CN116874717A - Thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN116874717A CN116874717A CN202210344254.XA CN202210344254A CN116874717A CN 116874717 A CN116874717 A CN 116874717A CN 202210344254 A CN202210344254 A CN 202210344254A CN 116874717 A CN116874717 A CN 116874717A
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- polyurethane elastomer
- thermoplastic polyurethane
- polyether polyol
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 44
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 44
- 229920001971 elastomer Polymers 0.000 title claims abstract description 38
- 239000000806 elastomer Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 45
- 229920000570 polyether Polymers 0.000 claims abstract description 45
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 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 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 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 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- 230000000704 physical effect Effects 0.000 description 10
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- -1 tetrahydrofuran cations Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention relates to a thermoplastic polyurethane elastomer and a preparation method thereof, which mainly solve the problems of high raw material cost and complex process in the prior art for preparing the thermoplastic polyurethane elastomer by PTMEG. The invention adopts a novel thermoplastic polyurethane elastomer, which comprises the following components in parts by weight: 40 to 50 parts of polytetramethylene ether glycol, 5 to 20 parts of polyether polyol, 18 to 20 parts of chain extender, 0.01 to 0.2 part of catalyst and 65 to 70 parts of isocyanate; the polyether polyol has the molecular weight of 600-3000, the functionality of 2-6 and the primary hydroxyl content of more than 90%, which solves the problem well and can be used in the industrial production of thermoplastic polyurethane elastomer.
Description
Technical Field
The invention relates to a thermoplastic polyurethane elastomer and a preparation method thereof.
Background
Thermoplastic polyurethane elastomers, TPU for short, are high molecular materials which can be heated, plasticized and dissolved in solvents, and are generally block copolymers formed by addition polymerization of polyalcohol (polyether or polyester) and polyisocyanate (MDI, TDI, HDI, IPDI or TMXDI) under the action of catalysts such as organotin, organozinc, organobismuth and the like. The structure of the TPU determines that the TPU has excellent properties such as high strength, high wear resistance, tear resistance, chemical corrosion resistance, high elasticity and the like, and meanwhile, the TPU also has good processability, which determines that the TPU becomes one of important thermoplastic elastomer materials and is widely applied to the fields of pipes, films, automobiles, papermaking textiles, wires and cables, medicine and health, ship materials and the like.
The thermoplastic polyurethane elastomer prepared from polyether polyol is called polyether TPU, and the flexible long chain of the polyether polyol determines the advantages of low temperature resistance, hydrolysis resistance, high elasticity and the like of the polyether TPU, but has poor mechanical properties such as hardness, tensile tearing and the like. Polytetrahydrofuran ether glycol (PTMEG) is a linear polyether glycol obtained by ring opening tetrahydrofuran cations, and a thermoplastic polyurethane elastomer synthesized by PTMEG and diisocyanate has the advantages of high tensile strength, wear resistance, flex fatigue resistance, small hysteresis loss, good rebound resilience and the like, and has been successfully applied to a plurality of fields. However, PTMEG has high raw material cost, complex synthesis process, high equipment requirement and low conversion rate, thus limiting the large-scale production of PTMEG.
Chinese patent CN111499826a discloses a thermoplastic polyurethane elastomer and a method for preparing the same. The thermoplastic polyurethane elastomer comprises the following raw material components in parts by weight: 50-80 parts of polyether polyol, 20-50 parts of polyester polyol, 77-92 parts of isocyanate, 17-28 parts of chain extender and 0.1-0.12 part of catalyst, wherein the polyether polyol is polyethylene glycol and/or polypropylene glycol. The invention discloses a preparation method of a thermoplastic polyurethane elastomer, which adopts polyethylene glycol and/or polypropylene glycol as main raw materials, and utilizes polyester polyol to improve a block structure, thereby improving the mechanical properties of the thermoplastic polyurethane elastomer. However, the invention utilizes the addition of polyester polyol to achieve the aim of improving mechanical properties, and the polyester polyol has the defects of high viscosity and easy hydrolysis.
The invention aims to solve the problems of high production cost and complex process, and simultaneously, the obtained thermoplastic elastomer still maintains good mechanical properties, and the polyether polyol can replace part of PTMEG used in TPU, reduces the demand quantity for PTMEG.
