CN107325259A - A kind of polytetrahydrofuran diol type polyurethane elastomer and its preparation method and application - Google Patents
A kind of polytetrahydrofuran diol type polyurethane elastomer and its preparation method and application Download PDFInfo
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- CN107325259A CN107325259A CN201710753693.5A CN201710753693A CN107325259A CN 107325259 A CN107325259 A CN 107325259A CN 201710753693 A CN201710753693 A CN 201710753693A CN 107325259 A CN107325259 A CN 107325259A
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/40—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
- 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
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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 invention discloses a kind of polytetrahydrofuran diol type polyurethane elastomer and its preparation method and application, including component A and component B, the component A and component B are with mass ratio 100:16.5 17.5 are constituted；The component A includes polyalcohol and polyisocyanates, in terms of parts by weight, wherein 100 105 parts of polyalcohol, and 42 43 parts of polyisocyanates, described polyalcohol is that isocyanate group content is 7%（Mass fraction）, hydroxyl value is 109 ~ 115mg KOH/g polytetrahydrofuran diol, and described polyisocyanates is methyl diphenylene diisocyanate；The component B includes polytetrahydrofuran diol, Isosorbide-5-Nitrae butanediol and the organotin catalysts that hydroxyl value is 109 ~ 115mgKOH/g, in terms of parts by weight, wherein 60 ~ 65 parts of polytetrahydrofuran diol, 35 ~ 40 parts of Isosorbide-5-Nitrae butanediol, 2 parts of organotin catalysts；By castor made from this programme, the ground handling environment of out-of-flatness can be used in, because of its excellent elasticity, starts and rolling resistance is small, be applicable trolley, it is very laborsaving.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of polytetrahydrofuran diol type polyurethane elastomer and its
Preparation method and application.
Background technology
Polyurethane elastomer, also known as polyurethane rubber, are that a class contains more carbamate in strand（-
NHCOO-）The elastic polymer material of characteristic group.They are generally by polyisocyanates and oligomer polyol and polyalcohol
Or prepared by aromatic diamine etc..The performance range of polyurethane elastomer is very wide, is between the family macromolecule from rubber to plastics
Material.For upper, polyurethane is as a kind of high polymer material with the characteristic such as high intensity, tear-proof, wear-resisting, daily
The field extensive use such as life, industrial and agricultural production, medical science, specifically, polyurethane elastomer may be used as roller, conveyer belt,
Flexible pipe, auto parts, sole, synthetic leather, electric wire and medical artificial organ etc..But polyurethane also has following lack
Point：1st, endogenous heat is big, and resistance to elevated temperatures is general.Normal temperature in use scope is -40 ~ 120 DEG C and used.2nd, intolerant to intensive polar solvent
With strong acid alkaline media.At a certain temperature, alcohol, acid, ketone can make polyurethane elastomer be swelled and degrade, chloroform, dichloromethane, two
NMF, trichloro ethylene equal solvent will be swelled polyurethane elastomer at normal temperatures.Therefore, how to polyurethane product
Performance adjustable extent broadens, strengthens its adaptability, meets the variation requirement in market, is those skilled in the art in the prior art
Need what is solved.
The content of the invention
First purpose of the present invention, is to provide a kind of polytetrahydrofuran diol type polyurethane elastomer, to pure polyurethane
Elastomer is modified, so that its product can adapt to the requirement of a variety of particular surroundings.
Second object of the present invention, is to provide a kind of polytetrahydrofuran diol type polyurethane method for producing elastomers.
Third object of the present invention, is to provide a kind of application of polytetrahydrofuran diol type polyurethane elastomer.
