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CN106854270A - Many durometric polyurethane elastomers and preparation method thereof - Google Patents

Many durometric polyurethane elastomers and preparation method thereof Download PDF

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Publication number
CN106854270A
CN106854270A CN201611251779.XA CN201611251779A CN106854270A CN 106854270 A CN106854270 A CN 106854270A CN 201611251779 A CN201611251779 A CN 201611251779A CN 106854270 A CN106854270 A CN 106854270A
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CN
China
Prior art keywords
many
component
polyurethane
durometric
pepa
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.)
Pending
Application number
CN201611251779.XA
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Chinese (zh)
Inventor
徐军
陈海良
刘兆阳
孙聚涛
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.)
Shandong Inov Polyurethane Co Ltd
Original Assignee
Shandong Inov Polyurethane 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
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Priority to CN201611251779.XA priority Critical patent/CN106854270A/en
Publication of CN106854270A publication Critical patent/CN106854270A/en
Pending legal-status Critical Current

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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
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols

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  • 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 present invention relates to a kind of many durometric polyurethane elastomers and preparation method thereof, belong to polyurethane applied technical field.Many durometric polyurethane elastomers, including component A and B component, wherein, (1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage:PEPA 80.9~90.2%, diisocyanate 9.8~19.1%, the degree of functionality of the PEPA is 2, and number-average molecular weight is 1500~3000;The diisocyanate is TDI 100;(2) B component is chain extender.Many durometric polyurethane elastomers of the present invention, solidifying same performed polymer using different curing agent can obtain the polyurethane elastomer of many hardness, shorten the production cycle, reduce production cost, and the hardness range of the polyurethane elastomer of preparation is Shao A50~93;Described many durometric polyurethane method for producing elastomers, it is simple and easy to apply, beneficial to industrialized production.

