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CN-121991488-A - Cold-resistant TPU material and preparation method thereof

CN121991488ACN 121991488 ACN121991488 ACN 121991488ACN-121991488-A

Abstract

The application relates to the field of polyurethane materials, and in particular discloses a cold-resistant TPU and a preparation method thereof, wherein the cold-resistant TPU comprises, by weight, 40-60 parts of polytetrahydrofuran ether glycol, 20-30 parts of polycaprolactone diol, 5-20 parts of fluorocarbon polyether diol, 1-10 parts of hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol, 30-40 parts of diphenylmethane diisocyanate, 5-20 parts of isophorone diisocyanate, 2-15 parts of chain extender, 0.1-3.0 parts of filler, 0.01-0.5 parts of catalyst and 0.5-3.0 parts of auxiliary agent. The polyurethane material of the application is excellent in cold environment.

Inventors

  • ZHANG ZHENGQIAN
  • HU PING

Assignees

  • 苏州新七浦新材料科技有限公司

Dates

Publication Date
20260508
Application Date
20260206

Claims (9)

  1. 1. The cold-resistant TPU material is characterized by comprising, by weight, 40-60 parts of polytetrahydrofuran ether glycol, 20-30 parts of polycaprolactone glycol, 5-20 parts of fluorocarbon polyether glycol, 1-10 parts of hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol, 30-40 parts of diphenylmethane diisocyanate, 5-20 parts of isophorone diisocyanate, 2-15 parts of chain extender, 0.1-3.0 parts of filler, 0.01-0.5 parts of catalyst and 0.5-3.0 parts of auxiliary agent.
  2. 2. The cold-resistant TPU material according to claim 1, wherein the polyether polyol of the hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol has a number average molecular weight of 1000-5000g/mol and a functionality of 1-3.
  3. 3. The cold-resistant TPU material of claim 1 wherein the filler comprises a cerium doped modified filler.
  4. 4. The cold-resistant TPU material according to claim 1, wherein the preparation step of the cerium doped modified filler comprises the following steps: dispersing cerium nitrate, diammonium hydrogen phosphate and calcium hydroxide in deionized water, regulating pH of the system, heating for reaction, centrifuging, washing, vacuum drying to obtain Ce-HAP, Mixing KH570 with MPEG and p-toluene sulfonic acid, heating and refluxing to react to obtain the hybrid modifier, Dispersing Ce-HAP in ethanol water solution, performing ultrasonic dispersion, adding a hybridization modifier, heating and stirring for reaction, filtering, washing and vacuum drying to obtain the cerium doped modified filler.
  5. 5. The cold-resistant TPU material according to claim 4, wherein in the preparation step of the cerium doped modified filler, the mass ratio of cerium nitrate, diammonium hydrogen phosphate and calcium hydroxide is 2 (2-5) to 6-7.
  6. 6. The cold-resistant TPU material according to claim 4, wherein in the preparation step of the cerium doped modified filler, the MPEG number average molecular weight is 500-800g/mol.
  7. 7. A cold-resistant TPU material according to claim 3, wherein the mass ratio of the hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol to the cerium doped modified filler is (2-5): 1.
  8. 8. A process for preparing cold-resistant TPU according to any one of claims 1 to 7, which comprises the steps of respectively vacuum-drying and dehydrating polytetrahydrofuran ether glycol, polycaprolactone glycol, fluorocarbon polyether glycol, hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol, cooling to room temperature, mixing uniformly to obtain a mixture, Heating the pretreated mixture under the protection of nitrogen, slowly adding diphenylmethane diisocyanate and isophorone diisocyanate, stirring uniformly, adding a catalyst, heating to react, cooling, adding a chain extender, stirring, adding the rest components, continuing stirring to obtain TPU melt, And extruding and granulating the TPU melt, vacuum drying and curing to obtain the cold-resistant TPU material.
  9. 9. The method for preparing the cold-resistant TPU material according to claim 8, wherein the curing is carried out at 75-85 ℃ for 8-12 hours.

