyurethane elastomer has high mechanical strength, low elongation at break and poor elasticity; comparative examples 1 to 4 were obtained with or without modification with other types of silicon compounds, and the polyurethane elastomers obtained were inferior in mechanical properties, hydrolysis resistance and oil resistance.
Finally, it should be noted that the specific examples described herein are merely illustrative of the spirit of the invention and do not limit the embodiments of the invention. Various modifications, additions and substitutions for the embodiments described herein will occur to those skilled in the art, and all such embodiments are neither required nor possible. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (10)
1. A preparation method of a high-performance polyurethane elastomer is characterized by comprising the following steps:
(1) Mixing and heating polymer polyol and polyisocyanate to carry out prepolymerization reaction;
(2) Adding a catalyst and a chain extender into the reaction system in the step (1) for heating reaction;
(3) Adding bridged siloxane into the reaction system in the step (2), and uniformly stirring to obtain a material to be mixed;
(4) And extruding and granulating the materials to be mixed to obtain the high-performance polyurethane elastomer.
2. The method for preparing high-performance polyurethane elastomer according to claim 1, wherein the polymer polyol is one or both of polyester polyol and polyether polyol.
3. The method for preparing high-performance polyurethane elastomer according to claim 1, wherein the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
4. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein the chain extender is one or both of a diamine chain extender and an alcohol chain extender.
5. The method for preparing the high-performance polyurethane elastomer according to claim 1, wherein the catalyst is one or more of stannous octoate, dibutyltin dioctoate and dibutyltin laurate.
6. The method of claim 1, wherein the bridging siloxane is one or more of bis (3-triethoxysilylpropyl) amine, bis- (3- (triethoxysilyl) propyl) -disulfide, 1,2-bis (triethoxysilyl) ethane.
7. The preparation method of the high-performance polyurethane elastomer according to claim 1, wherein the weight parts of the raw materials are as follows: 45-70 parts of polymer polyol, 15-30 parts of polyisocyanate, 3-8 parts of chain extender, 0.05-0.1 part of catalyst and 0.5-3.0 parts of bridging siloxane.
8. The method for preparing a high-performance polyurethane elastomer according to claim 1, wherein the prepolymerization reaction in the step (1) is carried out at a temperature of 20 to 80 ℃ for 1 to 4 hours.
9. The method for preparing high-performance polyurethane elastomer according to claim 1, wherein the heating reaction in step (2) is carried out at a temperature of 20 to 80 ℃ for 1 to 4 hours.
10. A high-performance polyurethane elastomer obtained by the production method according to claim 1.
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