CN1092783A - The manufacture method of polyurethane elastomer glue stock - Google Patents
The manufacture method of polyurethane elastomer glue stock Download PDFInfo
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- CN1092783A CN1092783A CN 94110408 CN94110408A CN1092783A CN 1092783 A CN1092783 A CN 1092783A CN 94110408 CN94110408 CN 94110408 CN 94110408 A CN94110408 A CN 94110408A CN 1092783 A CN1092783 A CN 1092783A
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- prepolymer
- polyurethane elastomer
- glue stock
- elastomer glue
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Abstract
The present invention relates to a kind of is main raw material is used for the polyurethane elastomer glue stock of composite tyre aspect through the chemical reaction manufacturing production method with hydroxyl telechelic polyester (or polyethers), utilize hydroxy-terminated polymer also to use thing and isocyanic ester or its earlier also with thing reaction prepolymer (or semi prepolymer), generate polyurethane elastomer glue stock with the chainextender reaction again, this sizing material can be suitable for doing tire tread or carcass sizing material, its mechanical property, bond properties, hydrolytic resistance, thermostability and low-temperature performance all are better than prior art products.
Description
The present invention relates to a kind of is main raw material is used for the polyurethane elastomer glue stock of composite tyre aspect through the chemical reaction manufacturing method with hydroxyl telechelic polyester (or polyethers).
Which kind of tire no matter, through using for a long time, because road wear, the puncture of sharp object all can cause tire tread attenuation, chunk-out or breach, cavity occur, makes tire can't continue to use.Tire after the breakage must just can be reused after repairing or renovating.The rubber size identical with former tire still adopted in the repairing of conventional tire and renovation so far, and this sizing material also contains multiple additives such as vulcanizing agent, promotor, anti-aging agent, strengthening agent except that containing natural rubber or synthetic rubber.With the truck tyre of traditional rubber retreading, its wear resistance, thorn resistance is all undesirable, and its actual service life only is about 50,000 kilometers.
In order to improve the work-ing life of renovated tyre, begin polyurethane binder or polyurethane elastomer are used for the repairing and the renovation of tire both at home and abroad, relevant therewith patent has DE3124912, and 3333458; EP247469,358084,122480,199998; US4718469; Brit 1051351; J750879,7510379; CN1062692A etc.Wherein the technology of CN1062692A patent is with the poly-adipate glycol propylene glycol ester and 4 of terminal hydroxy group, 4 '-diphenylmethanediisocyanate reaction prepolymer or semi prepolymer, and then generate casting type polyurethane elastomers with reaction such as ethylene glycol (chainextender), TriMethylolPropane(TMP) (cross linking agent), it is filled into old rubber tyre tire top bit after the polishing, forms the urethanes composite tyre.Also there is the low and high shortcoming of product cost of automation technolo degree in this technology.
The objective of the invention is to overcome existing shortcoming of making composite tyre and the existence of used sizing material, seek to invent a kind of technology novelty, product performance are strong, and the hydroxyl telechelic polyester that cost is low (or polyethers) is produced the method for polyurethane elastomer glue stock through chemical reaction for main raw material.
In order to realize the foregoing invention purpose, the present invention utilizes hydroxyl telechelic polyester (or polyethers) and hydroxy-terminated polybutadienes also to use thing and isocyanic ester or its also with thing reaction prepolymer (or semi prepolymer), prepolymer component and chainextender and other additive agent mixture components are expelled in the tire-mold with reaction injection molding machine, thereby finish chain extension and crosslinking reaction is made the composite tyre that polyurethane elastomer is a tyre surface.After adopting common process equipment with poly-adipate glycol propylene glycol ester of a certain proportion of terminal hydroxy group and hydroxy-terminated polybutadienes mixing earlier, under the certain temperature condition, carry out vacuum hydro-extraction, lower the temperature then and remove vacuum, when stirring, add 4,4 '-diphenylmethanediisocyanate, and make temperature progressively rise to behind the certain value insulation reaction 1.5-3 hour, just make prepolymer (or semi prepolymer).Again with the prepolymer produced under the certain temperature condition, vacuumize and remove contained air, to avoid entrained air bubbles in the elastomerics that generates, to 2 of preheating then, 4-diamino-3.5-diformazan sulfenyl toluene and N, two (2-hydroxypropyl) aniline of N-add to rapidly in the prepolymer, after the high degree of agitation it is poured in the mold heat and promptly makes the elastomer glue stock test piece after the vulcanizing press sulfuration and the demoulding.
The present invention compared with prior art has the processing method novelty, and the product wear resisting property is good, is not prone to breach, and life cycle is long, and price is low and be convenient to advantage such as processing use etc.
