CN104017167A - Preparation method of heat-resistant polyester plastic polyurethane elastomer - Google Patents
Preparation method of heat-resistant polyester plastic polyurethane elastomer Download PDFInfo
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- CN104017167A CN104017167A CN201410265725.3A CN201410265725A CN104017167A CN 104017167 A CN104017167 A CN 104017167A CN 201410265725 A CN201410265725 A CN 201410265725A CN 104017167 A CN104017167 A CN 104017167A
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- Prior art keywords
- heat
- polyurethane elastomer
- acid
- thermoplastic polyurethane
- resistant polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 22
- 229920003225 polyurethane elastomer Polymers 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229920003023 plastic Polymers 0.000 title abstract 2
- 239000004033 plastic Substances 0.000 title abstract 2
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 22
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 21
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-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
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 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
- 238000010792 warming Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- 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 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SQAJRDHPLTWZQT-UHFFFAOYSA-N 3-methylhexane-1,6-diol Chemical compound OCCC(C)CCCO SQAJRDHPLTWZQT-UHFFFAOYSA-N 0.000 description 1
- QWVVPYMVEXVLMX-UHFFFAOYSA-N 4-ethylheptane-1,1-diol Chemical compound CCCC(CC)CCC(O)O QWVVPYMVEXVLMX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
-
- 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
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- 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
- C08G18/58—Epoxy resins
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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 discloses a preparation method of a heat-resistant polyester plastic polyurethane elastomer, which comprises the following steps: 1) adding polyester polyol and a catalyst into a reaction kettle, and dehydrating under the conditions of heating and vacuum to obtain a component A; respectively heating 1,5-naphthyldiisocyanate and a chain extender, evenly mixing with the component A, and carrying out extrusion reaction with a double screw extruder to obtain a polyester polyurethane elastomer; and 2) blending an epoxy resin with the polyester polyurethane elastomer obtained in the step 1) to obtain a blend, and drying the blend at 80-150 DEG C under the pressure of -0.08 to -0.1 MPa for 4-24 hours to obtain the heat-resistant polyester thermoplastic polyurethane elastomer. The heat-resistant polyester thermoplastic polyurethane elastomer prepared by the method is mainly used in the field of application of TPU (thermoplastic polyurethane) at higher temperature.
Description
Technical field
The present invention relates to a kind of method for preparing thermoplastic polyurethane elastomer, relate in particular to a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer.
Background technology
Polyurethane Thermoplastic Elastomer (being called again TPU) novel material is called as " epoch-making novel high polymer material ", is one of our times six synthetic materials greatly with development prospect.
Polyurethane elastomer has the excellent properties such as good mechanical property, abrasion performance, oil resistant, tear-resistant, resistance to chemical attack, resistance to x radiation x, cohesiveness is good, but its use temperature is generally no more than 80 ℃, 100 ℃ of above material meeting softening transforms, mechanical property obviously weakens, Short-range Temperature is no more than 120 ℃, has seriously limited its widespread use.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of can be for the heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer using under higher temperature conditions.
For solving the problems of the technologies described above the technical solution adopted in the present invention, be: a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) the elastomeric preparation of PAUR:
Polyester polyol, catalyzer are added in reactor, speed with 5～50 ℃/min is warming up to 100～200 ℃, intensification limit, limit vacuumizes, controlling reacting kettle inner pressure is that-0.08～-0.1MPa, temperature are 100～200 ℃ of dehydration 0.5～20h, then be cooled to 65～85 ℃, pass into nitrogen and remove vacuum, obtain A component;
After 1,5-naphthalene diisocyanate (NDI) is heated to respectively to 50-80 ℃ with chainextender, enter twin screw extruder with A component after casting molding machine mixes, in twin screw extruder, limit coronite is extruded, and forms PAUR elastomerics;
Described catalyzer account for polyester polyol total mass 0.01%～0.5%; Described 1, the mass ratio of 5-naphthalene diisocyanate and polyester polyol is 1:1-2; Described chainextender accounts for the 1%-10% of the total mass of vulcabond and polyester polyol;
2) Epoxy/Polyurethane is elastomer blended:
By epoxy resin and step 1) PAUR that obtains is elastomer blended, then blend is poured in the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in vacuum drying oven, the temperature of controlling vacuum drying oven is that 80～150 ℃, pressure are-0.08～-0.1MPa, after dry 4～24h, take out, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer;
Described epoxy resin accounts for 8%～12% of PAUR elastomerics quality.
Described polyester polyol is made through polycondensation by di-carboxylic acid and dibasic alcohol, and its number-average molecular weight is 1000～4000.
Described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol, 2,2-methyl isophthalic acid, the mixture of a kind of in ammediol or any two kinds.
