CN104017162B - A kind of polyurethane elastomer method of modifying - Google Patents
A kind of polyurethane elastomer method of modifying Download PDFInfo
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- CN104017162B CN104017162B CN201410282389.3A CN201410282389A CN104017162B CN 104017162 B CN104017162 B CN 104017162B CN 201410282389 A CN201410282389 A CN 201410282389A CN 104017162 B CN104017162 B CN 104017162B
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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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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- 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
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- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
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Abstract
The invention discloses a kind of polyurethane elastomer method of modifying, belong to polymer modification method and technology field, the modified PUE of core-shell latex particles is made up of the raw material of following weight ratio component: PTMG 51g, toluene di-isocyanate(TDI) 18.2g, 3,5-dimethythiotoluene diamine 6.65g, the top layer sub-6.12g of hydroxyl PBA-P (MMA-VA) core-shell latex particles；The step that its method of modifying adopts is: 1. the mensuration of hydroxyl value: adopt acetic anhydride-pyridine method to measure the hydroxyl value of PTMG and the top layer sub-mixture of hydroxyl PBA-P (MMA-VA) core-shell latex particles；The preparation of 2.PUE: by 50g PTMG vacuum dehydration 5 ~ 10min at 100 ~ 110 DEG C, weigh 6g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles and join in 50mL acetone, it is then added in PTMG, then vacuum sloughs acetone at 80 ~ 90 DEG C；Said mixture is cooled to 40 ~ 50 DEG C, adds 18.2g TDI-100, at 90 DEG C, react 20min, prepare base polyurethane prepolymer for use as, [NH in molar ratio2]: [NCO]=0.95:1, add 6.65g chain extender DMTDA, the vulcanizing press of 120 DEG C vulcanizes 20min, the demoulding can obtain PUE.
Description
Technical field
The present invention relates to a kind of polyurethane elastomer method of modifying, belong to polymer modification method and technology field.
Background technology
The development of polyurethane elastomer (PUE) is increasingly subject to people and payes attention to, and due to improving constantly of technical merit, in order to meet the requirement of different purposes, different performance, PUE modification technology is also developed rapidly.PUE modification technology includes physical modification and chemical modification, and physical modification is by organic or inorganic filler and the blended realization of PUE, and blended is simple physical mixed, does not have chemical bond to generate in Blending Processes；Chemical modification be by NCO (-NCO) or hydroxyl (-OH) with material modified upper with active group generation chemical reaction and will material modified introduce in PUE matrix, make the character of PUE improve.Usual chemical modification effect is significantly better than physical modification, and chemical modification is also the PUE modification technology of current most study.A kind of top layer sub-synthetic method of hydroxyl core-shell latex particles that the present inventor develops has declared patent, and its application number is: 201410204722.9, is that polyurethane elastomer is one of material modified.
Summary of the invention
It is an object of the invention to provide a kind of polyurethane elastomer method of modifying, it be using top layer hydroxyl butyl polyacrylate-poly-(methyl methacrylate-vinyl alcohol) (PBA-P (MMA-VA)) core-shell latex particles and PTMG (PTMG) mixture as soft section, toluene di-isocyanate(TDI) (TDI-100) be hard section, 3,5-dimethythiotoluene diamine (DMTDA) is chain extender, adopts prepolymer method to prepare the modified PUE of casting type core-shell latex particles.
The technical solution adopted for the present invention to solve the technical problems is: a kind of polyurethane elastomer method of modifying, and the modified PUE of core-shell latex particles is made up of the raw material of following weight ratio component:
PTMG PTMG51g
Toluene di-isocyanate(TDI) TDI-10018.2g
3,5-dimethythiotoluene diamine DMTDA6.65g
The top layer sub-6.12g of hydroxyl PBA-P (MMA-VA) core-shell latex particles
The raw material that hydroxyl PBA-P (MMA-VA) core-shell latex particles modified PUE in top layer uses: toluene di-isocyanate(TDI) TDI-100 is chemical pure；Sodium hydroxide NaOH, acetone, pyridine, benzene, acetic anhydride, phenolphthalein are analytical pure；PTMG PTMG, molecular weight is 1000；3,5-dimethythiotoluene diamines (DMTDA), molecular weight is 214；Top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles.
