CN107325257A - A kind of method for preparing thermoplastic polyurethane elastomer - Google Patents

A kind of method for preparing thermoplastic polyurethane elastomer Download PDF

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Publication number
CN107325257A
CN107325257A CN201710695892.5A CN201710695892A CN107325257A CN 107325257 A CN107325257 A CN 107325257A CN 201710695892 A CN201710695892 A CN 201710695892A CN 107325257 A CN107325257 A CN 107325257A
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CN
China
Prior art keywords
diisocyanate
pepa
polyurethane elastomer
stirring
chain extender
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Pending
Application number
CN201710695892.5A
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Chinese (zh)
Inventor
史玉林
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CHUZHOU YULIN POLYURETHANE Co Ltd
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CHUZHOU YULIN POLYURETHANE Co Ltd
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Priority to CN201710695892.5A priority Critical patent/CN107325257A/en
Publication of CN107325257A publication Critical patent/CN107325257A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681Compounds 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
    • C08G18/6685Compounds 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 C08G18/3225 or polyamines of C08G18/38

Abstract

The invention discloses a kind of method for preparing thermoplastic polyurethane elastomer, comprise the following steps:S1, polyurethane elastomer raw material composition, S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition, for the first time S3, stirring mixing, S4, second of stirring mixing, S5, transporting molten reaction mass, S6, elastomer granulation, S7, drying and dehydrating.Method for preparing thermoplastic polyurethane elastomer of the present invention, low energy consumption, pollution-free, mechanical performance are significantly improved, it is wider using scope, preparation method is simple, efficient stable, it can be used for large-scale industrial production, PEPA, diisocyanate and chain extender dispensing improve properties of product by uniformly being mixed twice.

