CN105399917A - Organic silicon modified thermoplastic polyurethane elastomer (TPU) and preparation method thereof - Google Patents
Organic silicon modified thermoplastic polyurethane elastomer (TPU) and preparation method thereof Download PDFInfo
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- CN105399917A CN105399917A CN201510740025.XA CN201510740025A CN105399917A CN 105399917 A CN105399917 A CN 105399917A CN 201510740025 A CN201510740025 A CN 201510740025A CN 105399917 A CN105399917 A CN 105399917A
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 25
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 25
- 229920001971 elastomer Polymers 0.000 title claims abstract description 9
- 239000000806 elastomer Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract 3
- 229910052710 silicon Inorganic materials 0.000 title abstract 3
- 239000010703 silicon Substances 0.000 title abstract 3
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 32
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 19
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 239000004970 Chain extender Substances 0.000 claims abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 3
- 229920002635 polyurethane Polymers 0.000 claims description 33
- 239000004814 polyurethane Substances 0.000 claims description 33
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000003384 small molecules Chemical group 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920002521 macromolecule Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 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 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 229940124543 ultraviolet light absorber Drugs 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 33
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 2
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/4825—Polyethers containing two 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
- C08G18/61—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of high polymer material research, and provides an organic silicon modified thermoplastic polyurethane elastomer (TPU) in order to overcome the defects of poor temperature resistance and hydrophobic property of the existing TPU. The elastomer consists of the following components in parts by weight: 20-60 parts of macromolecular dihydric alcohol, 2-10 parts of terminal hydroxyalkyl end-blocked polydimethylsiloxane, 10-20 parts of diisocyanate, 2-8 parts of a micromolecular chain extender, 0.1-0.5 part of a catalyst, 0.1-0.5 part of an antioxidant and 0.1-0.5 part of an ultraviolet light absorber. Due to the unique chemical structure and composition, organic silicon has a series of excellent properties, such as high temperature and low temperature resistance and hydrophobic property, which just can make up the defects of the TPU. The invention also provides a preparation method of the elastomer, the preparation method adopts a prepolymer two-step process and is less in side reaction, and the prepared TPU is good in structural regularity.
Description
Technical field
The invention belongs to macromolecular material research field, be specifically related to a kind of organic-silicon-modified Polyurethane Thermoplastic Elastomer and preparation method thereof.
Background technology
Polyurethane Thermoplastic Elastomer (hereinafter referred to as TPU) is the linear polymeric material be polymerized by macromolecule dihydric alcohol, vulcabond and small molecules dibasic alcohol or diamine.TPU is a kind of segmented copolymer, is reacted and forms soft section, form hard section by vulcabond and small molecules diol reaction by vulcabond and macromolecule dihydric alcohol, and the soft section of molecular structure replaced with hard section forms microfacies district and produce micron-scale phase separation; In addition due to the existence of a large amount of polar group, can hydrogen bond be formed with intermolecular and produce physical crosslinking point in the molecule of TPU, thus when being out of shape, also can not slide between macromolecular chain, and present elasticity, and when heated, after cross-linking set melting, macromolecular chain is movable, just flows.The constructional feature of TPU uniqueness makes its process industrial art performance with plastics and the physical and mechanical properties of rubber.TPU is solvable fusible, not only has the premium propertiess such as durometer level is wide, intensity is high, wear-resisting, oil resistant, low temperature flexibility are good; And can significantly change product performance and purposes by adjustment raw material and proportioning thereof.Be widely used in the aspects such as health care, electronic apparatus, industry and physical culture.
Containing the amino-formate bond (-NH-COO-) structure that large quantitative response generates in the molecular structure of TPU, the carbamate that simultaneously excessive isocyanic ester can be formed with reaction respectively and urea react further and form allophanate and biuret structure, elastomeric mechanical property can be improved although it is so, but the thermostability of these groups is poor, thus the resistance toheat of TPU is poor, generally, its life-time service temperature can not more than 80 DEG C, and short-period used temperature can not more than 120 DEG C; In addition, TPU shows not good enough in water tolerance, and the deficiency of these performances limits the range of application of TPU.
Summary of the invention
For solving existing TPU temperature tolerance and hydrophobic deficiency, the invention provides a kind of organic-silicon-modified Polyurethane Thermoplastic Elastomer, organosilicon has a series of excellent properties because of the chemical structure composition of its uniqueness, as resistant of high or low temperature, hydrophobicity, just in time can make up the above-mentioned defect of TPU; The present invention also provides its preparation method, and adopt performed polymer two-step approach, side reaction is few, and the TPU structural regularity made is good.