Description

Many durometric polyurethane elastomers and preparation method thereof
Technical field
The present invention relates to a kind of many durometric polyurethane elastomers and preparation method thereof, belong to polyurethane applied technical field.
Background technology
Polyurethane elastomer is a kind of macromolecular material between rubber and plastics, combines caoutchouc elasticity and plastic hardness Advantage, while its mechanical performance anti-wear performance is excellent with rebound performance, be widely used in life, automobile, household electrical appliances etc. each Individual field.
Polyurethane elastomer is made up of hard section with soft section in structure, and microphase-separated, hard section occur between soft section and hard section The hardness of elastomer, the structure of the soft and hard segments block copolymer of uniqueness is influenceed to make it have to some extent with Soft segment Excellent comprehensive mechanical property especially anti-wear performance.The polyurethane elastomer of general production different hardness is by adjusting hard section With the ratio of soft section, that is, the isocyano of regulation prepolymer content, this technique productions different hardness elastomer cycle is long, High energy consumption, production cost is high, using cumbersome, is unfavorable for guest operation.
The content of the invention
It is an object of the invention to provide a kind of many durometric polyurethane elastomers and preparation method thereof, using different curing agent Solidifying same performed polymer can obtain the polyurethane elastomer of many hardness, and with short production cycle, simple to operate, production cost Low, excellent performance, preparation method is simple and easy to apply.
The technical solution adopted by the present invention is as follows:
A kind of many durometric polyurethane elastomers, including component A and B component, wherein,
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage:
PEPA 80.9~90.2%
Diisocyanate 9.8~19.1%
The degree of functionality of the PEPA is 2, and number-average molecular weight is 1500~3000;
The diisocyanate is TDI-100, wherein 2,4-TDI quality accounting is 98~99%;
(2) B component is chain extender.
The component A is 100/4.9~100/12.3 with the weight ratio of B component.
The PEPA is the polyadipate PEPA containing BDO, and wherein BDO accounts for small The molar percentage of molecule alcohol total amount>40%, the small molecular alcohol is the raw polyol used by synthesizing polyester polyalcohol, including Ethylene glycol, 1,2 propane diols and 1,4- butanediols.
The PEPA is the one kind or several in PE-2420, PE-4020, PE-4030, PE-2430 or PE-4015 Kind.
The B component is fine work MOCA, particle MOCA or E-300.
The polyurethane elastomer hardness range is Shao A50~90.
A kind of many durometric polyurethane method for producing elastomers, will component A mix with B component, mixing temperature is 75-85 DEG C, it is poured into mould that is warmed-up and scribbling releasing agent, pressing mold during gel point to be achieved, then through the demoulding, after cure Many durometric polyurethane elastomers are obtained.
The preparation method of the component A:PEPA reacts 4~5 hours with diisocyanate at 80~85 DEG C, obtains Isocyano-content is 2.1~4.3% prepolymer.
The mould is preheated to 100 DEG C~120 DEG C, the demoulding after 1~2 hour, the after cure 10 in 100~120 DEG C of environment ~16 hours.
The component A temperature is 70~85 DEG C, and the temperature of B component is 25~120 DEG C.
The present invention by change BDO/EG mol ratios in polyester with TDI the mass ratio influence elastomer of 2,4-TDI it is soft Hard section crystal property, i.e. TDI destroy the crystallinity of elastomer molecules chain in various degree with the molecular structure of polyester, so as to change bullet The hardness of gonosome, can solidify same prepolymer and obtain many durometric polyurethane elastomers using different curing agent.
The invention has the advantages that:
(1) many durometric polyurethane elastomers of the present invention, solidifying same performed polymer using different curing agent can obtain To the polyurethane elastomer of many hardness, shorten the production cycle, reduce production cost, the hardness range of the polyurethane elastomer of preparation It is Shao A50~93;
(2) many durometric polyurethane method for producing elastomers of the present invention, simple and easy to apply, beneficial to industrialized production.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit implementation of the invention.
Material therefor is as follows:
Embodiment 1
Prepolymer:(the quality accounting of wherein 2,4-TDI is for polyester diol PE-2430 90.2%, TDI-100 9.8% 98%) in 85 DEG C of reactions, 5 hours vacuum (- 0.095MPa) removing bubbles, the prepolymer that isocyano-content is 2.1% is obtained.
Prepolymer is heated up to 70 DEG C and particle MOCA 120 DEG C and is well mixed with 100/6 ratio, and mixing temperature is 80 DEG C It is poured into the mould that mold temperature is 120 DEG C, urethane cure times are 20min, and product is molded after 2 hours, in 100 DEG C of environment Middle after cure 16 hours, obtains the polyurethane elastomer product that hardness is Shao A50.
Prepolymer is heated up to 70 DEG C and fine work MOCA 120 DEG C and is well mixed with 100/6 ratio, and mixing temperature is 80 DEG C, It is poured into the mould that mold temperature is 110 DEG C, urethane cure times are 19min, and product is molded after 2 hours, in 110 DEG C of environment Middle after cure 13 hours, obtains the polyurethane elastomer product that hardness is Shao A70.
Prepolymer is heated up to 85 DEG C and E-300 25 DEG C and is well mixed with 100/4.9 ratio, and mixing temperature is 80 DEG C, is poured During injection mold temperature is 100 DEG C of mould, urethane cure times are 9min, and product is molded after 1 hour, in 120 DEG C of environment After cure 10 hours, obtains the polyurethane elastomer product that hardness is Shao A70.
Embodiment 2
Polyester diol PE-2420 85%, TDI-100 15% (the quality accounting of wherein 2,4-TDI is 98.5%) exist 85 DEG C of reactions, 4 hours vacuum (- 0.095MPa) removing bubbles, obtain the prepolymer that isocyano-content is 3.5%.
Prepolymer is heated up to 70 DEG C and particle MOCA 120 DEG C and is well mixed with 100/10 ratio, and mixing temperature is 80 DEG C, it is poured into the mould that mold temperature is 120 DEG C, urethane cure times are 13min, and product is molded after 1.5 hours, 100 After cure 16 hours in DEG C environment, obtains the polyurethane elastomer product that hardness is Shao A67.
Prepolymer is heated up to 70 DEG C and fine work MOCA 120 DEG C and is well mixed with 100/10 ratio, and mixing temperature is 80 DEG C, it is poured into the mould that mold temperature is 110 DEG C, urethane cure times are 12min, and product is molded after 1.5 hours, 110 After cure 13 hours in DEG C environment, obtains the polyurethane elastomer product that hardness is Shao A85.
Prepolymer is heated up to 85 DEG C and E-300 25 DEG C and is well mixed with 100/8.1 ratio, and mixing temperature is 75 DEG C, is poured During injection mold temperature is 100 DEG C of mould, urethane cure times are 5min, and product is molded after 1 hour, in 120 DEG C of environment After cure 10 hours, obtains the polyurethane elastomer product that hardness is Shao A82.
Embodiment 3
Polyester diol PE-4015 80.9%, TDI-100 19.1% (the quality accounting of wherein 2,4-TDI is 99%) In 80 DEG C of reactions, 4 hours vacuum (- 0.095MPa) removing bubbles, the prepolymer that isocyano-content is 4.3% is obtained.
Prepolymer is heated up to 70 DEG C and particle MOCA 120 DEG C and is well mixed with 100/12.3 ratio, and mixing temperature is 85 DEG C, it is poured into the mould that mold temperature is 120 DEG C, urethane cure times are 8min, and product is molded after 1 hour, in 100 DEG C of rings After cure 16 hours in border, obtain the polyurethane elastomer product that hardness is Shao A75.
Prepolymer is heated up to 70 DEG C and fine work MOCA 120 DEG C and is well mixed with 100/12.3 ratio, and mixing temperature is 85 DEG C, it is poured into the mould that mold temperature is 110 DEG C, urethane cure times are 7min, and product is molded after 1 hour, in 110 DEG C of rings After cure 13 hours in border, obtain the polyurethane elastomer product that hardness is Shao A90.
Prepolymer is heated up to 85 DEG C and E-300 25 DEG C and is well mixed with 100/10 ratio, and mixing temperature is 75 DEG C, is poured During injection mold temperature is 100 DEG C of mould, urethane cure times are 3min, and product is molded after 1 hour, in 120 DEG C of environment After cure 10 hours, obtains the polyurethane elastomer product that hardness is Shao A87.
Above example test result is shown in Table 1.
The performance test results of the embodiment of table 1