Description

Cold-resistant TPU material and preparation method thereof Technical Field The application relates to the field of polyurethane materials, in particular to a cold-resistant TPU material and a preparation method thereof. Background Thermoplastic polyurethane elastomer (TPU) is formed by copolymerizing diisocyanate, macromolecular polyol and a chain extender, has the processing convenience of plastics and the high elasticity of rubber, is increasingly widely applied in low-temperature scenes by virtue of excellent wear resistance, oil resistance and mechanical properties, covers the fields of cold chain conveying components, aerospace low-temperature sealing elements, automobile polar region sealing strips, deep sea equipment buffer elements, outdoor supplies, cold-resistant flexible circuit boards, unmanned aerial vehicle antifreezing and medical low-temperature catheters and the like, and is a core material for realizing the flexible sealing, shock absorption and buffer functions of low-temperature equipment. With outdoor exploration of people expanding to extreme environments such as polar regions, deep sea and the like, higher requirements are put on performance of TPU in cold environments. However, conventional TPU has significant performance deficiencies in low temperature environments, severely limiting its range of application and causing safety hazards. At low temperature, the thermal motion of the TPU soft segment molecular chain is weakened, when the temperature is reduced below the soft segment glass transition temperature, the molecular chain is frozen, so that the material is quickly embrittled, brittle failure is easy to occur due to external force, meanwhile, the compression set rate is increased, the phase separation is aggravated at low temperature, the interface binding force of the hard and soft segments is reduced, microcrack expansion is easy to occur, and the sealing and damping requirements cannot be met. Not only shortens the service life of the product, but also can cause serious consequences such as equipment failure, safety accidents and the like, thereby causing great economic loss. At present, the prior art mainly improves the low-temperature performance of TPU by means of molecular structure design, formula modification, process optimization, composite modification and the like, wherein a low Tg soft segment is selected to reduce embrittlement temperature, a cold-resistant plasticizer is added to improve low-temperature toughness, and the low-temperature plasticizer is blended with an elastomer such as nitrile rubber and the like to form an interpenetrating network structure, or a filler such as nano silicon dioxide and the like is introduced to refine a phase structure. However, the method has obvious limitations that the use of the low Tg soft segment can reduce the mechanical strength of the material, the plasticizer is easy to separate out at low temperature to influence the stability, the blending modification has the problem of poor compatibility, the nano filler is easy to agglomerate, the performance degradation of the existing cold-resistant TPU at low temperature is obvious, and the use requirement of an extremely low temperature scene cannot be well met. Disclosure of Invention In order to improve the performance of polyurethane under extremely cold conditions, the application provides a cold-resistant TPU material and a preparation method thereof. In the first aspect, the application provides a cold-resistant TPU material which comprises, by weight, 40-60 parts of polytetrahydrofuran ether glycol, 20-30 parts of polycaprolactone glycol, 5-20 parts of fluorocarbon polyether glycol, 1-10 parts of hydroxyphthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol, 30-40 parts of diphenylmethane diisocyanate, 5-20 parts of isophorone diisocyanate, 2-15 parts of chain extender, 0.1-3.0 parts of filler, 0.01-0.5 parts of catalyst and 0.5-3.0 parts of auxiliary agent. In the scheme, the composite soft segment consists of polytetrahydrofuran ether glycol, polycaprolactone glycol and fluorocarbon polyether glycol, the polytetrahydrofuran ether glycol molecular chain is a flexible polyether chain, the intermolecular force is weak, the basic low-temperature flexibility can be provided, the polycaprolactone glycol molecular chain contains ester bonds, a fine crystal region can be formed by moderate crystallization, the composite soft segment is used as a physical crosslinking point to compensate the mechanical strength loss of the low-Tg soft segment, and the fluorocarbon polyether glycol fluorocarbon carbon chain further reduces the overall Tg of the system, and simultaneously inhibits the water vapor adsorption at low temperature. The hydroxyl phthalic anhydride-polyethylene glycol monomethyl ether hybrid modified polyether polyol is a functional component, has a compact molecular structure and a certain steric hindrance, hydroxyl and carboxyl on t