Crystallization controllable thermoplastic polyurethane material and preparation method thereof

A thermoplastic polyurethane, crystallization technology, applied in the field of thermoplastic polyurethane materials and its preparation, can solve the problems of reducing crystallinity, inappropriate rapid prototyping, expensive, etc., achieve the effect of reducing shrinkage rate and improving biological utilization value

Active Publication Date: 2017-09-08
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] CN1439662A discloses a soft low-shrinkage thermoplastic polyurethane elastomer that is easy to demould, uses mixed soft segment polyols to control the crystallization performance of the soft segment, and achieves easy demoulding; CN102159612B discloses an improved and less crystallizable Polyurethanes of polyester diols, branched diols also promote significant inhibition of so-called soft-phase crystallization; but these approaches require complex and expensive soft-segment resins
[0007] CN1271108C discloses a thermoplastic polyurethane composition with high crystallization content that can be advantageously processed in an extruder. Adding a crystallization inhibitor component inhibits the rapid crystallization of TPU in the extruder to ensure extrusion processing performance. The added crystallization inhibitor The components are all alcohol structures containing steric hindrance, which w

Method used

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  • Crystallization controllable thermoplastic polyurethane material and preparation method thereof
  • Crystallization controllable thermoplastic polyurethane material and preparation method thereof
  • Crystallization controllable thermoplastic polyurethane material and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Polyethylene adipate diol with a number average molecular weight of 2000 g / mol, 1,4-butylene diamine, cyclodextrin derivative 2,6-diaminopentyl-β-cyclodextrin and 1, 4-Cyclohexyldimethanol was vacuum dehydrated at high temperature.

[0054] Heat 32.2 parts (parts by weight, the same below) of diphenylmethylene diisocyanate to 70°C, then add 50 ppm of dibutyltin dilaurate, based on the quality of diphenylmethylene diisocyanate and 60 parts of number average molecular weight 2000g / mol polyethylene adipate diol and 2 parts of 2,6-diaminopentyl-β-cyclodextrin were reacted at 70°C for 1h to obtain a stable prepolymer, and then 7.6 parts were expanded Chain agent, among them, 5.07 parts of the main chain extender 1,4-butylene diamine and 2.53 parts of the auxiliary chain extender 1,4-cyclohexyldimethanol are added to the prepolymer obtained before, after high-speed stirring and mixing, pour into Put it into the mold, put it into an oven at 80° C., and mature it for 20 hours,...

Embodiment 2

[0056] Polyethylene adipate diol with a number average molecular weight of 600 g / mol, cyclodextrin derivatives 2,6-dihydroxypentyl-β-cyclodextrin, 1,8-octyldiamine and spirocyclic Ethylene glycol is vacuum dehydrated at high temperature.

[0057] Heat 45.2 parts of diphenylmethylene diisocyanate to 100°C, then add 50 ppm of dibutyltin dilaurate, based on the mass of diphenylmethylene diisocyanate and 50 parts of polyhexamethylene diisocyanate with a number average molecular weight of 600 g / mol Acetate ethylene glycol ester diol and 2 parts of 2,6-dihydroxypentyl-β-cyclodextrin, react at 100°C for 1.5h to obtain a stable prepolymer, and then add 12 parts of chain extender, of which 4.5 parts Add the main chain extender 1,8-octanediamine and 7.5 parts of chain extender spiroethylene glycol to the prepolymer obtained before, stir and mix evenly at high speed, pour it into the mold, and put it in an oven at 120°C for curing After 24 hours, cool and pulverize the obtained thermopl...

Embodiment 3

[0059] Polytetrahydrofuran diol with a number average molecular weight of 800 g / mol, methyldiethanolamine, cyclodextrin derivatives 2,6-diaminooctyl-β-cyclodextrin and isophoronediamine were vacuum dehydrated at high temperature .

[0060] 27.8 parts of 4,4'-dicyclohexylmethane diisocyanate were heated to 50°C, followed by the addition of 100 ppm of bismuth isooctanoate, based on the mass of 4,4'-dicyclohexylmethane diisocyanate and 66.4 parts of number average molecular weight 800 g / mol Polytetrahydrofuran diol and 3 parts of 2,6-dihydroxyoctyl-β-cyclodextrin were reacted at 50°C for 0.5h to obtain a stable prepolymer, and then 5.8 parts of chain extenders were added, of which 4.35 parts were the main extenders Add the chain agent methyldiethanolamine and 1.45 parts of chain extender isophoronediamine to the prepolymer obtained before, stir and mix evenly at a high speed, pour it into a mold, put it in a 100°C oven for aging for 20 hours, cool, The obtained thermoplastic pol...

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PUM

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Abstract

The invention discloses a crystallization controllable thermoplastic polyurethane material and a preparation method of the crystallization controllable thermoplastic polyurethane material. The thermoplastic polyurethane material comprises and is prepared from the following components: 1) a diisocyanate compound; 2) a hydroxyl and/or amido end capped macromolecular compound; 3) a diamine or diol cyclodextrin derivative; 4) a chain extender. The types and the use amounts of a main chain extender and an auxiliary chain extender in the chain extender are controlled, meanwhile, the cyclodextrin derivative is introduced, so that the crystallization characteristic of the thermoplastic polyurethane material is controlled, the controllable degree of crystallinity and the improved viscosity temperature sensitivity are obtained, and the shrinkage percentage of the material is also changed correspondingly. The obtained thermoplastic polyurethane material can be used in a rapid forming method in the fusing processing, like a fused deposition rapid forming method or a selective laser sintering method.

Description

technical field [0001] The invention relates to a thermoplastic polyurethane material with controllable crystallization and a preparation method thereof, belonging to the field of elastomer materials. Background technique [0002] Thermoplastic Polyurethane (TPU for short) is a type of polyurethane that can be plasticized by heating and can be dissolved in solvents. There is no or little chemical crosslinking in the chemical structure, and its molecules are basically linear. The properties of the material can be adjusted by designing the ratio and length of the soft and hard segments of the molecule. The polyether or polyester in TPU endows the polyurethane with elasticity for the soft segment; the chain segment formed by the reaction of diisocyanate and the chain extender is the hard segment, and the existence of the -NHCOO- functional group in the hard segment makes a large number of hydrogen bonds between the molecular chains, mutual The force is strong, so the hard segm...

Claims

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Application Information

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IPC IPC(8): C08G18/66C08G18/64C08G18/42C08G18/48C08G18/44C08G18/50C08G18/69C08G18/32C08G18/12
CPCC08G18/12C08G18/4018C08G18/4081C08G18/4213C08G18/4238C08G18/4277C08G18/44C08G18/4854C08G18/5024C08G18/6484C08G18/69C08G18/3206C08G18/3228C08G18/3234C08G18/3212C08G18/3275
Inventor 杨杰黄岐善
Owner WANHUA CHEM GRP CO LTD
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