Disclosure of Invention
One of the technical problems to be solved by the invention is that in the prior art, when PTMEG is used for preparing the thermoplastic polyurethane elastomer, the raw material cost is high and the process is complex, and the novel thermoplastic polyurethane elastomer is provided. The second technical problem to be solved by the invention is to provide a preparation method of the thermoplastic polyurethane elastomer corresponding to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: the thermoplastic polyurethane elastomer comprises the following components in parts by weight: 40 to 50 parts of polytetramethylene ether glycol, 5 to 20 parts of polyether polyol, 18 to 20 parts of chain extender, 0.01 to 0.2 part of catalyst and 65 to 70 parts of isocyanate; wherein the molecular weight of the polyether polyol is 600-3000, the functionality is 2-6, and the primary hydroxyl content is more than 90%.
In the above technical solution, preferably, the molecular weight of the polytetramethylene ether glycol is 800-2000; the chain extender is at least one selected from ethylene glycol, propylene glycol, 1, 4-butanediol or hexanediol; the catalyst is at least one selected from organic tin or organic bismuth; the isocyanate is at least one selected from diphenylmethane-4, 4' -diisocyanate, toluene diisocyanate and hexamethylene diisocyanate.
In the above technical scheme, preferably, the weight part ratio of the polytetramethylene ether glycol to the polyether polyol is 1:2-9.
In the above technical scheme, preferably, the preparation method of the polyether polyol comprises the following steps:
(1) Adding at least one initiator of diethylene glycol, propylene glycol, glycerol, pentaerythritol or sorbitol into a pressure-resistant reaction kettle, using potassium hydroxide as a catalyst, replacing air in the kettle with nitrogen, keeping the vacuum state in the kettle, stirring slowly and heating to 115-120 ℃;
(2) Propylene oxide I is introduced into the kettle at a constant speed under the pressure of minus 0.1Mpa to minus 0.01Mpa, the pressure is controlled to be less than or equal to 0.4Mpa, and the kettle is cured for 2 to 4 hours;
(3) Then introducing mixed alkane of propylene oxide II and ethylene oxide I into the kettle under the pressure state of micro positive pressure of 0.01Mpa-0.05Mpa, controlling the pressure to be less than or equal to 0.4Mpa, and curing for 2-4 h; wherein the mass ratio of the epoxypropane II to the epoxyethane I is 1:1-3;
(4) Introducing ethylene oxide II into the kettle under the pressure state of micro-positive pressure of 0.01Mpa-0.05Mpa, controlling the pressure to be less than or equal to 0.4Mpa, and curing for 2-4 h; obtaining crude polyether;
(5) Refining the crude polyether to obtain a final product polyether polyol; wherein the ethylene oxide II accounts for 10-20% of the total mass of the crude polyether.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows:
the preparation method of the thermoplastic polyurethane elastomer comprises the following steps:
(1) Adding 40-50 parts of polytetramethylene ether glycol and 5-20 parts of polyether polyol into a reactor, starting stirring, controlling the stirring speed to be 1400-1800 r/min, carrying out vacuum dehydration at 85-95 ℃ for 1.5-3 h, and then adding 0.01-0.2 part of catalyst into a reaction kettle; stirring to uniformly mix the materials to form a mixture A;
(2) The method comprises the steps of accurately metering and introducing 65-70 parts of mixture A, 65-70 parts of isocyanate and 18-20 parts of chain extender into a double-screw premixing unit with the temperature of 55-75 ℃ and the rotating speed of 350-450 rpm through a metering pump and a flowmeter, extruding through a reactive double-screw extruder with the temperature of 180-210 ℃ and the rotating speed of 180-220 rpm, reacting for 55-70 seconds, and finally granulating under water and standing for 12-18 hours at the temperature of 80-90 ℃ to obtain the final product thermoplastic polyurethane elastomer.
The invention provides a thermoplastic polyurethane elastomer, which is prepared by adopting polyether polyol with high primary hydroxyl content to replace part PTMEG for producing the thermoplastic polyurethane elastomer, so that the raw material cost is reduced, and simultaneously, the hardness, the tensile strength and the elongation at break of the prepared thermoplastic polyurethane elastomer all meet the use requirements, and the better technical effect is achieved.