The step that its method of modifying adopts is:
1. the mensuration of hydroxyl value
Adopting acetic anhydride-pyridine method to measure the hydroxyl value of PTMG and the top layer sub-mixture of hydroxyl PBA-P (MMA-VA) core-shell latex particles, the step of its mensuration is:
(1) preparation of acylating agent: mixed for 12:88 with mass ratio with pyridine by acetic anhydride, places standby；
(2) 1gPTMG, 0.12g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles is accurately weighed; both mixing are placed in ground conical flask; add 10.00mL acylating agent with pipet, 100 DEG C of oil baths are heated to reflux 2h, after cooling, add 25mL benzene; and with 10mL distilled water flushing condensing tube; flushing liquor enters bottle, adds 5 phenolphthalein indicators, is titrated to terminal by the NaOH solution of 0.5mol/L; separately do blank assay, namely can be regarded as to obtain the hydroxyl value of mixture.
The preparation of 2.PUE
By 50gPTMG vacuum dehydration 5 ~ 10min at 100 ~ 110 DEG C, weigh 6g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles and join in 50mL acetone, vibrate 30min in numerical control ultrasonic cleaner, core-shell latex particles is made to be evenly dispersed in acetone, it is then added in PTMG, stirring 20min makes both mix homogeneously, then vacuum sloughs acetone at 80 ~ 90 DEG C；Said mixture being cooled to 40 ~ 50 DEG C, adds 18.2gTDI-100, react 20min, prepare base polyurethane prepolymer for use as at 90 DEG C, in performed polymer, NCO group mass fraction is 5.5%.50g base polyurethane prepolymer for use as is heated to 50 ~ 60 DEG C, and after vacuum defoamation, [NH in molar ratio2]: [NCO]=0.95:1, it is rapidly added 6.65g chain extender DMTDA, after being uniformly mixed, again after deaeration 10min, is poured into immediately in mould, the vulcanizing press of 120 DEG C vulcanizes 20min, the demoulding can obtain PUE.
The invention has the beneficial effects as follows: adopt this kind of method of modifying to prepare PUE, it is achieved that the purpose to PUE chemical modification, can also improve its heat resistance while improving PUE mechanical property further.
Detailed description of the invention
A kind of polyurethane elastomer method of modifying, the modified PUE of core-shell latex particles is made up of the raw material of following weight ratio example component:
The ratio component of its raw material is as follows:
PTMG PTMG51g
Toluene di-isocyanate(TDI) TDI-10018.2g
3,5-dimethythiotoluene diamine DMTDA6.65g
Top layer hydroxyl core-shell latex particles PBA-P (MMA-VA) 6.12g
The raw material that the modified PUE of PBA-P (MMA-VAc) core-shell latex particles uses: toluene di-isocyanate(TDI) TDI-100 is chemical pure；Sodium hydroxide NaOH, acetone, pyridine, benzene, acetic anhydride, phenolphthalein are analytical pure；PTMG PTMG, molecular weight is 1000；3,5-dimethythiotoluene diamine (DMTDA), molecular weight is 214；Top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles.
Described core-shell latex particles it be made up of the raw material of following ratio component:
Stratum nucleare:
Nuclear monomer BA30g cross-linking agent DVB1.5mL emulsifying agent SDS0.1g
Emulsifier op-10 0.1g initiator KPS0.16g deionized water H2O75mL
Grafting agent ALMA1mL
Shell:
Shell monomer MMA20g function monomer VAc4g emulsifying agent SDS0.1g
Emulsifier op-10 0.1g initiator KPS0.1g deionized water H2O10mL
PBA-P (MMA-VAc) core-shell latex particles synthesizes the raw material used: methyl methacrylate MMA, butyl acrylate BA, potassium peroxydisulfate KPS and vinylacetate VAc are analytical pure；Divinylbenzene DVB, allyl methacrylate ALMA, sodium lauryl sulphate SDS and NPE OP-10 are chemical pure.BA and MMA uses after decompression is distilled off polymerization inhibitor, and other reagent directly uses；Deionized water uses as disperse medium.