The present invention is achieved by the following technical solutions: a kind of organic-silicon-modified Polyurethane Thermoplastic Elastomer is made up of following component, and the weight part of each component is:
Described macromolecule dihydric alcohol is selected from one or more in polyether Glycols, polyester diol, and molecular weight is 1000-3000; As preferably, described polyether Glycols is selected from one or more in polypropylene glycol, polytetrahydrofuran diol; Described polyester diol is selected from one or more in polyethylene glycol adipate, poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester;
Described end hydroxyalkyl end-blocking polydimethylsiloxane is selected from one or more in hydroxybutyl end-blocking polydimethylsiloxane, hydroxypropyl end-blocking polydimethylsiloxane, and molecular weight is 1000-3000;
Described diisocyanate monomer is selected from 4,4 '-diphenylmethanediisocyanate, 4, in 4 '-dicyclohexyl methane diisocyanate, naphthalene diisocyanate, PPDI, hexamethylene diisocyanate one or more;
Described small molecule chain extender is selected from one or more in small molecules dibasic alcohol, small molecules diamine; As preferably, described small molecules dibasic alcohol is selected from one or more in ethylene glycol, 1,2-PD, BDO, glycol ether, 1,6-hexylene glycol; Described small molecules diamine is selected from 3,3 '-two chloro-4, in 4 '-diphenylmethanediamiand, 3,5-dimethyl sulfenyl tolylene diamines, 2,4-diamino-3,5-dimethyl sulphur-based chlorobenzenes one or more;
Described catalyzer is selected from one or more in stannous octoate, dibutyltin diacetate, dibutyl tin laurate, lead octoate 36;
Described antioxidant is selected from one or more in commercial Irganox1010, Irganox1076, Irganox259;
Described UV light absorber is selected from one or more in commercial Tinuvin770, Tinuvin234, Tinuvin571.
Described organic-silicon-modified method for preparing thermoplastic polyurethane elastomer is following steps:
(1) macromolecule dihydric alcohol is put in reactor, be warming up to about 100 ~ 120 DEG C, vacuum hydro-extraction 2 ~ 4h, then stop after being cooled to 50 ~ 60 DEG C vacuumizing, add end hydroxyalkyl end-blocking polydimethylsiloxane, vulcabond, after being stirred to temperature-stable, heat up and control temperature of reaction at 70 ~ 90 DEG C, the content of NCO in performed polymer is surveyed every 0.5h Di-n-Butyl Amine method, treat the degassed 0.5 ~ 1h of stable content final vacuum of NCO in performed polymer, obtain Polyurethane Thermoplastic Elastomer performed polymer;
As preferably, the vacuum tightness of vacuum described in step is 0.1-0.5kPa.
As preferably, end hydroxyalkyl end-blocking polydimethylsiloxane is drying regime, vulcabond is molten state.
(2) small molecules dibasic alcohol, catalyzer, antioxidant and UV light absorber are mixed, then Polyurethane Thermoplastic Elastomer performed polymer that step (1) obtains is added and after fully stirring, at 140 ~ 160 DEG C of heating 15 ~ 30min, then put to room temperature after 100 ~ 110 DEG C of slaking 12-16h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.
The organosilicon modifier used in the present invention is end hydroxyalkyl end-blocking polydimethylsiloxane, i.e. hydroxybutyl end-blocking polydimethylsiloxane or hydroxypropyl end-blocking polydimethylsiloxane, the original linearity molecular structure of TPU and performance can not be destroyed, the mode being simultaneously beneficial to chemical copolymerization improves the consistency of bi-material, with di-isocyanate reaction, generate the C-O-C key that hydrolytic resistance is good, but not the Si-O-C key of facile hydrolysis, therefore with this organic-silicon-modified urethane, there is better hydrophobic nature and thermostability;
The present invention relative to the beneficial effect of prior art is:
(1) organic-silicon-modified Polyurethane Thermoplastic Elastomer of the present invention has better hydrophobic nature and thermostability;
(2) the present invention is by performed polymer two-step approach, and side reaction is few, and the TPU structural regularity made is good;
(3) the organic-silicon-modified Polyurethane Thermoplastic Elastomer prepared of the present invention after measured, compared with unmodified Polyurethane Thermoplastic Elastomer, mechanical property change is little, but initial pyrolyzation temperature is higher than 290 DEG C, improve 70 DEG C, illustrate and effectively improve temperature tolerance; Water-intake rate, lower than 3.5%, reduces by more than 7%, illustrates and effectively improve water tolerance.
Embodiment
Be described further the present invention below in conjunction with embodiment, but embodiments of the present invention are not only in this, raw materials used all commercially available in embodiment, usage quantity all weight part represents.