Detailed Description
[ example 1 ]
The preparation method of the crude ether initiator comprises the following steps: 228g of propylene glycol as an initiator and 3.1g of potassium hydroxide as a catalyst were added to a 2L high temperature and high pressure resistant reaction vessel equipped with a stirring device. The air in the kettle is replaced by nitrogen, the vacuum state in the kettle is kept, the stirring is carried out slowly, the temperature is raised to 115 ℃, and meanwhile, the storage tank of propylene oxide is replaced by nitrogen. Propylene oxide is introduced into the kettle at a constant speed under the pressure of-0.01 Mpa, the pressure in the kettle is kept to be not more than 0.4Mpa, 972g is added, and the kettle is cured for 3 hours, so that the crude ether initiator-1 is obtained, the hydroxyl value is 280.5mgKOH/g, and the base value is 2.5mgKOH/g.
480g of crude ether initiator-1, 1.2g of potassium hydroxide was added as a catalyst to a 2L high temperature and high pressure resistant reaction vessel equipped with a stirring device. The air in the kettle is replaced by nitrogen, the vacuum state in the kettle is maintained, the kettle is stirred slowly and heated to 115 ℃, and meanwhile, the storage tank of PO is replaced by nitrogen. PO is introduced into the kettle at uniform speed under the pressure of-0.01 Mpa, the pressure in the kettle is kept not to exceed 0.4Mpa, 440g is added, and the kettle is cured for 3h. 100g of PO/EO mixed alkyl (PO 40g, EO 60 g) was introduced into the autoclave under a slight positive pressure, and the mixture was aged for 2 hours. 180g of EO is introduced into a kettle under a micro-positive pressure state, and the kettle is cured for 2 hours to obtain the crude ether I. 1000g of crude ether I was transferred to a 2L refining kettle, 65g of water was added, stirring was started, the temperature was raised to 85℃and 6.5g of magnesium silicate and 6.7 of aluminum silicate adsorbent were added to the kettle, stirring was started for 1 hour, vacuum dehydration was started, and the temperature was gradually raised to 115 ℃. Dehydrating until the water content is less than 0.1%, filtering to remove silicate to obtain polyether polyol-I, wherein specific physical property indexes are shown in Table 1.
[ example 2 ]
240g of crude ether initiator-1, 3.1g of potassium hydroxide was added as a catalyst to a 2L high temperature and high pressure resistant reaction vessel equipped with a stirring device. The air in the kettle is replaced by nitrogen, the vacuum state in the kettle is maintained, the kettle is stirred slowly and heated to 115 ℃, and meanwhile, the storage tank of PO is replaced by nitrogen. PO is introduced into the kettle at uniform speed under the pressure of-0.01 Mpa, the pressure in the kettle is kept not to exceed 0.4Mpa, 660g is added, and the kettle is cured for 3h. Under a slight positive pressure, 120g of PO/EO mixed alkyl (PO 60g, EO 60 g) was introduced into the autoclave, followed by aging for 2 hours. Under the micro-positive pressure state, 180g of EO is introduced into the kettle, and the kettle is cured for 2 hours to obtain crude ether II. 1000g of crude ether II was transferred to a 2L refining kettle, 72g of water was added, stirring was started, the temperature was raised to 85℃and 6.9g of magnesium silicate and 7.1 g of aluminum silicate adsorbent were added to the kettle, stirring was started for 1 hour, vacuum dehydration was started, and the temperature was gradually raised to 115 ℃. Dehydrating until the water content is less than 0.1%, filtering to remove silicate to obtain polyether polyol-II, wherein specific physical property indexes are shown in Table 1.
[ example 3 ]
160g of glycerin as an initiator and 3.2g of potassium hydroxide as a catalyst were added to a 2L high temperature and high pressure resistant reaction vessel equipped with a stirring device. The air in the kettle is replaced by nitrogen, the vacuum state in the kettle is kept, the stirring is carried out slowly, the temperature is raised to 115 ℃, and meanwhile, the storage tank of propylene oxide is replaced by nitrogen. Propylene oxide is introduced into the kettle at the average speed under the pressure of-0.01 Mpa, the pressure in the kettle is kept to be not more than 0.4Mpa, 1057g is added, and the kettle is cured for 3 hours, thus obtaining the crude ether initiator-3, the hydroxyl value of which is 240.4mgKOH/g and the base value of which is 2.6mgKOH/g.
