[go: up one dir, main page]

CN116162220B - A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application - Google Patents

A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application Download PDF

Info

Publication number
CN116162220B
CN116162220B CN202211578155.4A CN202211578155A CN116162220B CN 116162220 B CN116162220 B CN 116162220B CN 202211578155 A CN202211578155 A CN 202211578155A CN 116162220 B CN116162220 B CN 116162220B
Authority
CN
China
Prior art keywords
thermoplastic polyurethane
polyurethane elastomer
chain extender
diisocyanate
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211578155.4A
Other languages
Chinese (zh)
Other versions
CN116162220A (en
Inventor
杨永柱
付小亮
何勇
翟志斌
赵亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202211578155.4A priority Critical patent/CN116162220B/en
Publication of CN116162220A publication Critical patent/CN116162220A/en
Application granted granted Critical
Publication of CN116162220B publication Critical patent/CN116162220B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08G18/28—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
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

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 thermoplastic polyurethane elastomer material and a preparation method thereof. The thermoplastic polyurethane elastomer material comprises 25-45 wt% of aliphatic diisocyanate, 40-65 wt% of macromolecular dihydric alcohol, 4-25 wt% of chain extender A, 4-25 wt% of chain extender B and 0.01-0.2 wt% of catalyst. The polyurethane elastomer has tensile strength of more than 40MPa, light transmittance of more than 92%, haze of less than 1.0, rebound rate of more than 99%, rebound time of less than 1s and flame retardant grade V2, and can be used for preparing extruded films, sheets, wires and pipe products with higher requirements on transparency, rebound performance, UV resistance and flame retardant performance, and is particularly suitable for automobile coating film products.