In order to solve first purpose of the invention, following technical scheme is proposed：A kind of polytetrahydrofuran diol type polyurethane
Elastomer, including component A and component B, it is characterised in that：The component A and component B are with mass ratio 100:16.5-17.5 is constituted；
The component A includes polyalcohol and polyisocyanates, in terms of parts by weight, wherein polyalcohol 100-105 parts, polyisocyanates
42-43 parts, described polyalcohol is that isocyanate group content is 7%（Mass fraction）, hydroxyl value is the poly- of 109 ~ 115mg KOH/g
Erythritan, described polyisocyanates is methyl diphenylene diisocyanate；The component B include hydroxyl value be 109 ~
115mgKOH/g polytetrahydrofuran diol, BDO and organotin catalysts, in terms of parts by weight, wherein poly- tetrahydrochysene furan
Mutter 60 ~ 65 parts of glycol, 35 ~ 40 parts of BDO, 2 parts of organotin catalysts.
Preferably, the organotin catalysts are stannous octoate.
In order to solve second purpose of the invention, following technical scheme is proposed：A kind of polytetrahydrofuran diol type polyurethane
Method for producing elastomers, it is characterised in that follow the steps below：
1）Performed polymer is synthesized：The polytetrahydrofuran diol for taking 100 ~ 105 parts of hydroxyl values to be 109 ~ 115mgKOH/g by weight adds
Enter to be warming up in reactor after 110 ~ 120 DEG C of 2 ~ 3h of dehydrated under vacuum, when being less than 0.05% to moisture content, it is cooled to 50 ~
60 DEG C stand-by；Take 42 ~ 43 parts of methyl diphenylene diisocyanates to add reactor by weight, be warming up to after thawing, control
Temperature is added in methyl diphenylene diisocyanate under agitation at 50 ~ 60 DEG C, then the polytetrahydrofuran diol after dehydration,
It is to slowly warm up to 75-85 DEG C, insulation reaction 2 hours, sampling analysis isocyanate group content, when isocyanate group content is 7%
（Mass fraction）When, vacuum defoamation 20 ~ 30 minutes, inflated with nitrogen sealing preserve is stand-by；
2）Chain extending reaction：By step 1）Synthetic performed polymer is added in casting machine A batch cans, and it is 70-80 DEG C to control temperature；Again
Polytetrahydrofuran diol, 35 ~ 40 parts of BDOs and 2 that 60 ~ 65 parts of hydroxyl values are 109 ~ 115mgKOH/g are taken by weight
Part organotin catalysts are mixed to join in casting machine B batch cans, are warming up to 110 ~ 120 DEG C and are dehydrated 2 hours；Temperature control after dehydration
At 55-65 DEG C；Again by material in A batch cans and B batch cans with mass ratio 100:16.5-17.5 ratio, passes through head agitating device
Directly it is poured into mould；Solidified at ambient pressure, curing temperature control at 80-90 DEG C, product in after 30 ~ 40 minutes from mould
Taken out in tool；
3）After cure：By step 2）After cure is carried out after obtained product mould unloading, after cure temperature is 70-80 DEG C, during after cure
Between be 8 hours.
In order to solve the 3rd purpose of the invention, following technical scheme is proposed：A kind of polytetrahydrofuran diol type polyurethane
The application of elastomer, it is characterised in that：The polytetrahydrofuran diol type polyurethane elastomer is used for the castor on out-of-flatness ground.
It is preferred that application be trolley castor.
Polytetrahydrofuran diol is a kind of special PTMEG（Abbreviation PTMG）, chemical structural formula is HO [(CH2)4O]nH, is the equal polyethers of end primary hydroxyl straight chain obtained by tetrahydrofuran ring opening polymerization.Because it has ehter bond, thus have well
Compliance and hydrolytic resistance；It is free of unsaturated bond, thus with ageing-resistant performance.The polyurethane elastomer tool being made of PTMG
There are a high modulus and intensity, excellent resilience, wear-resisting, resistance to mould, oil resistivity, dynamic mechanical, electrical insulation capability and low
The performances such as tenderness, are a kind of modified polyurethane elastomers of good performance.And by castor made from this programme, can be used in
The ground handling environment of out-of-flatness, because of its excellent elasticity, starts and rolling resistance is small, be applicable trolley, very laborsaving.