The step of its synthetic method is:
The synthesis of 1.PBA core emulsion
First 30gBA monomer and two kinds of emulsifying agents (0.1gOP-10 and 0.1gSDS), 15mL deionized water, 0.08gKPS and 1.5mLDVB being joined in 250mL three-necked bottle, at room temperature stir, mixing speed 500r/min, pre-emulsification 1h prepares BA pre-emulsion；
Then in equipped with the 250mL four-necked bottle of stirring paddle, thermometer, reflux condenser and nitrogen inlet, 60mL deionized water is added, it is warming up to 85 DEG C, and pass into nitrogen, add 0.08gKPS, it is stirred continuously, mixing speed 230r/min, after stirring, using peristaltic pump to instill BA pre-emulsion, dripping speed is 2rpm, when BA pre-emulsion drops to half, 1mL grafting agent ALMA is added in BA pre-emulsion, being further continued for dropping after stirring, BA pre-emulsion controls to drip off at 2h, mixing speed 230r/min；Control temperature and continue reaction 2.5h at 85 DEG C, prepare PBA core emulsion.
The synthesis of 2.PBA-P (MMA-VAc) core-shell latex particles
First 20gMMA monomer and two kinds of emulsifying agents (0.1gOP-10 and 0.1gSDS), 0.1gKPS, deionized water 10mL are joined in 250mL three-necked bottle, at room temperature stir, mixing speed is 500r/min, to be mixed uniformly after, add 4.0g function monomer VAc, continuing stirring, mixing speed remains unchanged, and pre-emulsification 1h prepares shell pre-emulsion；
Then by passing into nitrogen in the above-mentioned four-necked bottle equipped with PBA core emulsion, being warming up to 85 DEG C, instill shell pre-emulsion with peristaltic pump, dripping speed is 2rpm, controls to drip off at 1.5h, and is stirred continuously, and mixing speed is 230r/min.Temperature control 85 DEG C continues reaction 2.5h under nitrogen protection, cools to 60 ~ 70 DEG C of dischargings, obtains PBA-P (MMA-VA) core-shell emulsion.
Finally PBA-P (MMA-VA) core-shell emulsion is placed in beaker, instills, with glue head dropper, the aluminum chloride aqueous solution that concentration is 5% wherein, and continuous Glass rod stirs.When PBA-P (MMA-VA) core-shell emulsion becomes thick, stop dropping, at room temperature it is transferred in the funnel being covered with a metafiltration paper pressure-reduction filter device after static 10min, wash several times with 300mL deionized water, and be stirred continuously with Glass rod, filter to neutrality, dry 12h at 60 DEG C, obtain PBA-P (MMA-VA) core-shell latex particles.
The alcoholysis of 3.PBA-P (MMA-VAc) core-shell latex particles
First being mixed for 1:3 with mass ratio with methanol by dried PBA-P (MMA-VA) core-shell latex particles, be placed in beaker, make its swelling 1 ~ 2h in numerical control ultrasonic cleaner, numerical control ultrasonic cleaner frequency setting is 3000Hz；Mixing with volume ratio 1:1 with the NaOH methanol solution that concentration is 3%, stir 2 ~ 3h under room temperature, mixing speed is 800r/min so that it is fully alcoholysis；
Then it is transferred in the funnel being covered with a metafiltration paper pressure-reduction filter device after at room temperature standing 1h, wash several times with 1000mL deionized water, and be stirred continuously with Glass rod, filter to neutrality, dry 12h at 60 DEG C, finally gives top layer hydroxyl butyl polyacrylate-poly-(methyl methacrylate-vinyl alcohol) (PBA-P (MMA-VA)) core-shell latex particles.