Description

High-transparency high-resilience flame-retardant thermoplastic polyurethane elastomer and preparation method and application thereof
Technical Field
The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a high-transparency high-resilience flame-retardant thermoplastic polyurethane elastomer, a preparation method and application thereof, which have high transparency, high resilience and flame retardance, and are particularly suitable for preparing films, sheets, pipes and the like with transparency and flame retardance.
Technical Field
The thermoplastic polyurethane elastomer has excellent physical and mechanical properties, wear resistance, medium resistance, environmental resistance and temperature resistance, has wide hardness adjustable range, is applicable to multiple processing modes and various molecular structures, can meet the requirements of different properties, and is widely applied to various industries.
With the popularization of automobiles, people have increasingly higher requirements on the comfort, the aesthetic degree and the health performance of automobiles. The automobile paint surface can change color under long-time insolation of sunlight, the automobile appearance is affected, the automobile protective film gradually appears under the background, the automobile coating film has the performances of super toughness, strength, tear resistance and the like, and the automobile paint surface can be isolated from air after being attached, so that the paint surface is permanently protected.
The existing car coating film in the market mainly uses two materials, namely a PVC film and a TPU film, but the PVC film has the defects of easy aging, poor repairability and the like. The TPU film is rich and various in types, and the TPU film prepared through certain polymerization can meet most performance requirements, such as UV resistance, super toughness, wear resistance, easy adhesion, collision and scratch resistance, oxidation resistance, scratch resistance and lasting protection of the automobile paint surface.
The conventional TPU substrate layer has the problems that (1) rebound resilience is slightly poor to influence construction efficiency, and (2) the conventional TPU substrate layer has no flame retardance, so that fire accidents are easy to cause in the processes of production, storage, transportation, vehicle film pasting construction and vehicle use of a vehicle film, and the conventional TPU substrate layer is inconsistent with the application requirements of the development of the conventional automobile.
Patent CN109438670a discloses a high-transparency soft thermoplastic polyurethane elastomer, a preparation method and application thereof, and the polyurethane material with improved transparency is obtained by introducing dihydroxysulfonic acid quaternary ammonium salt to destroy the molecular chain regularity and reduce the crystallization of a hard segment, but the physical and mechanical properties of a sample are low, and the sample does not have flame retardant property.
Patent CN111378272a discloses a thermoplastic polyurethane paint protective film and a preparation method thereof, and a polyurethane car cover film with good comprehensive performance is obtained by blending modified mixed thermoplastic polyolefin resin, but the sample also has no flame retardant property.
Patent CN111909504a discloses a polyurethane flame-retardant film for invisible car clothing, a preparation method and application thereof, polyvinylidene chloride and chlorinated polyethylene are introduced through blending modification, so that the extruded film has certain flame-retardant performance, but the tensile strength and transparency of the film are reduced.
Therefore, the preparation of the thermoplastic polyurethane elastomer material with high rebound, high transparency and flame retardant property has important significance for solving the related problems in the construction and use process of the existing car cover film.
Disclosure of Invention
The invention aims to provide a high-transparency high-resilience flame-retardant thermoplastic polyurethane elastomer, and a preparation method and application thereof. The thermoplastic polyurethane elastomer provided by the invention has better flame retardant property on the premise of not adding other flame retardants, the chain extender contains phosphorus element or halogen with flame retardant property, the flame retardant property is stable, no migration problem exists, and meanwhile, the material has excellent transparency, rebound performance, UV yellowing resistance, wet-hot hydrolysis resistance and weather resistance, can be applied to the fields of films, sheets, pipes, wires and the like, and is especially suitable for the application field of car cover films.