Description

A kind of method for preparing thermoplastic polyurethane elastomer
Technical field
The present invention relates to technical field of polyurethane elastomer, specially a kind of preparation side of TPUE Method.
Background technology
TPUE(Abbreviation TPU), it is the polyurethane products that class heating can dissolve.It is by big There is the high score of carbamate group obtained by molecule PEPA, small molecule dihydric alcohol and diisocyanate polymerization Sub- compound, the block copolymer being made up of in the molecular structure soft segment and hard section, the high resiliency of its existing elastomeric material, again There is the high intensity of engineering plastics;In very wide temperature(40-120)TPU has flexibility;Additionally there is good oil resistant The surrounding medium performance such as property, solvent resistance, resistance to weather and resistance to high-energy ray performance;Wearability, tear resistance, flexion are strong The mechanical property such as degree, tensile strength, elongation, resilience and shear strength and impact resistance is also very excellent.The characteristics of TPU is It is fusible solvable, it can be molded using a variety of processing methods, product can be extensively using making shaped body, tubing, film, adhesive, painting Material and fiber.So excellent physical and mechanical property, surrounding medium performance and processing characteristics, makes TPU in industrial aspect, doctor The application for treating the fields such as health, sports goods, daily necessities and military supplies achieves success.The repeatable processing of TPU simultaneously Utilize, and water and carbon dioxide can be degraded into automatically in nature, with the characteristic not polluted to environment, not Come in social development to be increasingly widely applied.
The content of the invention
It is an object of the invention to provide a kind of method for preparing thermoplastic polyurethane elastomer, to solve above-mentioned background skill The problem of being proposed in art.
A kind of method for preparing thermoplastic polyurethane elastomer, it is characterised in that comprise the following steps:
S1, polyurethane elastomer raw material composition:Polyurethane elastomer is by PEPA, diisocyanate and chain extender dispensing Form, PEPA include interior alcohol, polyalcohol urge, catalyst and light stabilizer, it is different that diisocyanate includes diphenyl-methane two Cyanate, toluene di-isocyanate(TDI) and plasticizer, chain extender include ethylene glycol, propane diols, dipropylene glycol and diethyl first Phenylenediamine.
S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition:(1)The preparation method of PEPA is such as Under:By weight percentage, 35-40%, catalyst 10%-20% and light stabilizer 5%- are urged by interior alcohol 30-45%, polyalcohol 15% composition PEPA;(2)The preparation method of diisocyanate is as follows:By weight percentage, it is different by diphenyl-methane two Cyanate 20%-55%, toluene di-isocyanate(TDI) 40%-70% and plasticizer 5%-10% composition diisocyanate;(3)Chain extension The preparation method of agent is as follows:By weight percentage, by ethylene glycol 15%-20%, propane diols 25%-30%, a contracting dipropyl two Alcohol 25%-30% and diethyl toluene diamine 25%-30% composition chain extenders;
S3, for the first time stirring mixing:PEPA and diisocyanate in S2 is poured into mixing drum and is sufficiently stirred for, Material heats up 70-80 degrees Celsius during stirring, now can release the vacuum inside mixing drum to addition nitrogen inside mixing drum, be allowed to Vacuumize stirring mixing 1-2h;
S4, second of stirring mixing:Chain extender is added into mixing drum after S3, quick stirring vacuumizes degassing, material Temperature gradually rises to 110-120 degrees Celsius, and viscosity substantially increases, and stops stirring;
S5, transporting molten reaction mass:Frit reaction material in S4 is discharged from mixing drum, and is poured into and is loaded in conveyer belt On coat in advance in the polytetrafluoroethyldisk disk of releasing agent, and conveyer belt is placed in 100-130 degrees Celsius of curing oven, is continuously poured The material of note moves heat aging on a moving belt;
S6, elastomer granulation:After material cooling 1-2h after S5 is cured, deliver in vacuum granulator and granulated;
S7, drying and dehydrating:Particle in S6 is dried into the moisture in 4-5h, removing particle under 85-90 degrees Celsius, then through note The type of being moulded into can be prepared by TPUE.
It is preferred that, the rotating speed of hybrid motor is stirred in the S3 for the first time for 400r/min, is stirred for the second time in the S4 Mix the rotating speed 300r/min of hybrid motor.
It is preferred that, frit reaction material viscosity is 6000-10000CPS in the S5.
Compared with prior art, the beneficial effects of the invention are as follows:Method for preparing thermoplastic polyurethane elastomer of the present invention, Low energy consumption, pollution-free, mechanical performance are significantly improved, wider using scope, and preparation method is simple, efficient stable, can be used for big The industrialized production of scale, PEPA, diisocyanate and chain extender dispensing are improved by uniformly being mixed twice Properties of product.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not For limiting the present invention.
Embodiment 1
A kind of method for preparing thermoplastic polyurethane elastomer, it is characterised in that comprise the following steps:
S1, polyurethane elastomer raw material composition:Polyurethane elastomer is by PEPA, diisocyanate and chain extender dispensing Form, PEPA include interior alcohol, polyalcohol urge, catalyst and light stabilizer, it is different that diisocyanate includes diphenyl-methane two Cyanate, toluene di-isocyanate(TDI) and plasticizer, chain extender include ethylene glycol, propane diols, dipropylene glycol and diethyl first Phenylenediamine.
S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition:(1)The preparation method of PEPA is such as Under:By weight percentage, to urge 37%, catalyst 15% and light stabilizer 15% to constitute polyester by interior alcohol 33%, polyalcohol more First alcohol;(2)The preparation method of diisocyanate is as follows:By weight percentage, by '-diphenylmethane diisocyanate 30%, toluene Diisocyanate 62% constitutes diisocyanate with plasticizer 8%;(3)The preparation method of chain extender is as follows:With percetage by weight Meter, chain extender is constituted by ethylene glycol 17%, propane diols 28%, dipropylene glycol 26% and diethyl toluene diamine 29%;
S3, for the first time stirring mixing:PEPA and diisocyanate in S2 is poured into mixing drum and is sufficiently stirred for, Material heats up 72 degrees Celsius during stirring, now can release the vacuum inside mixing drum to addition nitrogen inside mixing drum, be allowed to take out It is stirred under vacuum mixing 1.5h;