The step that polyurethane elastomer method of modifying adopts:
1. the mensuration of hydroxyl value
Adopting acetic anhydride-pyridine method to measure the hydroxyl value of PTMG and the top layer sub-mixture of hydroxyl PBA-P (MMA-VA) core-shell latex particles, the step of its mensuration is:
(1) preparation of acylating agent: mixed for 12:88 with mass ratio with pyridine by acetic anhydride, places standby.
(2) 1gPTMG, 0.12g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles is accurately weighed; both mixing are placed in ground conical flask; add 10.00mL acylating agent with pipet, 100 DEG C of oil baths are heated to reflux 2h, after cooling, add 25mL benzene; and with 10mL distilled water flushing condensing tube; flushing liquor enters bottle, adds 5 phenolphthalein indicators, is titrated to terminal by the NaOH solution of 0.5mol/L; separately do blank assay, the hydroxyl value of mixture can be sought.
The preparation of 2.PUE
By 50gPTMG vacuum dehydration 5 ~ 10min at 100 ~ 110 DEG C, weigh 6g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles and join in 50mL acetone, vibrate 30min in numerical control ultrasonic cleaner, core-shell latex particles is made to be evenly dispersed in acetone, it is then added in PTMG, stirring 20min makes both mix homogeneously, then vacuum sloughs acetone at 80 ~ 90 DEG C.The sub-mixture of above-mentioned PTMG and PBA-P (MMA-VA) core-shell latex particles being cooled to 40 ~ 50 DEG C, adds 18.2gTDI-100, react 20min, prepare base polyurethane prepolymer for use as at 90 DEG C, in performed polymer, NCO group mass fraction is 5.5%.Weigh 50g base polyurethane prepolymer for use as and be heated to 50 ~ 60 DEG C, and after vacuum defoamation, [NH in molar ratio2]: [NCO]=0.95:1, it is rapidly added 6.65g chain extender DMTDA, after being uniformly mixed, again after deaeration 10min, is poured into immediately in mould, the vulcanizing press of 120 DEG C vulcanizes 20min, the demoulding can obtain PUE.
Claims (2)
1. a polyurethane elastomer method of modifying, is characterized in that: the modified PUE of core-shell latex particles is made up of the raw material of following weight ratio example component:
The ratio component of its raw material is as follows:
PTMG PTMG51g
Toluene di-isocyanate(TDI) TDI-10018.2g
3,5-dimethythiotoluene diamine DMTDA6.65g
Top layer hydroxyl core-shell latex particles PBA-P (MMA-VA) 6.12g
The raw material that the modified PUE of PBA-P (MMA-VA) core-shell latex particles uses: toluene di-isocyanate(TDI) TDI-100 is chemical pure；Sodium hydroxide NaOH, acetone, pyridine, benzene, acetic anhydride, phenolphthalein are analytical pure；PTMG PTMG, molecular weight is 1000；3,5-dimethythiotoluene diamine DMTDA, molecular weight is 214；Top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles；
Described core-shell latex particles it be made up of the raw material of following ratio component:
Stratum nucleare: nuclear monomer BA30g cross-linking agent DVB1.5mL emulsifying agent SDS0.1g emulsifier op-10 0.1g initiator KPS0.16g deionized water H2O75mL grafting agent ALMA1mL
Shell: shell monomer MMA20g function monomer VAc4g emulsifying agent SDS0.1g emulsifier op-10 0.1g initiator KPS0.1g deionized water H2O10mL；
PBA-P (MMA-VAc) core-shell latex particles synthesizes the raw material used: methyl methacrylate MMA, butyl acrylate BA, potassium peroxydisulfate KPS and vinylacetate VAc are analytical pure；Divinylbenzene DVB, allyl methacrylate ALMA, sodium lauryl sulphate SDS and NPE OP-10 are chemical pure；BA and MMA uses after decompression is distilled off polymerization inhibitor, and other reagent directly uses；Deionized water uses as disperse medium；