Claims (10)

1. a kind of many durometric polyurethane elastomers, it is characterised in that:Including component A and B component, wherein,
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage:
PEPA 80.9~90.2%
Diisocyanate 9.8~19.1%
The degree of functionality of the PEPA is 2, and number-average molecular weight is 1500~3000;
The diisocyanate is TDI-100;
(2) B component is chain extender.
2. many durometric polyurethane elastomers according to claim 1, it is characterised in that:The weight of the component A and B component Than being 100/4.9~100/12.3.
3. many durometric polyurethane elastomers according to claim 1, it is characterised in that:The PEPA be containing 1, The polyadipate PEPA of 4- butanediols, wherein BDO account for the molar percentage of small molecular alcohol total amount>40%, institute State raw polyol of the small molecular alcohol used by synthesizing polyester polyalcohol, including ethylene glycol, 1,2 propane diols and BDO.
4. many durometric polyurethane elastomers according to claim 3, it is characterised in that:The PEPA is PE- 2420th, one or more in PE-4020, PE-4030, PE-2430 or PE-4015.
5. many durometric polyurethane elastomers according to claim 1-4 any one, it is characterised in that:The B component is Fine work MOCA, particle MOCA or E-300.
6. many durometric polyurethane elastomers according to claim 1-4 any one, it is characterised in that:The polyurethane bullet Gonosome hardness range is Shao A50~90.
7. a kind of many durometric polyurethane method for producing elastomers as claimed in any one of claims 1 to 6, it is characterised in that:Will Component A mixes with B component, and mixing temperature is 75-85 DEG C, is poured into mould that is warmed-up and scribbling releasing agent, to be achieved solidifying Pressing mold during glue point, is then obtained many durometric polyurethane elastomers through the demoulding, after cure.
8. many durometric polyurethane method for producing elastomers according to claim 7, it is characterised in that:The system of the component A Preparation Method:PEPA and diisocyanate react 4~5 hours at 80~85 DEG C, obtain isocyano-content for 2.1~ 4.3% prepolymer.
9. many durometric polyurethane method for producing elastomers according to claim 7 or 8, it is characterised in that:The mould is pre- Heat is to 100 DEG C~120 DEG C, the demoulding after 1~2 hour, after cure 10~16 hours in 100~120 DEG C of environment.
10. many durometric polyurethane method for producing elastomers according to claim 7 or 8, it is characterised in that:The A groups Temperature is divided to be 70~85 DEG C, the temperature of B component is 25~120 DEG C.
CN201611251779.XA 2016-12-30 2016-12-30 Many durometric polyurethane elastomers and preparation method thereof Pending CN106854270A (en)

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Application Number Priority Date Filing Date Title
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110156951A (en) * 2019-06-06 2019-08-23 浙江圣奥家具制造有限公司 A kind of different hardness shaping sponge cushion and preparation method thereof
CN111607060A (en) * 2020-07-13 2020-09-01 扬州雷应精密科技有限公司 High-entropy polyurethane and preparation method thereof
CN112045914A (en) * 2020-08-25 2020-12-08 河北华密橡胶科技股份有限公司 Method for manufacturing multilayer multi-hardness polyurethane rubber core

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Publication number Priority date Publication date Assignee Title
CN1342177A (en) * 1999-02-23 2002-03-27 陶氏化学公司 High temp. resistant polyurethane polymers
CN101348557A (en) * 2008-08-08 2009-01-21 山东东大一诺威聚氨酯有限公司 Wearing resistance enhanced pouring type urethane elastomer composition
CN104231222A (en) * 2014-09-19 2014-12-24 黎明化工研究设计院有限责任公司 High-wear-resistance polyurethane elastomer and preparation method thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
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CN101348557A (en) * 2008-08-08 2009-01-21 山东东大一诺威聚氨酯有限公司 Wearing resistance enhanced pouring type urethane elastomer composition
CN104231222A (en) * 2014-09-19 2014-12-24 黎明化工研究设计院有限责任公司 High-wear-resistance polyurethane elastomer and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110156951A (en) * 2019-06-06 2019-08-23 浙江圣奥家具制造有限公司 A kind of different hardness shaping sponge cushion and preparation method thereof
CN110156951B (en) * 2019-06-06 2021-04-27 浙江圣奥家具制造有限公司 Special-hardness shaped sponge cushion and preparation method thereof
CN111607060A (en) * 2020-07-13 2020-09-01 扬州雷应精密科技有限公司 High-entropy polyurethane and preparation method thereof
CN112045914A (en) * 2020-08-25 2020-12-08 河北华密橡胶科技股份有限公司 Method for manufacturing multilayer multi-hardness polyurethane rubber core

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Application publication date: 20170616

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