S4, second of stirring mixing:Chain extender is added into mixing drum after S3, quick stirring vacuumizes degassing, material Temperature gradually rises to 115 degrees Celsius, and viscosity substantially increases, and stops stirring;
S5, transporting molten reaction mass:Frit reaction material in S4 is discharged from mixing drum, and is poured into and is loaded in conveyer belt On coat in advance in the polytetrafluoroethyldisk disk of releasing agent, and conveyer belt is placed in 118 degrees Celsius of curing oven, is continuously poured into a mould Material moves heat aging on a moving belt;
S6, elastomer granulation:After material cooling 1.4h after S5 is cured, deliver in vacuum granulator and granulated;
S7, drying and dehydrating:Particle in S6 is dried into the moisture in 4.5h, removing particle under 86 degrees Celsius, then through injection Shaping can be prepared by TPUE.
The rotating speed for stirring hybrid motor in the S3 for the first time is second of stirring mixing electricity in 400r/min, the S4 The rotating speed 300r/min of motivation.
Frit reaction material viscosity is 6000-10000CPS in the S5.
Embodiment 2
A kind of method for preparing thermoplastic polyurethane elastomer, it is characterised in that comprise the following steps:
S1, polyurethane elastomer raw material composition:Polyurethane elastomer is by PEPA, diisocyanate and chain extender dispensing Form, PEPA include interior alcohol, polyalcohol urge, catalyst and light stabilizer, it is different that diisocyanate includes diphenyl-methane two Cyanate, toluene di-isocyanate(TDI) and plasticizer, chain extender include ethylene glycol, propane diols, dipropylene glycol and diethyl first Phenylenediamine.
S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition:(1)The preparation method of PEPA is such as Under:By weight percentage, to urge 37%, catalyst 12% and light stabilizer 13% to constitute polyester by interior alcohol 38%, polyalcohol more First alcohol;(2)The preparation method of diisocyanate is as follows:By weight percentage, by '-diphenylmethane diisocyanate 51%, toluene Diisocyanate 42% constitutes diisocyanate with plasticizer 7%;(3)The preparation method of chain extender is as follows:With percetage by weight Meter, chain extender is constituted by ethylene glycol 18%, propane diols 27%, dipropylene glycol 26% and diethyl toluene diamine 29%;
S3, for the first time stirring mixing:PEPA and diisocyanate in S2 is poured into mixing drum and is sufficiently stirred for, Material heats up 74 degrees Celsius during stirring, now can release the vacuum inside mixing drum to addition nitrogen inside mixing drum, be allowed to take out It is stirred under vacuum mixing 1.6h;
S4, second of stirring mixing:Chain extender is added into mixing drum after S3, quick stirring vacuumizes degassing, material Temperature gradually rises to 116 degrees Celsius, and viscosity substantially increases, and stops stirring;
S5, transporting molten reaction mass:Frit reaction material in S4 is discharged from mixing drum, and is poured into and is loaded in conveyer belt On coat in advance in the polytetrafluoroethyldisk disk of releasing agent, and conveyer belt is placed in 120 degrees Celsius of curing oven, is continuously poured into a mould Material moves heat aging on a moving belt;
S6, elastomer granulation:After material cooling 1.7h after S5 is cured, deliver in vacuum granulator and granulated;
S7, drying and dehydrating:Particle in S6 is dried into the moisture in 4.7h, removing particle under 87 degrees Celsius, then through injection Shaping can be prepared by TPUE.
The rotating speed for stirring hybrid motor in the S3 for the first time is second of stirring mixing electricity in 400r/min, the S4 The rotating speed 300r/min of motivation.
Frit reaction material viscosity is 6000-10000CPS in the S5.
Embodiment 3
A kind of method for preparing thermoplastic polyurethane elastomer, it is characterised in that comprise the following steps:
S1, polyurethane elastomer raw material composition:Polyurethane elastomer is by PEPA, diisocyanate and chain extender dispensing Form, PEPA include interior alcohol, polyalcohol urge, catalyst and light stabilizer, it is different that diisocyanate includes diphenyl-methane two Cyanate, toluene di-isocyanate(TDI) and plasticizer, chain extender include ethylene glycol, propane diols, dipropylene glycol and diethyl first Phenylenediamine.
S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition:(1)The preparation method of PEPA is such as Under:By weight percentage, to urge 36%, catalyst 19% and light stabilizer 14% to constitute polyester by interior alcohol 31%, polyalcohol more First alcohol;(2)The preparation method of diisocyanate is as follows:By weight percentage, by '-diphenylmethane diisocyanate 22%, toluene Diisocyanate 69% constitutes diisocyanate with plasticizer 9%;(3)The preparation method of chain extender is as follows:With percetage by weight Meter, chain extender is constituted by ethylene glycol 18%, propane diols 28%, dipropylene glycol 27% and diethyl toluene diamine 27%;
S3, for the first time stirring mixing:PEPA and diisocyanate in S2 is poured into mixing drum and is sufficiently stirred for, Material heats up 79 degrees Celsius during stirring, now can release the vacuum inside mixing drum to addition nitrogen inside mixing drum, be allowed to take out It is stirred under vacuum mixing 2h;
S4, second of stirring mixing:Chain extender is added into mixing drum after S3, quick stirring vacuumizes degassing, material Temperature gradually rises to 120 degrees Celsius, and viscosity substantially increases, and stops stirring;
S5, transporting molten reaction mass:Frit reaction material in S4 is discharged from mixing drum, and is poured into and is loaded in conveyer belt On coat in advance in the polytetrafluoroethyldisk disk of releasing agent, and conveyer belt is placed in 130 degrees Celsius of curing oven, is continuously poured into a mould Material moves heat aging on a moving belt;
S6, elastomer granulation:After material cooling 2h after S5 is cured, deliver in vacuum granulator and granulated;
S7, drying and dehydrating:Particle in S6 is dried into the moisture in 5h, removing particle under 90 degrees Celsius, then through being molded into Type can be prepared by TPUE.
The rotating speed for stirring hybrid motor in the S3 for the first time is second of stirring mixing electricity in 400r/min, the S4 The rotating speed 300r/min of motivation.
Frit reaction material viscosity is 6000-10000CPS in the S5.
Method for preparing thermoplastic polyurethane elastomer of the present invention, low energy consumption, pollution-free, mechanical performance are significantly improved, and are made Wider with scope, preparation method is simple, and efficient stable can be used for large-scale industrial production, PEPA, two isocyanides Acid esters and chain extender dispensing improve properties of product by uniformly being mixed twice.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (3)