The step of its synthetic method is:
One, the synthesis of PBA core emulsion: first 30gBA monomer and two kinds of emulsifying agent 0.1gOP-10 and 0.1gSDS, 15mL deionized water, 0.08gKPS and 1.5mLDVB are joined in 250mL three-necked bottle, at room temperature stir, mixing speed 500r/min, pre-emulsification 1h prepare BA pre-emulsion；
Then in equipped with the 250mL four-necked bottle of stirring paddle, thermometer, reflux condenser and nitrogen inlet, 60mL deionized water is added, it is warming up to 85 DEG C, and pass into nitrogen, add 0.08gKPS, it is stirred continuously, mixing speed 230r/min, after stirring, using peristaltic pump to instill BA pre-emulsion, dripping speed is 2rpm, when BA pre-emulsion drops to half, 1mL grafting agent ALMA is added in BA pre-emulsion, being further continued for dropping after stirring, BA pre-emulsion controls to drip off at 2h, mixing speed 230r/min；Control temperature and continue reaction 2.5h at 85 DEG C, prepare PBA core emulsion；
Two, the synthesis of PBA-P (MMA-VAc) core-shell latex particles
First 20gMMA monomer and two kinds of emulsifying agent 0.1gOP-10 and 0.1gSDS, 0.1gKPS, deionized water 10mL are joined in 250mL three-necked bottle, at room temperature stir, mixing speed is 500r/min, to be mixed uniformly after, add 4.0g function monomer VAc, continuing stirring, mixing speed remains unchanged, and pre-emulsification 1h prepares shell pre-emulsion；
Then by passing into nitrogen in the above-mentioned four-necked bottle equipped with PBA core emulsion, being warming up to 85 DEG C, instill shell pre-emulsion with peristaltic pump, dripping speed is 2rpm, controls to drip off at 1.5h, and is stirred continuously, and mixing speed is 230r/min；Temperature control 85 DEG C continues reaction 2.5h under nitrogen protection, cools to 60 ~ 70 DEG C of dischargings, obtains PBA-P (MMA-VAc) core-shell emulsion；
Finally PBA-P (MMA-VAc) core-shell emulsion is placed in beaker, instills, with glue head dropper, the aluminum chloride aqueous solution that concentration is 5% wherein, and continuous Glass rod stirs；When PBA-P (MMA-VAc) core-shell emulsion becomes thick, stop dropping, at room temperature it is transferred in the funnel being covered with a metafiltration paper pressure-reduction filter device after static 10min, wash several times with 300mL deionized water, and be stirred continuously with Glass rod, filter to neutrality, dry 12h at 60 DEG C, obtain PBA-P (MMA-VAc) core-shell latex particles；
Three, the alcoholysis of PBA-P (MMA-VAc) core-shell latex particles
First being mixed for 1:3 with mass ratio with methanol by dried PBA-P (MMA-VAc) core-shell latex particles, be placed in beaker, make its swelling 1 ~ 2h in numerical control ultrasonic cleaner, numerical control ultrasonic cleaner frequency setting is 3000Hz；Mixing with volume ratio 1:1 with the NaOH methanol solution that concentration is 3%, stir 2 ~ 3h under room temperature, mixing speed is 800r/min so that it is fully alcoholysis；
Then it is transferred in the funnel being covered with a metafiltration paper pressure-reduction filter device after at room temperature standing 1h, wash several times with 1000mL deionized water, and be stirred continuously with Glass rod, filter to neutrality, dry 12h at 60 DEG C, finally gives top layer hydroxyl butyl polyacrylate-poly-(methyl methacrylate-vinyl alcohol) (PBA-P (MMA-VA)) core-shell latex particles.