The invention also aims to provide a preparation method of the thermoplastic polyurethane elastomer material, which adopts a one-step method for continuous production and has simple and feasible process.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A thermoplastic polyurethane elastomer material comprising, based on 100% by total weight of components (1) - (4), the following components:
Wherein the chain extender B has the following structure:
Wherein:
W is OH or NH 2 group, M is C or N or O atom, x is an integer from 0 to 20, y is an integer from 0 to 20, z is an integer from 0 to 20;
R 1 and R 2 are each independently selected from C1-C20 linear or branched alkyl or C1-C20 linear or branched haloalkyl, preferably one or more of methyl, ethyl, propyl, isopropyl, isobutyl 、-CH2Cl、-CH2Br、-CH2F、-CH2-CH2Cl、-CH2-CH2Br、-CH2-CH2F、-CH2-CH2-CH2Cl、-CH2-CH2-CH2Br、-CH2-CH2-CH2F、-CH(CH3)-CH2Cl、-CH(CH3)-CH2Br、-CH(CH3)-CH2F、-CH(CH2Cl)-CH2Cl、-CH(CH2Br)-CH2Br、-CH(CH2F)-CH2F.
The aliphatic diisocyanate according to the invention is selected from one or more of 4,4 '-methylenedicyclohexyl diisocyanate, 2,4' -methylenedicyclohexyl diisocyanate and/or 2,2 '-methylenedicyclohexyl diisocyanate (H 12 MDI), hexamethylene Diisocyanate (HDI) and 1-isocyanato-3, 5-trimethyl-5-isocyanatomethyl cyclohexane, pentamethylene 1, 5-diisocyanate, butylene 1, 4-diisocyanate, 1, 10-decane diisocyanate, isophorone diisocyanate (IPDI), 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, 1, 4-cyclohexanedimethylene diisocyanate, 1, 3-cyclohexanediisocyanate or 1, 4-Cyclohexanediisocyanate (CHDI), preferably 4,4' -methylenedicyclohexyl diisocyanate, 2,4 '-methylenedicyclohexyl diisocyanate and/or 2,2' -methylenedicyclohexyl diisocyanate (H 12), hexamethylene Diisocyanate (HDI), 1, 3-cyclohexanediisocyanate or 1, 4-Cyclohexanediisocyanate (CHDI).
The polyol is one or more selected from polyester polyol, polylactone polyol, polyether polyol or polycarbonate polyol, preferably one or more selected from polycaprolactone diol, polycarbonate diol and polytetramethylene ether diol, and the number average molecular weight of the polyol is 700-4000g/mol, preferably 1000-3000g/mol;
The polyester polyol can be prepared by esterification or transesterification of dihydric alcohol and dicarboxylic acid, anhydride or carboxylic ester;
The diols used in the preparation of the polyester polyols of the present invention are preferably one or more of aliphatic and aromatic diols, more preferably one or more of diols having 2 to 12 carbon atoms, including but not limited to ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, decanediol and dodecanediol, further preferred diols are 1, 4-butanediol or 1, 6-hexanediol;
the dicarboxylic acid, acid anhydride or carboxylic acid ester used in the preparation of the polyester polyol of the present invention is one or more of aliphatic and aromatic dicarboxylic acid or acid anhydride or carboxylic acid ester, preferably one or more of dicarboxylic acid, acid anhydride or carboxylic acid ester having 4 to 15 carbon atoms, more preferably one or more of phthalic acid, phthalic anhydride, dimethyl phthalate, dimethyl terephthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, phthalic anhydride and tetrahydrophthalic anhydride, still more preferably one or more of adipic acid, phthalic anhydride and tetrahydrophthalic anhydride;
in the preparation of the polyester polyol according to the present invention, the molar ratio of the diol to the dicarboxylic acid, anhydride or carboxylate is preferably 1.0 to 3.0, more preferably 1.02 to 2.0.
The polylactone polyol is preferably polycaprolactone polyol, and is prepared from epsilon-caprolactone monomers and an initiator under the initiation of a catalyst;
The initiator used in the preparation of the polylactone polyol is one or more of glycol, diamine, alcohol amine and polyol, preferably one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, trimethylolpropane, pentaerythritol, 3 '-dichloro-4, 4' -diaminodiphenylmethane, diethyltoluenediamine, monoethanolamine and diethanolamine, more preferably one or more of ethylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol, TMP and pentaerythritol.
The polycarbonate polyol can be synthesized by adopting a phosgene method, a carbon dioxide regulating copolymerization method, a cyclic carbonate ring-opening polymerization method or an ester exchange method;