Described aliphatic dicarboxylic acid is selected from the mixture of a kind of in pentanedioic acid, hexanodioic acid, suberic acid and sebacic acid or any two kinds; Described aromatic binary carboxylic acid is selected from the mixture of a kind of in phthalic acid, m-phthalic acid, terephthalic acid or any two kinds.
Described catalyzer is organic tin catalyzer, is selected from the mixture of a kind of in stannous octoate, dibutyltin diacetate, dibutyl tin laurate or any two kinds.
Described chainextender is selected from BDO, 1,3-PD, Isosorbide-5-Nitrae-hexalin, neopentyl glycol, 1, the mixture of a kind of in 6-hexylene glycol or any two kinds.
Described is cosolvent blend, ultrasonic dispersion or Screw Extrusion by epoxy resin and the elastomer blended method of PAUR.
The invention has the beneficial effects as follows: adopt heat-resistant polyester type Polyurethane Thermoplastic Elastomer that preparation method of the present invention makes for the TPU Application Areas under comparatively high temps, be mainly to adopt following methods:
1) adopt resistance toheat good 1,5-naphthalene diisocyanate (NDI) is as hard section, NDI is owing to having aromatic naphthalene ring, molecular chain height is regular, with its synthetic polyurethane elastomer, have excellent dynamic property, resistance toheat is better than the polyurethane elastomer of TDI type, MDI type.
2) using the graft modification of epoxy resin as properties-correcting agent, epoxy resin and polyurethane reaction can introduce on molecular chain that internal cohesive energy is large, heat decomposition temperature is high, the organic heterocyclic group-oxazolidone of Heat stability is good, forming section reticulated structure, the resistance toheat of raising polyurethane elastomer.
The key technical indexes of the type Polyurethane Thermoplastic Elastomer obtaining by the present invention: tensile strength 38～48MPa; And conventional MDI type Polyurethane Thermoplastic Elastomer tensile strength < 35MPa.
Embodiment
Describe specific embodiment of the invention scheme below in detail.
Embodiment 1
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by hexanodioic acid and the polycondensation of 1,6-hexylene glycol, add positive tetrabutyl titanate 2g, with the speed of 5 ℃/min, slowly heat up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, vacuum hydro-extraction 2h.Polyvalent alcohol 280g and 1,5-naphthalene diisocyanate 173g after dehydration and 2-methyl butyleneglycol 35g are heated to respectively to 50 ℃ and after casting molding machine mixing, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 55 seconds that whole reaction finds time.
Add in the ultrasonic instrument that the above-mentioned elastomerics of 65gE-51 and 650g is 1200w at power and obtain heat-resistant thermoplastic polyurethane elastomer after ultrasonic dispersion 3min.
Embodiment 2
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by suberic acid and BDO polycondensation, add positive tetrabutyl titanate 1.9g, speed with 5 ℃/min slowly heats up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, and simultaneous temperature rises to 220 ℃, reacts 1.5 hours at this temperature.
Polyvalent alcohol 300g and 1,5-naphthalene diisocyanate 190g after dehydration and 4-ethyl heptanediol 40g are heated to respectively to 50 ℃ and after casting molding machine mixing, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 58 seconds that whole reaction finds time.
Add the above-mentioned elastomerics of 44gE-51 and 550g at appropriate solvent N, in dinethylformamide (DMF), with magnetic stirring apparatus, heat while stirring after 5min, be poured into the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in 120 ℃ of vacuum drying ovens, keep vacuum tightness to be-0.09MPa, after 12h, take out, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 3
In 2 liters of reactors, add by hexanodioic acid and 1, the polyvalent alcohol 500g that the polycondensation of 4-butyleneglycol forms, add titanium propanolate 2.1g, organobentonite 20g, speed with 6 ℃/min slowly heats up, intensification limit, limit is evacuated to vacuum tightness 0.045MPa, and simultaneous temperature rises to 210 ℃, reacts 2 hours at this temperature.
Above-mentioned reaction product 288g and 1,5-naphthalene diisocyanate 160g and 3-methyl hexylene glycol 43g are heated to respectively to 50 ℃ and after casting molding machine mixes, enter twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 150 ℃, 190 ℃, 220 ℃, 180 ℃, 150 ℃, it is 45 seconds that whole reaction finds time.
By 72gE-51 and the above-mentioned elastomerics of 600g, limit coronite in twin screw extruder is extruded.In the present embodiment, each district's set temperature of twin screw is as follows: 90 ℃, 160 ℃, 190 ℃, 230 ℃, 190 ℃, 155 ℃, whole reaction finds time as 60s.Extrudate is poured into the polytetrafluoroethyldisk disk of clean dried, be placed horizontally in 100 ℃ of vacuum drying ovens, keep vacuum tightness to be-0.1MPa, after 8h, take out, obtain heat-resistant thermoplastic polyurethane elastomer.
Comparative example 1
In 2 liters of reactors, add the polyvalent alcohol 500g being formed by hexanodioic acid and the polycondensation of 1,6-hexylene glycol, add positive tetrabutyl titanate 2g, with the speed of 5 ℃/min, slowly heat up, intensification limit, limit is evacuated to vacuum tightness 0.04MPa, vacuum hydro-extraction 2h.Polyvalent alcohol 280g after dehydration is heated to respectively to 50 ℃ with MDI173g and 2-methyl butyleneglycol 35g and after casting molding machine mixes, enters twin screw extruder, in twin screw extruder, limit coronite is extruded.In the present embodiment, each district's set temperature of screw rod is as follows: 80 ℃, 120 ℃, 180 ℃, 200 ℃, 180 ℃, 150 ℃, it is 55 seconds that whole reaction finds time.
Tensile strength, unit elongation, tear strength measuring method: ISO37-2005.
The mechanical property of heat resistant type TPU under differing temps in MDI type PU elastomerics and embodiment 1
From upper table, at high temperature, the conservation rate of the hardness of heat resistant type polyurethane elastomer, tensile strength, elongation at break and tear strength is better than MDI type polyurethane elastomerics.
Claims (8)
1. a heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) polyester polyol, catalyzer are added in reactor, speed with 5～50 ℃/min is warming up to 100～200 ℃, intensification limit, limit vacuumizes, controlling reacting kettle inner pressure is that-0.08～-0.1MPa, temperature are 100～200 ℃ of dehydration 0.5～20h, then be cooled to 65～85 ℃, pass into nitrogen and remove vacuum, obtain A component;
After 1,5-naphthalene diisocyanate, chainextender are heated to respectively to 50-80 ℃, mix with A component, then, by twin screw extruder extrusion reaction, obtain PAUR elastomerics;
Described catalyzer account for polyester polyol total mass 0.01%～0.5%; Described 1, the mass ratio of 5-naphthalene diisocyanate and polyester polyol is 1:1～2; Described chainextender accounts for the 1%-10% of the total mass of 1,5-naphthalene diisocyanate and polyester polyol;
2) by epoxy resin and step 1) PAUR that obtains elastomer blended blend, then blend being placed in to temperature and being 80～150 ℃, pressure is under-0.08～-0.1MPa condition, dry 4～24h, obtains heat-resistant polyester type Polyurethane Thermoplastic Elastomer;
Described epoxy resin accounts for 8%～12% of PAUR elastomerics quality.
2. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described polyester polyol is made through polycondensation by di-carboxylic acid and dibasic alcohol, and its number-average molecular weight is 1000～4000.
3. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 2, is characterized in that: described di-carboxylic acid is aliphatic dicarboxylic acid or aromatic binary carboxylic acid; Described dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol, 2,2-methyl isophthalic acid, the mixture of a kind of in ammediol or any two kinds.
4. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 3, is characterized in that: described aliphatic dicarboxylic acid is selected from the mixture of a kind of in pentanedioic acid, hexanodioic acid, suberic acid and sebacic acid or any two kinds; Described aromatic binary carboxylic acid is selected from the mixture of a kind of in phthalic acid, m-phthalic acid, terephthalic acid or any two kinds.
5. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described catalyzer is organic tin catalyzer.
6. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 5, is characterized in that: described organic tin catalyzer is selected from the mixture of a kind of in stannous octoate, dibutyltin diacetate, dibutyl tin laurate or any two kinds.
7. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, it is characterized in that: described chainextender is selected from BDO, 1,3-PD, 1,4-hexalin, neopentyl glycol, 1, the mixture of a kind of in 6-hexylene glycol or any two kinds.
8. a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer according to claim 1, is characterized in that: described is cosolvent blend, ultrasonic dispersion or Screw Extrusion by epoxy resin and the elastomer blended method of PAUR.
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| CN104650319A (en) * | 2015-01-08 | 2015-05-27 | 大连理工大学 | Heat-resistant polyurethane thermoplastic elastomer and preparation method thereof |
| CN104804173A (en) * | 2015-05-18 | 2015-07-29 | 吴江市宏宇机械有限公司 | High-temperature-resistant polyurethane elastomer for mold resin and preparation method of polyurethane elastomer |
| CN105384908A (en) * | 2015-11-13 | 2016-03-09 | 成都多力多新材料有限公司 | Thermoplastic polyurethane elastomer and polyurethane prepolymer material and preparation method thereof |
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