2. a kind of polyurethane elastomer method of modifying according to claim 1, is characterized in that: the step that polyurethane elastomer method of modifying adopts:
One, the mensuration of hydroxyl value
Adopting acetic anhydride-pyridine method to measure the hydroxyl value of PTMG and the top layer sub-mixture of hydroxyl PBA-P (MMA-VA) core-shell latex particles, the step of its mensuration is:
(1) preparation of acylating agent: mixed for 12:88 with mass ratio with pyridine by acetic anhydride, places standby；
(2) 1gPTMG, 0.12g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles is accurately weighed; both mixing are placed in ground conical flask; add 10.00mL acylating agent with pipet, 100 DEG C of oil baths are heated to reflux 2h, after cooling, add 25mL benzene; and with 10mL distilled water flushing condensing tube; flushing liquor enters bottle, adds 5 phenolphthalein indicators, is titrated to terminal by the NaOH solution of 0.5mol/L; separately do blank assay, the hydroxyl value of mixture can be sought；
Two, the preparation of PUE
By 50gPTMG vacuum dehydration 5 ~ 10min at 100 ~ 110 DEG C, weigh 6g top layer hydroxyl PBA-P (MMA-VA) core-shell latex particles and join in 50mL acetone, vibrate 30min in numerical control ultrasonic cleaner, core-shell latex particles is made to be evenly dispersed in acetone, it is then added in PTMG, stirring 20min makes both mix homogeneously, then vacuum sloughs acetone at 80 ~ 90 DEG C；The sub-mixture of above-mentioned PTMG and PBA-P (MMA-VA) core-shell latex particles being cooled to 40 ~ 50 DEG C, adds 18.2gTDI-100, react 20min, prepare base polyurethane prepolymer for use as at 90 DEG C, in performed polymer, NCO group mass fraction is 5.5%；Weigh 50g base polyurethane prepolymer for use as and be heated to 50 ~ 60 DEG C, and after vacuum defoamation, [NH in molar ratio2]: [NCO]=0.95:1, it is rapidly added 6.65g chain extender DMTDA, after being uniformly mixed, again after deaeration 10min, is poured into immediately in mould, the vulcanizing press of 120 DEG C vulcanizes 20min, the demoulding can obtain PUE.
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| JP6936734B2 (en) * | 2015-12-11 | 2021-09-22 | 株式会社カネカ | Polyurethane-based curable composition containing polymer fine particles with excellent mechanical strength |
| CN106433423A (en) * | 2016-10-18 | 2017-02-22 | 盘锦首源新材料有限公司 | Environment-friendly manual polyurea plastic surface layer material and preparation method thereof |
| CN109651587B (en) * | 2018-12-07 | 2021-04-20 | 南京工程学院 | Phenolphthalein derivative-containing material-based photochromic high polymer material with rapid self-recovery property and preparation method thereof |
| CN112048047B (en) * | 2020-08-24 | 2022-05-10 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827325A (en) * | 2012-08-27 | 2012-12-19 | 上海涂料有限公司技术中心 | Preparation method and application of core-shell polyurethane/acrylic acid composite emulsion |
| CN103360561A (en) * | 2013-07-02 | 2013-10-23 | 广东海顺新材料科技有限公司 | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone |
| CN103709729A (en) * | 2013-12-20 | 2014-04-09 | 上海锦湖日丽塑料有限公司 | Yellowing resistant thermoplastic polyurethane composition and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827325A (en) * | 2012-08-27 | 2012-12-19 | 上海涂料有限公司技术中心 | Preparation method and application of core-shell polyurethane/acrylic acid composite emulsion |
| CN103360561A (en) * | 2013-07-02 | 2013-10-23 | 广东海顺新材料科技有限公司 | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone |
| CN103709729A (en) * | 2013-12-20 | 2014-04-09 | 上海锦湖日丽塑料有限公司 | Yellowing resistant thermoplastic polyurethane composition and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HTBN/PTMG双软段聚氨酯弹性体的制备及力学性能研究;陶海涛等;《聚氨酯工业》;20101231;第25卷(第06期);第13-16页 * |
| PBA/P(MMA-ITA)核壳胶乳粒子的合成;刘喜军等;《合成树脂及塑料》;20091231;第26卷(第06期);27-30页 * |
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