the polycarbonate polyol is preferably synthesized by transesterification of dihydric alcohol and carbonic ester;
In the process of synthesizing a polycarbonate polyol by the transesterification method, the dihydric alcohol is preferably one or more of 1, 2-ethylene glycol, 1, 4-Butanediol (BDO), 1, 5-Pentanediol (PDO) and 1, 6-Hexanediol (HDO), and more preferably 1, 4-Butanediol (BDO) and/or 1, 5-Pentanediol (PDO). The carbonate is preferably dimethyl carbonate and diethyl carbonate, more preferably dimethyl carbonate;
the polyether polyol is prepared by reacting an initiator with an epoxy compound containing 2 to 6 carbon atoms;
the initiator used in the preparation process of the polyether polyol is one or more of small molecular polyol, small molecular polyamine and small molecular alcohol amine, and the initiator is preferably one or more of water, propylene glycol, glycerol, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylenediamine, sorbitol, ethylene glycol, bisphenol A and toluenediamine;
The epoxy compound used in the preparation process of the polyether polyol is preferably one or more of ethylene oxide, propylene oxide and Tetrahydrofuran (THF);
The polyether polyol is preferably polytetramethylene ether glycol (PTMEG) prepared from polyethylene glycol prepared by reacting ethylene oxide with ethylene glycol, polypropylene glycol prepared by reacting propylene oxide with propylene glycol or polytetramethylene ether glycol (PTMEG) prepared by reacting water with Tetrahydrofuran (THF), or copolyethers prepared from reaction products of THF with ethylene oxide or THF with propylene oxide, and more preferably the polyether polyol is polytetramethylene ether glycol (PTMEG).
The chain extender A comprises small molecular dihydric alcohol and/or diamine, has 2 to 15 carbon atoms, and is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, isopentane diol, neopentyl glycol, 2-methyl-2, 4-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, 1, 4-cyclohexanedimethanol, decanediol and dodecanediol, 1, 3-propanediol, 1, 4-butanediamine, p-phenylenediamine and biphenyldiamine, and is preferably selected from one or more of 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, isopentane diol and 3-methyl-1, 5-pentanediol.
The chain extender B of the present invention is preferably one or more of the following structures:
the molar ratio of the chain extender A to the chain extender B is 10:1 to 1:8.
The isocyanate index (-NCO to-OH molar ratio) of the thermoplastic polyurethane elastomer material disclosed by the invention is 0.9-1.1, preferably 0.98-1.02.
The catalyst is one or more selected from an organic bismuth catalyst, an organic tin catalyst, an organic zinc catalyst and a titanate catalyst, preferably one or more selected from dibutyl tin dilaurate, stannous octoate, dibutyl tin diacetate, tetraisopropyl titanate, bismuth isooctanoate, bismuth neodecanoate and tetrabutyl titanate.
The preparation raw materials of the thermoplastic polyurethane elastomer material can also comprise a mixing auxiliary agent, wherein the mixing auxiliary agent comprises a light stabilizer, an antioxidant and a hydrolysis stabilizer, and the addition amount of the mixing auxiliary agent is 0.5-3wt% based on the total mass of diisocyanate, polyalcohol, chain extender and catalyst.
The invention relates to a preparation method of a high-transparency high-resilience flame-retardant thermoplastic polyurethane elastomer, which comprises the following steps:
The isocyanate, the polyol, the chain extender, the catalyst and the optional mixed auxiliary agent are sent into a screw rod of a double-screw extruder through a feeding and pouring system, then melt extrusion reaction is carried out, underwater pelletization, curing and drying are carried out, and the high-transparency high-resilience flame-retardant thermoplastic polyurethane elastomer can be obtained;
the extrusion temperature of the double-screw extruder is 120-240 ℃;
the actual screw speed of the twin-screw extruder is 100-300 rpm.
The polyurethane elastomer has tensile strength of more than 40MPa, light transmittance of more than 92%, haze of less than 1.0, rebound rate of more than 99%, rebound time of less than 1s and flame retardant grade V2, and can be used for preparing extruded films, sheets, wires and pipe products with higher requirements on transparency, rebound performance, UV resistance and flame retardant performance, and is particularly suitable for automobile coating film products.