280g of crude ether initiator-3, 3.5g of potassium hydroxide are added as a catalyst to a 2L high temperature and high pressure resistant reaction kettle equipped with a stirring device. The air in the kettle is replaced by nitrogen, the vacuum state in the kettle is maintained, the kettle is stirred slowly and heated to 115 ℃, and meanwhile, the storage tank of PO is replaced by nitrogen. PO is introduced into the kettle at uniform speed under the pressure of-0.01 Mpa, the pressure in the kettle is kept not to exceed 0.4Mpa, 440g is added, and the kettle is cured for 3h. 240g of PO/EO mixed alkane (PO 120g, EO 120 g) was introduced into the autoclave under a slight positive pressure, and the mixture was aged for 2 hours. 240g of EO is introduced into the kettle under the micro-positive pressure state, and the kettle is cured for 2 hours to obtain the crude ether III. 1000g of crude ether III was transferred to a 2L refining kettle, 76g of water was added, stirring was started, the temperature was raised to 85 ℃, 7.2g of magnesium silicate and 7.3 of aluminum silicate adsorbent were added to the kettle, stirring was started for 1 hour, vacuum dehydration was started, and the temperature was gradually raised to 115 ℃. Dehydrating until the water content is less than 0.1%, filtering to remove silicate to obtain polyether polyol-III, wherein specific physical property indexes are shown in table 1.
[ example 4 ]
(1) 5.5 parts of polyether polyol-I obtained in example 1 and 49.5 parts of PTMEG-1000 (Basf company) are weighed in parts by weight, added into a reactor, the stirring speed is controlled to 1600r/min, vacuum dehydration is carried out for 2 hours at 90 ℃, then 0.03 part of catalyst dibutyltin dilaurate is added into the reactor, and the mixture is stirred to be uniformly mixed to form a mixture A;
(2) The mixture A and isocyanate are MDI, micromolecular diol is 1,4 Butanediol (BDO), the three components are respectively introduced into a double-screw premixing unit with the temperature of 60 ℃ and the rotating speed of 400rpm through a metering pump and a flow meter according to the proportion of 55 parts, 65 parts and 18 parts, then are extruded through a reactive double-screw extruder with the temperature of 200 ℃ and the rotating speed of 200rpm, the reaction time is 1min, and finally, the finished thermoplastic polyurethane elastomer is obtained after underwater pelleting and drying at the temperature of 85 ℃ for 15h, and the physical property test data are shown in Table 2.
[ example 5 ]
(1) Adding 12 parts by weight of polyether polyol-II and 1000 48 parts by weight of PTMEG-1000 48 parts by weight obtained in example 2 into a reactor, controlling the stirring speed to 1600r/min, carrying out vacuum dehydration at 90 ℃ for 2 hours, then adding 0.05 part by weight of dibutyltin dilaurate serving as a catalyst, and stirring to uniformly mix the materials to form a mixture A;
(2) The mixture A and isocyanate are MDI, micromolecular diol is 1,4 Butanediol (BDO), the three components are respectively introduced into a double-screw premixing unit with the temperature of 60 ℃ and the rotating speed of 400rpm through a metering pump and a flow meter according to the proportion of 60 parts, 70 parts and 20 parts, then are extruded through a reactive double-screw extruder with the temperature of 200 ℃ and the rotating speed of 200rpm, the reaction time is 1min, and finally, the finished thermoplastic polyurethane elastomer is obtained after underwater pelleting and drying at the temperature of 85 ℃ for 15h, and the physical property test data are shown in Table 2.