Embodiment 1
(1) polypropylene glycol being 1000 by 20 weight part molecular weight is put in reactor, be warming up to about 100 DEG C, vacuum hydro-extraction 2h, then stop after being cooled to 50 DEG C vacuumizing, the molecular weight adding 2 weight part dryings is the end group butyl end-capping polydimethylsiloxane of 1000, 10 weight parts melted 4, 4 '-diphenylmethanediisocyanate, rapid stirring, after treating temperature-stable, slow intensification also controls temperature of reaction at 70 DEG C, the content of NCO in performed polymer is surveyed every 0.5h Di-n-Butyl Amine method, after NCO stable content, connect vacuum unit and carry out vacuum outgas 0.5h, obtain Polyurethane Thermoplastic Elastomer performed polymer, the vacuum tightness of described vacuum is 0.5kPa.
(2) by 5 weight parts 1,4-butyleneglycol, 0.1 weight part dibutyl tin laurate, 0.1 weight part Irganox1010 and 0.1 weight part Tinuvin770 mix, then Polyurethane Thermoplastic Elastomer performed polymer prepared by step (1) is added and after fully stirring fast, at 140 DEG C of heating 15min, then put to room temperature after 100 DEG C of slaking 12h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.
Embodiment 2
(1) poly adipate succinic acid ester being 2000 by 40 weight part molecular weight is put in reactor, be warming up to about 120 DEG C, vacuum hydro-extraction 4h, then stop after being cooled to 60 DEG C vacuumizing, the molecular weight adding 5 weight part dryings is the end group butyl end-capping polydimethylsiloxane of 2000, the hexamethylene diisocyanate that 15 weight parts have melted, rapid stirring, after treating temperature-stable, slow intensification also controls temperature of reaction at 80 DEG C, the content of NCO in performed polymer is surveyed every 0.5h Di-n-Butyl Amine method, after NCO stable content, connect vacuum unit and carry out vacuum outgas 1h, obtain Polyurethane Thermoplastic Elastomer performed polymer, the vacuum tightness of described vacuum is 0.1kPa.
(2) by 8 weight parts 3,3 '-two chloro-4,4 '-diphenylmethanediamiand, 0.2 parts by weight of octanoic acid sub-tin, 0.2 weight part Irganox1076 and 0.1 weight part Tinuvin571 mix, then Polyurethane Thermoplastic Elastomer performed polymer prepared by step (1) is added and after fully stirring fast, at 160 DEG C of heating 15min, then put to room temperature after 110 DEG C of slaking 14h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.
Embodiment 3
(1) polytetrahydrofuran diol being 3000 by 60 weight part molecular weight is put in reactor, be warming up to about 110 DEG C, vacuum hydro-extraction 3h, then stop after being cooled to 55 DEG C vacuumizing, the molecular weight adding 10 weight part dryings is the hydroxypropyl end-blocking polydimethylsiloxane of 3000, 20 weight parts melted 4, 4 '-dicyclohexyl methane diisocyanate, rapid stirring, after treating temperature-stable, slow intensification also controls temperature of reaction at 90 DEG C, the content of NCO in performed polymer is surveyed every 0.5h Di-n-Butyl Amine method, after NCO stable content, connect vacuum unit and carry out vacuum outgas 1h, obtain Polyurethane Thermoplastic Elastomer performed polymer, the vacuum tightness of described vacuum is 0.3kPa.
(2) by 6 weight parts 1,4-butyleneglycol, 0.5 weight part dibutyl tin laurate, 0.5 weight part Irganox1010 and 0.5 weight part Tinuvin770 mix, then Polyurethane Thermoplastic Elastomer performed polymer prepared by step (1) is added and after fully stirring fast, at 140 DEG C of heating 30min, then put to room temperature after 100 DEG C of slaking 16h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.Embodiment 4
(1) by 20 weight part molecular weight be 2000 poly-hexanodioic acid hexylene glycol ester put in reactor, be warming up to about 100 DEG C, vacuum hydro-extraction 2h, then stop after being cooled to 50 DEG C vacuumizing, the molecular weight adding 2 weight part dryings is the end group propyl group end-blocking polydimethylsiloxane of 2000, 10 weight parts melted 4, 4 '-diphenylmethanediisocyanate, rapid stirring, after treating temperature-stable, slow intensification also controls temperature of reaction at 70 DEG C, the content of NCO in performed polymer is surveyed every 0.5h Di-n-Butyl Amine method, after NCO stable content, connect vacuum unit and carry out vacuum outgas 0.5h, obtain Polyurethane Thermoplastic Elastomer performed polymer, the vacuum tightness of described vacuum is 0.5kPa.
(2) by 2 weight parts 1,6-hexylene glycol, 0.3 parts by weight of octanoic acid are plumbous, 0.3 weight part Irganox259 and 0.3 weight part Tinuvin234 mixes, then Polyurethane Thermoplastic Elastomer performed polymer prepared by step (1) is added and after fully stirring fast, at 150 DEG C of heating 20min, then put to room temperature after 105 DEG C of slaking 12h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.