The invention also relates to application of the thermoplastic polyurethane elastomer in the fields of preparing films, sheets, extruded pipes, extruded cables and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) The special chain extender B with a larger side group is used as the mixed chain extender to prepare the TPU material, the steric hindrance effect of the larger side group is utilized to destroy the regularity of a molecular chain, the crystallization degree of the material is reduced, the transparency is improved, and the extruded film material with low haze and excellent transparency is obtained.
2) According to the invention, the special chain extender B introduces the phosphorus element or/and halogen element with flame retardant property into the TPU molecular chain, so that the TPU material has intrinsic flame retardant property, and the problem of unstable migration of the flame retardant is avoided.
3) The special chain extender B used in the invention contains at least one primary amine group, and polyurea groups are introduced into the TPU main chain, so that the intermolecular hydrogen bond acting force is increased, the physical and mechanical properties of the material are improved, the rebound resilience of the extruded film is improved, and the construction efficiency of finished automobile coating films is improved.
Detailed Description
The present invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
Some of the component sources in the examples and comparative examples are as follows:
H 12 MDI, wanhua chemical group Co., ltd;
HXDI, wanhua chemical group Co., ltd;
polycaprolactone polyol 1, injevelet, number average molecular weight 1000;
polycaprolactone polyol 2, enjevelet, number average molecular weight 2000;
Polycaprolactone polyol 3, injevelet, number average molecular weight 3000;
polytetramethylene ether polyol 1: basf, number average molecular weight 1000;
Polytetramethylene ether polyol 2, basf, number average molecular weight 2000;
Polycarbonate polyol 1, dazui, number average molecular weight 2000;
Chain extender 1:1, 4-butanediol;
chain extender 2 (refer to the following patent synthesis ：Organophosphorusflame retardant hardener and a manufacturing method thereof Republic of KR2016043195 A2016-04-21)
Chain extender 3:
chain extender 4:
Catalyst 1 is stannous octoate and catalyst 2 is bismuth neodecanoate
The auxiliary agent package is prepared by self-preparing an auxiliary agent package containing an antioxidant, a light stabilizer and a hydrolysis-resistant auxiliary agent, wherein the auxiliary agent package comprises the following components in percentage by mass (antioxidant 1010/UV 292/carbodiimide monomer=1:3:1).
The polyurethane elastomers obtained were tested by the prescribed method for the following properties:
1) Tensile Strength and elongation at break ASTM D412
2) Light transmittance and haze ASTM D1003
3) Heat and humidity aging resistance (double 85) cast 0.15mm films were placed in a constant temperature and humidity cabinet at 85 ℃ and 85% humidity for 2 weeks and tested for tensile strength according to ASTM D412.
4) UV aging resistance, UVA340 (0.15 mmTPU film), irradiation intensity 0.77W/m 2, conditions 70 ℃ and 8h irradiation, and then 50 ℃ and 4h condensation, and testing for 3000h total, and investigating the change of chromatic aberration dE.
5) Rebound time and rebound rate: film thickness 0.15mm, 30mm x 150mm long bar, stretching 30%, standing for 30s, film bar rebound, timing rebound time, standing for 5min, and testing rebound rate.
6) Flame retardant property UL94.
Example 1
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:35.39wt%;
2) 1:50wt% of polycaprolactone polyol;
3) Chain extender 1+ chain extender 2:14.6wt%;
4) Catalyst 1:0.01wt%;
wherein the mol ratio of the chain extender 1 to the chain extender 2 is 1:1;
The preparation method comprises the following steps:
The components (H 12 MDI, polycaprolactone polyol 1, chain extender 2 and catalyst 1) are added into a double-screw extruder through a feeding and pouring system, thermoplastic polyurethane elastomer particles are obtained after reactive extrusion, underwater pelleting and drying, the particles are processed and prepared into finished pieces, the finished pieces are tested according to a related test method, the temperature of the extruder is set to 120-240 ℃, and the screw rotating speed is 200rpm.
Example 2
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:36.3wt%;
2) 2:52wt% of polycaprolactone polyol;
3) Chain extender 1+ chain extender 3:11.68wt%;
4) Catalyst 2:0.02wt%;