1. a kind of method for preparing thermoplastic polyurethane elastomer, it is characterised in that comprise the following steps:
S1, polyurethane elastomer raw material composition:Polyurethane elastomer is by PEPA, diisocyanate and chain extender dispensing Form, PEPA include interior alcohol, polyalcohol urge, catalyst and light stabilizer, it is different that diisocyanate includes diphenyl-methane two Cyanate, toluene di-isocyanate(TDI) and plasticizer, chain extender include ethylene glycol, propane diols, dipropylene glycol and diethyl first Phenylenediamine;
S2, PEPA, the system of diisocyanate and chain extender match somebody with somebody composition:(1)The preparation method of PEPA is as follows:With Percent by weight, 35-40%, catalyst 10%-20% and light stabilizer 5%-15% are urged by interior alcohol 30-45%, polyalcohol Constitute PEPA;(2)The preparation method of diisocyanate is as follows:By weight percentage, by diphenylmethane diisocyanates Ester 20%-55%, toluene di-isocyanate(TDI) 40%-70% and plasticizer 5%-10% composition diisocyanate;(3)Chain extender Preparation method is as follows:By weight percentage, by ethylene glycol 15%-20%, propane diols 25%-30%, dipropylene glycol 25%-30% and diethyl toluene diamine 25%-30% composition chain extenders;
S3, for the first time stirring mixing:PEPA and diisocyanate in S2 is poured into mixing drum and is sufficiently stirred for, Material heats up 70-80 degrees Celsius during stirring, now can release the vacuum inside mixing drum to addition nitrogen inside mixing drum, be allowed to Vacuumize stirring mixing 1-2h;
S4, second of stirring mixing:Chain extender is added into mixing drum after S3, quick stirring vacuumizes degassing, material Temperature gradually rises to 110-120 degrees Celsius, and viscosity substantially increases, and stops stirring;
S5, transporting molten reaction mass:Frit reaction material in S4 is discharged from mixing drum, and is poured into and is loaded in conveyer belt On coat in advance in the polytetrafluoroethyldisk disk of releasing agent, and conveyer belt is placed in 100-130 degrees Celsius of curing oven, is continuously poured The material of note moves heat aging on a moving belt;
S6, elastomer granulation:After material cooling 1-2h after S5 is cured, deliver in vacuum granulator and granulated;
S7, drying and dehydrating:Particle in S6 is dried into the moisture in 4-5h, removing particle under 85-90 degrees Celsius, then through note The type of being moulded into can be prepared by TPUE.
2. a kind of method for preparing thermoplastic polyurethane elastomer according to claim 1, it is characterised in that:In the S3 The rotating speed of stirring hybrid motor is the rotating speed 300r/ of second of stirring hybrid motor in 400r/min, the S4 for the first time min。
3. a kind of method for preparing thermoplastic polyurethane elastomer according to claim 1, it is characterised in that:In the S5 Frit reaction material viscosity is 6000-10000CPS.
CN201710695892.5A 2017-08-15 2017-08-15 A kind of method for preparing thermoplastic polyurethane elastomer Pending CN107325257A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912760A (en) * 2017-12-13 2019-06-21 上海优迈材料科技有限公司 A kind of oil-resisting type floor-cleaning machine water suction adhesive tape and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130981A (en) * 2013-03-20 2013-06-05 黎明化工研究设计院有限责任公司 High-hardness thermoplastic polyurethane elastomer and preparation method thereof
CN103724591A (en) * 2013-12-09 2014-04-16 山东一诺威聚氨酯股份有限公司 Preparation method of biologically degradable thermoplastic polyurethane elastomer
CN104387560A (en) * 2014-12-16 2015-03-04 山东一诺威聚氨酯股份有限公司 Thermoplastic polyurethane elastomer and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130981A (en) * 2013-03-20 2013-06-05 黎明化工研究设计院有限责任公司 High-hardness thermoplastic polyurethane elastomer and preparation method thereof
CN103724591A (en) * 2013-12-09 2014-04-16 山东一诺威聚氨酯股份有限公司 Preparation method of biologically degradable thermoplastic polyurethane elastomer
CN104387560A (en) * 2014-12-16 2015-03-04 山东一诺威聚氨酯股份有限公司 Thermoplastic polyurethane elastomer and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912760A (en) * 2017-12-13 2019-06-21 上海优迈材料科技有限公司 A kind of oil-resisting type floor-cleaning machine water suction adhesive tape and preparation method thereof

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Application publication date: 20171107