[ example 6 ]
(1) 20 parts of polyether polyol-III obtained in example 3 and 1000 40 parts of PTMEG-are added into a reactor, the stirring speed is controlled to 1600r/min, vacuum dehydration is carried out for 2 hours at 90 ℃, then 0.04 part of catalyst dibutyl tin dilaurate is added into the mixture, and the mixture is stirred to be uniformly mixed to form a mixture A;
(2) The mixture A and isocyanate are MDI, micromolecular diol is 1,4 Butanediol (BDO), the three components are respectively introduced into a double-screw premixing unit with the temperature of 60 ℃ and the rotating speed of 400rpm through a metering pump and a flow meter according to the proportion of 60 parts, 68 parts and 20 parts, then are extruded through a reactive double-screw extruder with the temperature of 200 ℃ and the rotating speed of 200rpm, the reaction time is 1min, and finally, the finished thermoplastic polyurethane elastomer is obtained after underwater pelleting and 15h drying at the temperature of 85 ℃, and the physical property test data are shown in Table 2.
[ comparative example 1 ]
(1) 60 parts of polytetrahydrofuran ether glycol PTMEG-1000 (Basf company) is weighed according to parts by weight and added into a reactor, the stirring speed is controlled to 1600r/min, the vacuum dehydration is carried out for 2 hours at 90 ℃, then 0.05 part of catalyst dibutyltin dilaurate is added into the reactor, and the mixture is stirred to be uniformly mixed to form a mixture A;
(2) The mixture A and isocyanate are MDI, micromolecular diol is 1,4 Butanediol (BDO), the three components are respectively introduced into a double-screw premixing unit with the temperature of 60 ℃ and the rotating speed of 400rpm through a metering pump and a flow meter according to the proportion of 60 parts and 65 parts and the precise metering of 18 parts, then are extruded through a reactive double-screw extruder with the temperature of 200 ℃ and the rotating speed of 200rpm, the reaction time is 1min, and finally, the finished thermoplastic polyurethane elastomer is obtained after underwater granulating and standing for 15h at the temperature of 85 ℃ for drying, and the physical property test data are shown in Table 2.
[ comparative example 2 ]
(1) Adding 5.5 parts of CHE-210 (Changhua chemical technology Co., ltd.) and 49.5 parts of polytetrahydrofuran ether glycol PTMEG-1000 (Basf Co.) into a reactor, controlling the stirring speed to 1600r/min, vacuum dehydrating for 2 hours at 90 ℃, adding 0.05 part of dibutyltin dilaurate serving as a catalyst, and stirring to uniformly mix to form a mixture A;
(2) The mixture A and isocyanate are MDI, micromolecular diol is 1,4 Butanediol (BDO), the three components are respectively introduced into a double-screw premixing unit with the temperature of 60 ℃ and the rotating speed of 400rpm through a metering pump and a flow meter according to the proportion of 55 parts, 65 parts and 18 parts, then are extruded through a reactive double-screw extruder with the temperature of 200 ℃ and the rotating speed of 200rpm, the reaction time is 1min, and finally, the finished thermoplastic polyurethane elastomer is obtained after underwater pelleting and drying at the temperature of 85 ℃ for 15h, and the physical property test data are shown in Table 2.
Table 1 physical Properties index of polyether polyol obtained in examples 1 to 3
Table 2 physical Property test data of thermoplastic polyurethane elastomer obtained in examples 4 to 6 and comparative examples 1 to 2
Example 4, example 5, example 6 are polyurethane elastomers made from polyether polyol-I, polyether polyol-II, polyether polyol-III in place of 10%,20%,33% PTMEG-1000, respectively. From the test results, it can be seen that the replacement of 10% of PTMEG-1000 has little effect on the mechanical properties of the elastomer, the mechanical properties of the PTMEG-1000 elastomer are slightly reduced by replacing 20% of PTMEG-1000, and when 33% of PTMEG-1000 is replaced, the mechanical properties are reduced but still much better than those of the PTMEG-1000 by replacing 10% of PTMEG-1000 with polypropylene glycol, which indicates that the polyether polyol with the structure can be used for replacing part of PTMEG when being used for preparing the polyurethane elastomer. The polyether for producing the polyurethane elastomer has larger consumption, and the PTMEG has complex production process and high cost, so the production of the polyurethane elastomer is limited. The polyether has the advantages of simple structure, high content of terminal primary hydroxyl, low cost of raw materials, easy mass production, low cost due to the fact that PTMEG is partially replaced for producing the polyurethane elastomer, and almost no influence on the properties such as hardness, tensile strength, elongation at break, tear strength and the like. The polyether polyol in comparative example 2 has a pure propylene oxide structure, and it can be seen that the mechanical properties of the polyurethane elastomer obtained are very poor. The examples listed in the invention can effectively replace PTMEG to be applied to the production of thermoplastic polyurethane elastomer, the effect is equivalent to that of polytetrahydrofuran ether glycol, but the invention is not limited to the examples, and other similar structural proportion adjustment belongs to the polyether polyol and is protected.