wherein the mol ratio of the chain extender 1 to the chain extender 3 is 10:1;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 3
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:28.05wt%;
2) 3:55wt% of polycaprolactone polyol;
3) Chain extender 1+ chain extender 3:16.85wt%;
4) Catalyst 1:0.1wt%;
Wherein the mol ratio of the chain extender 1 to the chain extender 3 is 1:3;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 4
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:34wt%;
2) 1:45wt% of polytetramethylene ether polyol;
3) Chain extender 1+ chain extender 4:20.95wt%;
4) Catalyst 2:0.05wt%;
Wherein the mol ratio of the chain extender 1 to the chain extender 4 is 1:8, and the preparation method of the thermoplastic polyurethane is the same as that of the example 1.
Example 5
A thermoplastic polyurethane elastomer comprising the following components:
1)HXDI:38.3wt%;
2) Polytetramethylene ether polyol 2:40wt%;
3) Chain extender 1+ chain extender 4:21.6wt%;
4) Catalyst 1:0.1wt%;
Wherein the mol ratio of the chain extender 1 to the chain extender 4 is 5:1, and the preparation method of the thermoplastic polyurethane is the same as that of the example 1.
Example 6
A thermoplastic polyurethane elastomer comprising the following components:
1)HXDI:26.9wt%;
2) 1:60wt% of polycarbonate polyol;
3) Chain extender 1+ chain extender 4:13wt%;
4) Catalyst 2:0.1wt%;
Wherein the mol ratio of the chain extender 1 to the chain extender 4 is 5:1, and the preparation method of the thermoplastic polyurethane is the same as that of the example 1.
Example 7
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:36.1wt%;
2) Polycaprolactone polymer polyol 1:55wt%;
3) Chain extender 1+ chain extender 2:8.7wt%;
4) Catalyst 1:0.2wt%;
wherein the mol ratio of the chain extender 1 to the chain extender 2 is 8:1;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 8
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:38.7wt%;
2) 1:40wt% of polytetramethylene ether polyol;
3) Chain extender 1+ chain extender 3:21.27wt%;
4) Catalyst 2:0.03wt%;
wherein the mol ratio of the chain extender 1 to the chain extender 3 is 1:5;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Example 9
A thermoplastic polyurethane elastomer comprising the following components:
1)H12MDI:32.7wt%;
2) Polycaprolactone polyol 1:48wt%;
3) Chain extender 1+ chain extender 4:19.27wt%;
4) Catalyst 1:0.03wt%;
5) The additive package is 1.5% of the total mass of the components 1)/2)/3) 4), and is dissolved in the polyalcohol and added into the extruder through a feeding and pouring system;
wherein the mol ratio of the chain extender 1 to the chain extender 4 is 1:8;
the above thermoplastic polyurethane preparation method is the same as in example 1.
Comparative example 1
A thermoplastic polyurethane elastomer comprising the following components 1) H 12 MDI 37.36 wt.%;
2) 2:52wt% of polycaprolactone polyol;
3) Chain extender 1:10.62wt%;
4) Catalyst 2:0.02wt%;
the preparation method is the same as in example 1.
Comparative example 2
A thermoplastic polyurethane elastomer comprising the following components 1) H 12 MDI 43.9 wt.%;
2) 1:45wt% of polytetramethylene ether polyol;
3) 11.05wt% of chain extender;
4) Catalyst 2:0.05wt%;
the preparation method is the same as in example 1.
Comparative example 3
A thermoplastic polyurethane elastomer comprising the following components 1) HXDI 32.3wt%;
2) 1:55wt% of a polycarbonate polyol;
3) Chain extender 1:12.6wt%;
4) Catalyst 2:0.1wt%;
the preparation method is the same as in example 1.
The products prepared in the above examples and comparative examples were subjected to performance tests in which the light transmittance and haze test samples were cast films of 0.15mm, the tensile strength and elongation at break test were carried out on the films of 0.15mm according to ASTM D412, and the flame retardant test sample was a 3mm injection molded test piece, which was tested with reference to UL 94. The test results are shown in Table 1 below:
table 1 results of performance testing of examples and comparative products
The thermoplastic polyurethane elastomer prepared by the invention has excellent physical and mechanical properties, transparency, rebound resilience, hydrolysis resistance and UV aging resistance, and meanwhile, the material has better flame retardant property, wherein the tensile strength is more than 40MPa, the light transmittance is more than 92%, the haze is less than 1.0, the rebound rate is more than 99%, the rebound time is less than 1s, and the flame retardant grade is more than V2.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (12)