Comparative example 1-4
Comparative example 1-4 is unmodified Polyurethane Thermoplastic Elastomer, and its preparation is accordingly replaced by the macromolecule dihydric alcohol of the same molecular amount of same molar via hydroxyalkyl end-blocking polydimethylsiloxane in embodiment 1-4.
Test case
To embodiment 1 ~ 4, the organic-silicon-modified Polyurethane Thermoplastic Elastomer that comparative example 1 ~ 4 obtains carries out following test, and organic-silicon-modified Polyurethane Thermoplastic Elastomer the performance test results is as table 1:
Shao A measurement of hardness method: GB/T531.1-2008;
Stretching strength determination method: GB/T528-2009;
Water-intake rate measuring method: GB/T1690-2006;
Initial pyrolyzation temperature measuring method: obtain according to thermogravimetric analysis.
Table 1: organic-silicon-modified Polyurethane Thermoplastic Elastomer test result
| Numbering | Shao A hardness | Tensile strength/MPa | Initial pyrolyzation temperature/DEG C | Water-intake rate/wt% |
| Embodiment 1 | 92 | 48.6 | 290 | 3.5 |
| Comparative example 1 | 93 | 48.8 | 220 | 10.8 |
| Embodiment 2 | 89 | 42.5 | 292 | 2.9 |
| Comparative example 2 | 89 | 42.3 | 217 | 10.5 |
| Embodiment 3 | 86 | 40.7 | 298 | 2.6 |
| Comparative example 3 | 87 | 40.8 | 215 | 10.2 |
| Embodiment 4 | 91 | 47.9 | 291 | 3.2 |
| Comparative example 4 | 90 | 47.8 | 218 | 10.5 |
Compared with unmodified Polyurethane Thermoplastic Elastomer, mechanical property change is little, but initial pyrolyzation temperature is higher than 290 DEG C, improves 70 DEG C, illustrates and effectively improve temperature tolerance; Water-intake rate, lower than 3.5%, reduces by more than 7%, illustrates and effectively improve water tolerance.
The above is only the reasonable embodiment of the present invention, the restriction not to other form of the present invention.Change, the modification made under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplification etc., all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. an organic-silicon-modified Polyurethane Thermoplastic Elastomer, is characterized in that, described elastomerics is made up of following component, and the weight part of each component is:
。
2. organic-silicon-modified Polyurethane Thermoplastic Elastomer according to claim 1, is characterized in that, described macromolecule dihydric alcohol is selected from one or more in polyether Glycols, polyester diol, and molecular weight is 1000-3000; Described end hydroxyalkyl end-blocking polydimethylsiloxane is selected from one or more in hydroxybutyl end-blocking polydimethylsiloxane, hydroxypropyl end-blocking polydimethylsiloxane, and molecular weight is 1000-3000; Described diisocyanate monomer is selected from 4,4 '-diphenylmethanediisocyanate, 4, in 4 '-dicyclohexyl methane diisocyanate, naphthalene diisocyanate, PPDI, hexamethylene diisocyanate one or more; Described small molecule chain extender is selected from one or more in small molecules dibasic alcohol, small molecules diamine; Described catalyzer is selected from one or more in stannous octoate, dibutyltin diacetate, dibutyl tin laurate, lead octoate 36.
3. an organic-silicon-modified method for preparing thermoplastic polyurethane elastomer as claimed in claim 1 or 2, is characterized in that, comprise the steps:
(1) macromolecule dihydric alcohol is put in reactor, be warming up to about 100 ~ 120 DEG C, vacuum hydro-extraction 2 ~ 4h, then stop after being cooled to 50 ~ 60 DEG C vacuumizing, add end hydroxyalkyl end-blocking polydimethylsiloxane, vulcabond, after being stirred to temperature-stable, heating up and control temperature of reaction at 70 ~ 90 DEG C, treat the degassed 0.5 ~ 1h of stable content final vacuum of NCO in performed polymer, obtain Polyurethane Thermoplastic Elastomer performed polymer;
(2) small molecules dibasic alcohol, catalyzer, antioxidant and UV light absorber are mixed, then Polyurethane Thermoplastic Elastomer performed polymer that step (1) obtains is added and after stirring, at 140 ~ 160 DEG C of heating 15 ~ 30min, then put to room temperature after 100 ~ 110 DEG C of slaking 12-16h, products therefrom granulation, shapingly namely obtain described organic-silicon-modified Polyurethane Thermoplastic Elastomer.
4. want the organic-silicon-modified method for preparing thermoplastic polyurethane elastomer described in 3 according to right, it is characterized in that, described in step (1), the vacuum tightness of vacuum is 0.1-0.5kPa.
5. want the organic-silicon-modified method for preparing thermoplastic polyurethane elastomer described in 3 according to right, it is characterized in that, step (1) middle-end hydroxyalkyl end-blocking polydimethylsiloxane is drying regime, vulcabond is molten state.
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