Embodiment
Embodiment 1.The present embodiment includes component A and component B, and the component A and component B are with mass ratio 100:16.5 structures
Into；It is 7% that the component A, which includes isocyanate group content,（Mass fraction）, hydroxyl value is 109mg KOH/g PolyTHF two
Alcohol and methyl diphenylene diisocyanate, in terms of parts by weight, wherein 100 parts of polytetrahydrofuran diol, diphenyl methane two is different
42 parts of cyanate；It is sub- for 109mgKOH/g polytetrahydrofuran diol, 1,4- butanediols and octanoic acid that the component B includes hydroxyl value
Tin, in terms of parts by weight, wherein 60 parts of polytetrahydrofuran diol, 35 parts of BDO, 2 parts of stannous octoate.
Above-mentioned polytetrahydrofuran diol type polyurethane method for producing elastomers, is followed the steps below：
1）Performed polymer is synthesized：The polytetrahydrofuran diol that 100 parts of hydroxyl values are 109mgKOH/g is taken to add reactor by weight
In be warming up to after 110 DEG C of dehydrated under vacuum 2h, to moisture content be less than 0.05% when, be cooled to 50 DEG C it is stand-by；By weight
Number takes 42 parts of methyl diphenylene diisocyanates to add reactor, is warming up to after thawing, controls temperature at 50 DEG C, then after dehydration
Polytetrahydrofuran diol be added under agitation in methyl diphenylene diisocyanate, be to slowly warm up to 75 DEG C, insulation reaction 2
Hour, sampling analysis isocyanate group content, when isocyanate group content is 7%（Mass fraction）When, vacuum defoamation 20 minutes,
Inflated with nitrogen sealing preserve is stand-by；
2）Chain extending reaction：By step 1）Synthetic performed polymer is added in casting machine A batch cans, and it is 70 DEG C to control temperature；Press again
Parts by weight take the polytetrahydrofuran diol that 60 parts of hydroxyl values are 109mgKOH/g, 35 parts of BDOs and 2 parts of stannous octoates to mix
Conjunction is added in casting machine B batch cans, is warming up to 110 DEG C and is dehydrated 2 hours；Temperature control is at 55 DEG C after dehydration；Again by A batch cans and B
Material is with mass ratio 100 in batch can:16.5 ratio, is directly poured into mould by head agitating device；Enter at ambient pressure
Row solidification, curing temperature is controlled at 80 DEG C, and product is removed from the molds in after 30 minutes；
3）After cure：By step 2）Carry out after cure after obtained product mould unloading, after cure temperature is 70 DEG C, the after cure time is
8 hours.
Embodiment 2.The present embodiment includes component A and component B, and the component A and component B are with mass ratio 100:17 are constituted；
It is 7% that the component A, which includes isocyanate group content,（Mass fraction）, hydroxyl value for 112mg KOH/g polytetrahydrofuran diol and
Methyl diphenylene diisocyanate, in terms of parts by weight, wherein 13 parts of polytetrahydrofuran diol, methyl diphenylene diisocyanate
42.5 parts；The component B includes polytetrahydrofuran diol, BDO and the stannous octoate that hydroxyl value is 112mgKOH/g, with
Parts by weight meter, wherein 63 parts of polytetrahydrofuran diol, 38 parts of BDO, 2 parts of stannous octoate.