1. A thermoplastic polyurethane elastomer comprising, based on 100% by total weight of components (1) - (4), the following components:
(1) 25 to 45wt% of at least one aliphatic diisocyanate
Wherein the aliphatic diisocyanate is selected from one or more of 4,4 '-methylene dicyclohexyl diisocyanate, 2' -methylene dicyclohexyl diisocyanate, hexamethylene diisocyanate, 1-isocyanato-3, 5-trimethyl-5-isocyanatomethyl cyclohexane, pentamethylene 1, 5-diisocyanate, butylene 1, 4-diisocyanate, 1, 10-decane diisocyanate, isophorone diisocyanate, 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, 1, 4-cyclohexane dimethylene diisocyanate, 1, 3-cyclohexane diisocyanate or 1, 4-cyclohexane diisocyanate;
(2) 40-65wt% of at least one polyol;
(3) 4-25wt% of at least one chain extender A and at least one chain extender B;
Wherein the molar ratio of the chain extender A to the chain extender B is 10:1 to 1:8;
(4) 0.01-0.2wt% of a catalyst;
wherein the chain extender A is at least one of micromolecular dihydric alcohol and/or diamine with 2 to 15 carbon atoms, and the chain extender B has the following structure:
Wherein:
W is OH or NH 2 group, M is C or N or O atom, x is an integer from 0 to 20, y is an integer from 0 to 20, z is an integer from 0 to 20;
R 1 and R 2 are each independently selected from the group consisting of C1-C20 linear or branched alkyl or C1-C20 linear or branched haloalkyl.
2. The thermoplastic polyurethane elastomer according to claim 1, wherein the contents of the components are:
3. the thermoplastic polyurethane elastomer according to claim 1, wherein R 1 and R 2 in the chain extender B are each independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, isobutyl 、-CH2Cl、-CH2Br、-CH2F、-CH2-CH2Cl、-CH2-CH2Br、-CH2-CH2F、-CH2-CH2-CH2Cl、-CH2-CH2-CH2Br、-CH2-CH2-CH2F、-CH(CH3)-CH2Cl、-CH(CH3)-CH2Br、-CH(CH3)-CH2F、-CH(CH2Cl)-CH2Cl、-CH(CH2Br)-CH2Br、-CH(CH2F)-CH2F.
4. The thermoplastic polyurethane elastomer according to any one of claims 1-2, wherein the polyol is selected from one or more of a polyester polyol, a polyether polyol or a polycarbonate polyol;
The number average molecular weight of the polyol is 700-4000g/mol.
5. The thermoplastic polyurethane elastomer according to claim 4, wherein the polyol is selected from one or more of polycaprolactone diol, polycarbonate diol, polytetramethylene ether diol;
The number average molecular weight of the polyol is 1000-3000g/mol.
6. The thermoplastic polyurethane elastomer according to claim 1 or 2, wherein the chain extender a is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, isopentane diol, neopentyl glycol, 2-methyl-2, 4-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, 1, 4-cyclohexanedimethanol, decanediol and dodecanediol, 1, 3-propanediol, 1, 4-butanediamine, p-phenylenediamine, biphenyl diamine.
7. A thermoplastic polyurethane elastomer according to any one of claims 1 to 3, wherein the chain extender B is selected from one or more of the following structures:
8. the thermoplastic polyurethane elastomer according to any one of claims 1-2, wherein the catalyst is selected from one or more of organobismuth catalysts, organotin catalysts, organozinc catalysts or titanate-based catalysts.
9. The thermoplastic polyurethane elastomer of claim 8 wherein the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, tetraisopropyl titanate, bismuth isooctanoate, bismuth neodecanoate, and tetrabutyl titanate.
10. A process for the preparation of a thermoplastic polyurethane elastomer according to any one of claims 1 to 9, characterized by comprising the steps of:
Aliphatic diisocyanate, polyol, chain extender and catalyst are fed into a screw of a double-screw extruder through a feeding and pouring system, then melt extrusion reaction is carried out, underwater pelletization and drying are carried out, and the thermoplastic polyurethane elastomer is obtained.
11. The preparation method of claim 10, wherein the extrusion temperature of the twin-screw extruder is 120-240 ℃;
the actual screw speed of the twin-screw extruder is 100-300 rpm.
12. Use of the thermoplastic polyurethane elastomer according to any of claims 1-9 for the preparation of a film, sheet, extruded tubing, extruded cable.
CN202211578155.4A 2022-12-09 2022-12-09 A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application Active CN116162220B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211578155.4A CN116162220B (en) 2022-12-09 2022-12-09 A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211578155.4A CN116162220B (en) 2022-12-09 2022-12-09 A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application