Claims (5)
1. The thermoplastic polyurethane elastomer comprises the following components in parts by weight: 40 to 50 parts of polytetramethylene ether glycol, 5 to 20 parts of polyether polyol, 18 to 20 parts of chain extender, 0.01 to 0.2 part of catalyst and 65 to 70 parts of isocyanate; wherein the molecular weight of the polyether polyol is 600-3000, the functionality is 2-6, and the primary hydroxyl content is more than 90%.
2. The thermoplastic polyurethane elastomer according to claim 1, wherein the molecular weight of the polytetramethylene ether glycol is 800 to 2000; the chain extender is at least one selected from ethylene glycol, propylene glycol, 1, 4-butanediol or hexanediol; the catalyst is at least one selected from organic tin or organic bismuth; the isocyanate is at least one selected from diphenylmethane-4, 4' -diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.
3. The thermoplastic polyurethane elastomer according to claim 1, wherein the weight ratio of the polytetramethylene ether glycol to the polyether polyol is 1:2-9.
4. The thermoplastic polyurethane elastomer of claim 1, wherein the polyether polyol is prepared by a process comprising the steps of:
(1) Adding at least one of diethylene glycol, propylene glycol, glycerol, pentaerythritol or sorbitol as an initiator, potassium hydroxide as a catalyst into a pressure-resistant reaction kettle, replacing air in the kettle with nitrogen, keeping the vacuum state in the kettle, stirring slowly and heating to 115-120 ℃;
(2) Propylene oxide I is introduced into the kettle at a constant speed under the pressure of minus 0.1Mpa to minus 0.01Mpa, the pressure is controlled to be less than or equal to 0.4Mpa, and the kettle is cured for 2 to 4 hours;
(3) Then introducing mixed alkane of propylene oxide II and ethylene oxide I into the kettle under the pressure state of micro positive pressure of 0.01Mpa-0.05Mpa, controlling the pressure to be less than or equal to 0.4Mpa, and curing for 2-4 h; wherein the mass ratio of the epoxypropane II to the epoxyethane I is 1:1-3;
(4) Introducing ethylene oxide II into the kettle under the pressure state of micro-positive pressure of 0.01Mpa-0.05Mpa, controlling the pressure to be less than or equal to 0.4Mpa, and curing for 2-4 h; obtaining crude polyether;
(5) Refining the crude polyether to obtain a final product polyether polyol; wherein the ethylene oxide II accounts for 10-20% of the total mass of the crude polyether.
5. A process for preparing the thermoplastic polyurethane elastomer of claim 1, comprising the steps of:
(1) Adding 40-50 parts of polytetramethylene ether glycol and 5-20 parts of polyether polyol into a reactor, starting stirring, controlling the stirring speed to be 1400-1800 r/min, carrying out vacuum dehydration at 85-95 ℃ for 1.5-3 h, and then adding 0.01-0.2 part of catalyst into a reaction kettle; stirring to uniformly mix the materials to form a mixture A;
(2) The method comprises the steps of accurately metering and introducing 65-70 parts of mixture A, 65-70 parts of isocyanate and 18-20 parts of chain extender into a double-screw premixing unit with the temperature of 55-75 ℃ and the rotating speed of 350-450 rpm through a metering pump and a flowmeter, extruding through a reactive double-screw extruder with the temperature of 180-210 ℃ and the rotating speed of 180-220 rpm, reacting for 55-70 seconds, and finally granulating under water and standing for 12-18 hours at the temperature of 80-90 ℃ to obtain the final product thermoplastic polyurethane elastomer.
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