Above-mentioned polytetrahydrofuran diol type polyurethane method for producing elastomers, is followed the steps below：
1）Performed polymer is synthesized：The polytetrahydrofuran diol that 103 parts of hydroxyl values are 112mgKOH/g is taken to add reactor by weight
In be warming up to after 115 DEG C of dehydrated under vacuum 2.5h, to moisture content be less than 0.05% when, be cooled to 55 DEG C it is stand-by；By weight
Number takes 42.5 parts of methyl diphenylene diisocyanates to add reactor, is warming up to after thawing, controls temperature at 55 DEG C, then de-
Polytetrahydrofuran diol after water is added in methyl diphenylene diisocyanate under agitation, is to slowly warm up to 80 DEG C, insulation
Reaction 2 hours, sampling analysis isocyanate group content, when isocyanate group content is 7%（Mass fraction）When, vacuum defoamation 25
Minute, inflated with nitrogen sealing preserve is stand-by；
2）Chain extending reaction：By step 1）Synthetic performed polymer is added in casting machine A batch cans, and it is 75 DEG C to control temperature；Press again
Parts by weight take the polytetrahydrofuran diol that 63 parts of hydroxyl values are 112mgKOH/g, 38 parts of BDOs and 2 parts of stannous octoates to mix
Conjunction is added in casting machine B batch cans, is warming up to 115 DEG C and is dehydrated 2 hours；Temperature control is at 60 DEG C after dehydration；Again by A batch cans and B
Material is with mass ratio 100 in batch can:17 ratio, is directly poured into mould by head agitating device；Carry out at ambient pressure
Solidification, curing temperature is controlled at 85 DEG C, and product is removed from the molds in after 35 minutes；
3）After cure：By step 2）Carry out after cure after obtained product mould unloading, after cure temperature is 75 DEG C, the after cure time is
8 hours.
Embodiment 3.The present embodiment includes component A and component B, and the component A and component B are with mass ratio 100:17.5 structures
Into；It is 7% that the component A, which includes isocyanate group content,（Mass fraction）, hydroxyl value is 115mg KOH/g PolyTHF two
Alcohol and methyl diphenylene diisocyanate, in terms of parts by weight, wherein 105 parts of polytetrahydrofuran diol, diphenyl methane two is different
43 parts of cyanate；It is sub- for 115mgKOH/g polytetrahydrofuran diol, 1,4- butanediols and octanoic acid that the component B includes hydroxyl value
Tin, in terms of parts by weight, wherein 65 parts of polytetrahydrofuran diol, 40 parts of BDO, 2 parts of stannous octoate.
Above-mentioned polytetrahydrofuran diol type polyurethane method for producing elastomers, is followed the steps below：
1）Performed polymer is synthesized：The polytetrahydrofuran diol that 105 parts of hydroxyl values are 115mgKOH/g is taken to add reactor by weight
In be warming up to after 120 DEG C of 2 ~ 3h of dehydrated under vacuum, to moisture content be less than 0.05% when, be cooled to 60 DEG C it is stand-by；By weight
Number takes 43 parts of methyl diphenylene diisocyanates to add reactor, is warming up to after thawing, controls temperature at 60 DEG C, then dehydration
Polytetrahydrofuran diol afterwards is added in methyl diphenylene diisocyanate under agitation, is to slowly warm up to 85 DEG C, insulation is anti-
Answer 2 hours, sampling analysis isocyanate group content, when isocyanate group content is 7%（Mass fraction）When, 30 points of vacuum defoamation
Clock, inflated with nitrogen sealing preserve is stand-by；
2）Chain extending reaction：By step 1）Synthetic performed polymer is added in casting machine A batch cans, and it is 80 DEG C to control temperature；Press again
Parts by weight take the polytetrahydrofuran diol that 65 parts of hydroxyl values are 115mgKOH/g, 40 parts of BDOs and 2 parts of stannous octoates to mix
Conjunction is added in casting machine B batch cans, is warming up to 120 DEG C and is dehydrated 2 hours；Temperature control is at 65 DEG C after dehydration；Again by A batch cans and B
Material is with mass ratio 100 in batch can:17.5 ratio, is directly poured into mould by head agitating device；Enter at ambient pressure
Row solidification, curing temperature is controlled at 90 DEG C, and product is removed from the molds in after 40 minutes；
3）After cure：By step 2）Carry out after cure after obtained product mould unloading, after cure temperature is 80 DEG C, the after cure time is
8 hours.
Embodiment 4.The polytetrahydrofuran diol type polyurethane elastomer obtained by any schemes of embodiment 1-3 is applied to
The castor on out-of-flatness ground, preferred application is the castor of trolley.