Publications (2)

Publication Number Publication Date
CN116162220A CN116162220A (en) 2023-05-26
CN116162220B true CN116162220B (en) 2025-02-18

Family

ID=86412187

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211578155.4A Active CN116162220B (en) 2022-12-09 2022-12-09 A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application

Country Status (1)

Country Link
CN (1) CN116162220B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119285892B (en) * 2024-09-03 2025-05-16 太原工业学院 A colorless and transparent polyurethane elastomer and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160043195A (en) * 2014-10-10 2016-04-21 이승준 Organic Phosphorus Flame-Resistant Curing Agents And Methods thereof
CN109134802A (en) * 2017-06-27 2019-01-04 万华化学集团股份有限公司 A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160043195A (en) * 2014-10-10 2016-04-21 이승준 Organic Phosphorus Flame-Resistant Curing Agents And Methods thereof
CN109134802A (en) * 2017-06-27 2019-01-04 万华化学集团股份有限公司 A kind of phosphor-containing halogen-free flame retardant thermoplastic polyurethane elastomer composition and its preparation method and application

Also Published As

Publication number Publication date
CN116162220A (en) 2023-05-26

Similar Documents

Publication Publication Date Title
KR0143394B1 (en) Process for producing impact-resistant polyacetal resin composition
CN109134802B (en) Phosphorus-containing halogen-free flame-retardant thermoplastic polyurethane elastomer composition and preparation method and application thereof
CN107129674B (en) Low-gloss thermoplastic polyurethane composition and preparation method and application thereof
US11053343B2 (en) Thermoplastic polyurethane resin composition and molded body using said resin composition
CN106928693B (en) Low-gloss thermoplastic polyurethane composition and preparation method and application thereof
KR100583215B1 (en) Polyester urethane elastomer and preparation method thereof
WO2008045853A1 (en) Thermoplastic polyurethanes containing a salt of zirconium phosphate
CN116162220B (en) A highly transparent, highly resilient, flame-retardant thermoplastic polyurethane elastomer and its preparation method and application
CN106928694B (en) Low-gloss thermoplastic polyurethane composition and preparation method and application thereof
US20200332117A1 (en) Thermoplastic Polyurethane Composition
US8822624B2 (en) Thermoplastic polyurethane with reduced formation of deposit
WO2018155396A1 (en) Thermoplastic polyurethane resin composition and molded body using said resin composition
TW201802183A (en) Melt processable thermoplastic polyurethane-urea elastomers
CN120173200A (en) Thermoplastic polyurethane elastomer and preparation method and application thereof
EP2279218B1 (en) Thermoplastic polyurethanes with good fuel resistance
EP3720895A1 (en) Chemical and stain resistant thermoplastic polyurethane composition
JP2853118B2 (en) Method for producing thermoplastic polyurethane elastomer
JPH02160820A (en) Polyurethane resin composition
US20150175736A1 (en) Stable thermoplastic polyurethane elastomers
CN118373962B (en) Thermoplastic polyurethane elastomer and preparation method thereof
JP7563172B2 (en) Resin composition, resin film and molded article
KR101831854B1 (en) Copolyester resin composition having excellent hydrolysis resistant and biodegradable
KR20230079951A (en) Thermoplastic urethane resin for flexible display and manufacturing method thereof
WO2024099905A1 (en) Thermoplastic polyurethane, polyurethane resin composition comprising the same, and molded product obtained from the same
WO2023025638A1 (en) Antistatic masterbatch based on thermoplastic polyurethan with improved properties for the use in polymers

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant