CN104017167B - A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer - Google Patents
A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer Download PDFInfo
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- CN104017167B CN104017167B CN201410265725.3A CN201410265725A CN104017167B CN 104017167 B CN104017167 B CN 104017167B CN 201410265725 A CN201410265725 A CN 201410265725A CN 104017167 B CN104017167 B CN 104017167B
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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
- C08G18/70—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
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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
- C08G18/40—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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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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
- C08G18/6633—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
Abstract
The invention discloses a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include: 1) PEPA, catalyst are added in reactor, under heating, vacuum condition, it is dehydrated to obtain component A；By 1,5 naphthalene diisocyanates, chain extender are mixed homogeneously with component A after heating respectively, then by double screw extruder extrusion reaction, obtain PAUR elastomer；2) by epoxy resin and step 1) PAUR that obtains elastomer blended blend, then blend is placed in temperature be 80～150 DEG C, under the conditions of pressure is 0.08～0.1MPa, it is dried 4～24h, obtains heat-resistant polyester type Polyurethane Thermoplastic Elastomer.Utilize the heat-resistant polyester type thermoplastic polyurethane elastic that this disclosure of the invention method prepares, the TPU application being mainly used under higher temperature.
Description
Technical field
The present invention relates to a kind of method for preparing thermoplastic polyurethane elastomer, particularly relate to a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer.
Background technology
Polyurethane Thermoplastic Elastomer (being also called TPU) new material is referred to as " epoch-making novel high polymer material ", is one of our times six synthetic material with development prospect greatly.
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, caking property is good, but it uses temperature to be usually no more than 80 DEG C, more than 100 DEG C material meeting softening transforms, mechanical performance substantially weakens, Short-range Temperature is less than 120 DEG C, seriously limits it and extensively applies.
Summary of the invention
The technical problem to be solved is: provide a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer that can be used under higher temperature conditions and using.
For solving above-mentioned technical problem the technical solution adopted in the present invention it is: a kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) preparation of PAUR elastomer:
PEPA, catalyst are added in reactor, it is warming up to 100～200 DEG C with the speed of 5～50 DEG C/min, intensification limit, limit evacuation, control reacting kettle inner pressure is-0.08～-0.1MPa, temperature is 100～200 DEG C of dehydrations 0.5～20h, it is subsequently cooled to 65～85 DEG C, it is passed through nitrogen and releases vacuum, obtain component A；
By 1,5-naphthalene diisocyanate (NDI) enters double screw extruder with component A after being separately heated to 50-80 DEG C with chain extender after casting machine mixes, limit border ring extrusion in double screw extruder, forms PAUR elastomer；
Described catalyst accounts for the 0.01%～0.5% of the gross mass of PEPA；Described 1,5-naphthalene diisocyanate is 1:1-2 with the mass ratio of PEPA；Described chain extender accounts for the 1%-10% of diisocyanate and the gross mass of PEPA；
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, it is placed horizontally in vacuum drying oven, the temperature controlling vacuum drying oven is 80～150 DEG C, pressure is-0.08～-0.1MPa, take out after being dried 4～24h, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer；
Described epoxy resin accounts for the 8%～12% of PAUR elastomeric mass.
Described PEPA is prepared through polycondensation reaction by dicarboxylic acids and dihydroxylic alcohols, and its number-average molecular weight is 1000～4000.
Described dicarboxylic acids is aliphatic dicarboxylic acid or aromatic binary carboxylic acid；Described dihydroxylic alcohols selected from ethylene glycol, BDO, 1,6-hexanediol, 2-methyl isophthalic acid, a kind of or mixture of any two kinds in ammediol.
The described the aliphatic dicarboxylic acid a kind of or mixture of any two kinds in 1,3-propanedicarboxylic acid, adipic acid, suberic acid and decanedioic acid；The described the aromatic binary carboxylic acid a kind of or mixture of any two kinds in phthalic acid, M-phthalic acid, p-phthalic acid.
Described catalyst is organic tin catalyst, a kind of or mixture of any two kinds in stannous octoate, dibutyltin diacetate, dibutyl tin laurate.
Described chain extender selected from BDO, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, neopentyl glycol, 1, a kind of or mixture of any two kinds in 6-hexanediol.
Described by method elastomer blended to epoxy resin and PAUR is, and cosolvent is blended, ultrasonic disperse or Screw Extrusion.
The invention has the beneficial effects as follows: use the heat-resistant polyester type Polyurethane Thermoplastic Elastomer TPU application under higher temperature that preparation method of the present invention prepares, essentially consist in employing following methods:
1) heat resistance preferable 1 is used, 5-naphthalene diisocyanate (NDI) is as hard section, NDI is owing to having aromatic naphthalene ring, strand height is regular, have the dynamic property of excellence with its polyurethane elastomer synthesized, heat resistance is better than the polyurethane elastomer of TDI type, MDI type.
2) using epoxy resin as the graft modification of modifying agent, epoxy resin and polyurethane reaction can introduce on strand that cohesive energy is big, heat decomposition temperature is high, the organic heterocyclic of Heat stability is good group-oxazolidone, forming part network structure, improves the heat resistance of polyurethane elastomer.
By the key technical indexes of the type Polyurethane Thermoplastic Elastomer that the present invention obtains: hot strength 38～48MPa；And commonly use MDI type Polyurethane Thermoplastic Elastomer hot strength ＜ 35MPa.
Detailed description of the invention
Specific embodiments of the present invention are described below in detail.
Embodiment 1
Adding in 2 liters of reactors by adipic acid and 1, the polyhydric alcohol 500g of 6-hexanediol polycondensation, add positive tetrabutyl titanate 2g, slowly heat up with the speed of 5 DEG C/min, intensification limit, limit is evacuated to vacuum 0.04MPa, vacuum dehydration 2h.Polyhydric alcohol 280g and 1,5-naphthalene diisocyanate 173g after dehydration and 2-methyl butanediol 35g is separately heated to 50 DEG C after casting machine mixes, enters double screw extruder, limit border ring extrusion in double screw extruder.In the present embodiment, it is as follows that each district of screw rod arranges temperature: 80 DEG C, 120 DEG C, 180 DEG C, 200 DEG C, 180 DEG C, 150 DEG C, the whole reactive extrursion time is 55 seconds.
Add the above-mentioned elastomer of 65gE-51 Yu 650g and obtain heat-resistant thermoplastic polyurethane elastomer after ultrasonic disperse 3min in the ultrasonic instrument that power is 1200w.
Embodiment 2
2 liters of reactors add by the polyhydric alcohol 500g of suberic acid with BDO polycondensation, add positive tetrabutyl titanate 1.9g, slowly heat up with the speed of 5 DEG C/min, intensification limit, limit is evacuated to vacuum 0.04MPa, and temperature rises to 220 DEG C simultaneously, at this temperature reaction 1.5 hours.
Polyhydric alcohol 300g and 1,5-naphthalene diisocyanate 190g after dehydration and 4-ethyl heptandiol 40g is separately heated to 50 DEG C after casting machine mixes, enters double screw extruder, limit border ring extrusion in double screw extruder.In the present embodiment, it is as follows that each district of screw rod arranges temperature: 80 DEG C, 120 DEG C, 180 DEG C, 200 DEG C, 180 DEG C, 150 DEG C, the whole reactive extrursion time is 58 seconds.
Add the above-mentioned elastomer of 44gE-51 Yu 550g at appropriate solvent N, dinethylformamide (DMF) heat while stirring after 5min with magnetic stirring apparatus, it is poured into the polytetrafluoroethyldisk disk of clean dried, it is placed horizontally in 120 DEG C of vacuum drying ovens, holding vacuum is-0.09MPa, take out after 12h, obtain heat-resistant polyester type Polyurethane Thermoplastic Elastomer.
Embodiment 3
2 liters of reactors add by adipic acid and 1, the polyhydric alcohol 500g of 4-butanediol polycondensation, add titanium propanolate 2.1g, organobentonite 20g, slowly heat up with the speed of 6 DEG C/min, intensification limit, limit is evacuated to vacuum 0.045MPa, and temperature rises to 210 DEG C simultaneously, at this temperature reaction 2 hours.
Above-mentioned product 288g and 1,5-naphthalene diisocyanate 160g and 3-methyl hexanediol 43g are separately heated to 50 DEG C after casting machine mixes, enter double screw extruder, limit border ring extrusion in double screw extruder.In the present embodiment, it is as follows that each district of screw rod arranges temperature: 80 DEG C, 150 DEG C, 190 DEG C, 220 DEG C, 180 DEG C, 150 DEG C, the whole reactive extrursion time is 45 seconds.
By above-mentioned for 72gE-51 Yu 600g elastomer border ring extrusion in limit in double screw extruder.In the present embodiment, it is as follows that each district of twin screw arranges temperature: 90 DEG C, 160 DEG C, 190 DEG C, 230 DEG C, 190 DEG C, 155 DEG C, the whole reactive extrursion time is 60s.Extrudate being poured into the polytetrafluoroethyldisk disk of clean dried, is placed horizontally in 100 DEG C of vacuum drying ovens, holding vacuum is-0.1MPa, takes out, obtain heat-resistant thermoplastic polyurethane elastomer after 8h.
Comparative example 1
Adding in 2 liters of reactors by adipic acid and 1, the polyhydric alcohol 500g of 6-hexanediol polycondensation, add positive tetrabutyl titanate 2g, slowly heat up with the speed of 5 DEG C/min, intensification limit, limit is evacuated to vacuum 0.04MPa, vacuum dehydration 2h.Polyhydric alcohol 280g with MDI173g after dehydration and 2-methyl butanediol 35g is separately heated to 50 DEG C after casting machine mixes, enters double screw extruder, limit border ring extrusion in double screw extruder.In the present embodiment, it is as follows that each district of screw rod arranges temperature: 80 DEG C, 120 DEG C, 180 DEG C, 200 DEG C, 180 DEG C, 150 DEG C, the whole reactive extrursion time is 55 seconds.
Hot strength, elongation percentage, tearing strength assay method: ISO 37-2005.
Heat resistant type TPU mechanical property at different temperatures in MDI type PU elastomer and embodiment 1
From upper table, at high temperature, the conservation rate of the hardness of heat resistant type polyurethane elastomer, hot strength, elongation at break and tearing strength is better than MDI type polyurethane elastomer.
Claims (5)
1. a heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer, the steps include:
1) PEPA, catalyst are added in reactor, be warming up to the speed of 5～50 DEG C/min
100～200 DEG C, intensification limit, limit evacuation, control reacting kettle inner pressure is-0.08～-0.1MPa, temperature is
100～200 DEG C of dehydrations 0.5～20h, are subsequently cooled to 65～85 DEG C, are passed through nitrogen and release vacuum, obtain component A；
By 1,5-naphthalene diisocyanate, chain extender are mixed homogeneously with component A after being separately heated to 50-80 DEG C,
Then by double screw extruder extrusion reaction, PAUR elastomer is obtained；
Described catalyst accounts for the 0.01%～0.5% of the gross mass of PEPA；Described 1,5-naphthalene two is different
Cyanate is 1:1～2 with the mass ratio of PEPA；Described chain extender accounts for 1,5-naphthalene diisocyanate with
The 1%-10% of the gross mass of PEPA；
2) by epoxy resin and step 1) PAUR that obtains elastomer blended blend, then
Blend is placed in temperature be 80～150 DEG C, pressure under the conditions of-0.08～-0.1MPa, be dried 4～24h,
Heat-resistant polyester type Polyurethane Thermoplastic Elastomer；
Described epoxy resin accounts for the 8%～12% of PAUR elastomeric mass；
Described PEPA is prepared through polycondensation reaction by dicarboxylic acids and dihydroxylic alcohols, and its number-average molecular weight is
1000～4000；
Described dicarboxylic acids is aliphatic dicarboxylic acid or aromatic binary carboxylic acid；Described dihydroxylic alcohols is selected from
Ethylene glycol, BDO, 1,6-hexanediol, 2-methyl isophthalic acid, the one in ammediol or any two kinds
Mixture；
Described aliphatic dicarboxylic acid one in 1,3-propanedicarboxylic acid, adipic acid, suberic acid and decanedioic acid or
The mixture of any two kinds；Described aromatic binary carboxylic acid is selected from phthalic acid, M-phthalic acid, right
A kind of or the mixture of any two kinds in phthalic acid.
A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer the most according to claim 1,
It is characterized in that: described catalyst is organic tin catalyst.
A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer the most according to claim 2,
It is characterized in that: described organic tin catalyst is selected from stannous octoate, dibutyltin diacetate, two Laurels
A kind of or the mixture of any two kinds in acid dibutyl tin.
A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer the most according to claim 1,
It is characterized in that: described chain extender selected from BDO, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol,
Neopentyl glycol, 1, a kind of or mixture of any two kinds in 6-hexanediol.
A kind of heat-resistant polyester type method for preparing thermoplastic polyurethane elastomer the most according to claim 1,
It is characterized in that: described is that cosolvent is total to by method elastomer blended to epoxy resin and PAUR
Mixed, ultrasonic disperse or Screw Extrusion.
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| CN104231204B (en) * | 2014-09-18 | 2017-08-29 | 东莞市吉鑫高分子科技有限公司 | A kind of TPUE used for solar batteries and preparation method thereof |
| CN104650319A (en) * | 2015-01-08 | 2015-05-27 | 大连理工大学 | Heat-resistant polyurethane thermoplastic elastomer and preparation method thereof |
| CN104804173B (en) * | 2015-05-18 | 2017-10-17 | 吴江市宏宇机械有限公司 | It is a kind of resistant to elevated temperatures for polyurethane elastomer of resin mould and preparation method thereof |
| 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 |
| CN107880243A (en) * | 2017-11-23 | 2018-04-06 | 广东元星工业新材料有限公司 | A kind of high heat-resistant high-performance polyurethane elastomer and preparation method thereof |
| CN108192063A (en) * | 2017-12-28 | 2018-06-22 | 山东诺威聚氨酯股份有限公司 | High rigidity thermoplastic polyurethane elastomer and preparation method thereof |
| CN109111725A (en) * | 2018-07-20 | 2019-01-01 | 滁州市玉林聚氨酯有限公司 | A kind of preparation method of elastane |
| CN111410729A (en) * | 2020-04-24 | 2020-07-14 | 黎哲华 | High-heat-resistance flame-retardant phosphorus-nitrogen synergistic reaction type polyurethane material and preparation method thereof |
| CN112646355A (en) * | 2021-01-14 | 2021-04-13 | 江苏威久科技发展有限公司 | High-strength wear-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115926240A (en) * | 2022-07-25 | 2023-04-07 | 万华化学集团股份有限公司 | High-support thermoplastic polyurethane foam material and preparation method thereof |
| CN115558281B (en) * | 2022-08-25 | 2023-12-05 | 浙江华峰热塑性聚氨酯有限公司 | High-hardness thermoplastic polyurethane copolymer and preparation method thereof |
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| WO1993024549A1 (en) * | 1992-06-04 | 1993-12-09 | Olin Corporation | Hard thermoplastic polyurethane elastomers |
| CN101698695B (en) * | 2009-10-22 | 2011-08-10 | 陕西科技大学 | Method for synthesizing heat-resistance epoxy resin modified thermoplastic linear polyurethane elastomer |
| CN102352176A (en) * | 2011-05-27 | 2012-02-15 | 厦门固克涂料集团有限公司 | Combination of polyurethane modified epoxy resin and modified secondary amine delayed-hardening agent as primer of polyurea elastomer |
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