Claims (5)
1. a kind of polytetrahydrofuran diol type polyurethane elastomer, including component A and component B, it is characterised in that：The component A
With component B with mass ratio 100:16.5-17.5 is constituted；The component A includes polyalcohol and polyisocyanates, with parts by weight
Meter, wherein polyalcohol 100-105 parts, 42-43 parts of polyisocyanates, described polyalcohol is that isocyanate group content is 7%（Matter
Measure fraction）, hydroxyl value is 109 ~ 115mg KOH/g polytetrahydrofuran diol, and described polyisocyanates is diphenyl methane two
Isocyanates；The component B includes polytetrahydrofuran diol, 1,4- butanediols and the organotin that hydroxyl value is 109 ~ 115mgKOH/g
Catalyst, in terms of parts by weight, wherein 60 ~ 65 parts of polytetrahydrofuran diol, 35 ~ 40 parts of BDO, organotin catalysts 2
Part.
2. according to a kind of polytetrahydrofuran diol type polyurethane elastomer described in claim 1, it is characterised in that：It is described organic
Tin catalyst is stannous octoate.
3. a kind of polytetrahydrofuran diol type polyurethane method for producing elastomers, it is characterised in that follow the steps below：
1）Performed polymer is synthesized：The polytetrahydrofuran diol for taking 100 ~ 105 parts of hydroxyl values to be 109 ~ 115mgKOH/g by weight adds
Enter to be warming up in reactor after 110 ~ 120 DEG C of 2 ~ 3h of dehydrated under vacuum, when being less than 0.05% to moisture content, it is cooled to 50 ~
60 DEG C stand-by；Take 42 ~ 43 parts of methyl diphenylene diisocyanates to add reactor by weight, be warming up to after thawing, control
Temperature is added in methyl diphenylene diisocyanate under agitation at 50 ~ 60 DEG C, then the polytetrahydrofuran diol after dehydration,
It is to slowly warm up to 75-85 DEG C, insulation reaction 2 hours, sampling analysis isocyanate group content, when isocyanate group content is 7%
（Mass fraction）When, vacuum defoamation 20 ~ 30 minutes, inflated with nitrogen sealing preserve is stand-by；
2）Chain extending reaction：By step 1）Synthetic performed polymer is added in casting machine A batch cans, and it is 70-80 DEG C to control temperature；Again
Polytetrahydrofuran diol, 35 ~ 40 parts of BDOs and 2 that 60 ~ 65 parts of hydroxyl values are 109 ~ 115mgKOH/g are taken by weight
Part organotin catalysts are mixed to join in casting machine B batch cans, are warming up to 110 ~ 120 DEG C and are dehydrated 2 hours；Temperature control after dehydration
At 55-65 DEG C；Again by material in A batch cans and B batch cans with mass ratio 100:16.5-17.5 ratio, passes through head agitating device
Directly it is poured into mould；Solidified at ambient pressure, curing temperature control at 80-90 DEG C, product in after 30 ~ 40 minutes from mould
Taken out in tool；
3）After cure：By step 2）After cure is carried out after obtained product mould unloading, after cure temperature is 70-80 DEG C, during after cure
Between be 8 hours.
4. a kind of application of polytetrahydrofuran diol type polyurethane elastomer, it is characterised in that：The polytetrahydrofuran diol type
Polyurethane elastomer is used for the castor on out-of-flatness ground.
5. according to a kind of application of polytetrahydrofuran diol type polyurethane elastomer described in claim 4, it is characterised in that：Institute
Polytetrahydrofuran diol type polyurethane elastomer is stated using the castor for trolley.
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Cited By (2)
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| CN109111562A (en) * | 2018-07-23 | 2019-01-01 | 中国科学院深圳先进技术研究院 | Selfreparing polyurethane and preparation method thereof and self-repair method |
| CN109810236A (en) * | 2018-09-21 | 2019-05-28 | 张东井 | A kind of production method of polyurethane shoe-sole and urethane raw for this method |
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| CN109810236A (en) * | 2018-09-21 | 2019-05-28 | 张东井 | A kind of production method of polyurethane shoe-sole and urethane raw for this method |
| CN109810236B (en) * | 2018-09-21 | 2022-04-12 | 张东井 | Method for manufacturing polyurethane sole and polyurethane raw material used for method |
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