Enforcement of the present invention is divided into two steps, promptly produces prepolymer earlier, produces elastomer glue stock again, and made polyurethane elastomer glue stock is made tire tread compound on the vulcanized rubber tire carcass.Concrete enforcement can be finished by following content: polyurethane elastomer glue stock is to be 1000-2000 by molecular-weight average, hydroxy functionality is that hydroxyl telechelic polyester (or polyethers) and the molecular-weight average of 2-2.2 is 1800-4000, hydroxy functionality be 2-2.39 hydroxy-terminated polybutadienes and with thing (polyester (or polyethers)/polyhutadiene=40-90/60-10) and excessive isocyanic ester or its are also used thing, generate the polyurethane prepolymer (or semi prepolymer) of two end groups by polyaddition for-NCO, prepolymerization reaction is to carry out under high degree of agitation, temperature of reaction 60-90 ℃, reaction times 1.5-3 hour, the free-NCO content that generates prepolymer was controlled at 4-6% and is advisable.The prepolymer that generates must be further and chainextender carry out to be the reaction of purpose, just can be formed with the polyurethane elastomer of use value to increase molecular chain length and between molecular chain, to produce chemically crosslinked.The present invention adopts 2,4-diamino-3.5-diformazan sulfenyl toluene and dibasic alcohol are also made chainextender with thing (being 1.0-3/2-0.5 with equivalence ratio also), the equivalence ratio of chainextender and prepolymer is 0.8-0.95/1, the mixing temperature of chainextender and prepolymer is 30-100 ℃, and mixing can be stirred by hand and be implemented or reaction injection molding machine enforcement.When making composite tyre with reaction injection molding machine, prepolymer is as a kind of component, the mixture of chainextender and catalyzer etc. is as another kind of component, the accurate measurement of two kinds of component process volume pumps is sent into respectively in the mixing head that has high-speed stirring, and the rapid mould that the vulcanized rubber tire carcass is housed that injects, under 80-120 ℃, reacted 30-60 minute, promptly get urethane/vulcanized rubber composite tyre.
Embodiment 1
Sizing compound formula:
Terminal hydroxy group gathers 50 parts of adipate glycol propylene glycol esters (molecular weight 2000)
50 parts of hydroxy-terminated polybutadieness (molecular weight 3100)
4,4 '-32.2 parts of diphenylmethanediisocyanates
2,9.5 parts of 4-diamino-3.5-diformazan sulfenyl toluene
N, 4.6 parts of two (2-hydroxypropyl) aniline of N-
The prepolymer preparation:
With the poly-adipate glycol propylene glycol ester of terminal hydroxy group and hydroxy-terminated polybutadienes mixture under 120 ℃, vacuumize dewater to water-content less than 0.05%.Be cooled to 50-60 ℃, removing vacuum under agitation adds 4,4 in above-mentioned polyol blends '-diphenylmethanediisocyanate, make the temperature of reaction system progressively rise to 80 ℃, and reaction 1.5-3 hour under this temperature.
Elastomer production:
Adopt the manual mixing casting.Prepolymer is removed contained air to avoid entrained air bubbles in the elastomerics that generates vacuumizing under 70-80 ℃.Be preheating to 40-70 ℃ 2,4-diamino-3,5-diformazan sulfenyl toluene and N, two (2-hydroxypropyl) aniline of N-, add in the prepolymer rapidly, with agitator or manual high degree of agitation 40-60 second, mixture is poured in the mold heat (100 ℃), again mould is put into 120 ℃ vulcanizing press.The demoulding after 1 hour, ready-made elastomerics test piece are parked 7 hours test performances 100 ℃ of post curings 24 hours under the room temperature.
Embodiment 2
Sizing compound formula:
Terminal hydroxy group gathers 60 parts of adipate glycol propylene glycol esters (molecular weight 2000)
40 parts of hydroxy-terminated polybutadieness (molecular weight 3100)
(isomery is than 2,4/2,6=80/20) 30.5 parts for tolylene diisocyanate
2,4-diamino-3,10.7 parts of 5-diformazan sulfenyl toluene
N, 4.3 parts of two (2-hydroxypropyl) aniline of N-
Performed polymer and method for producing elastomers are with embodiment 1.
Under 25 ℃ of temperature condition, the performance of testing this sizing material with the XLL-100A electronic tensile machine is as follows:
Performance embodiment 1 embodiment 2
Shore a hardness 80 78
300% fixed stretching strength (mpa) 12.5 10.2
Tensile strength (mpa) 30.7 23.6
Elongation rate of tensile failure (%) 480 524
Tensile set (%) 13 15
Tear strength (KN/M) 71 65
Claims (5)
- It is 1, a kind of that to be main raw material with hydroxyl telechelic polyester (or polyethers) be used for the method for the polyurethane elastomer glue stock of composite tyre aspect through the chemical reaction manufacturing, it is characterized in that utilizing hydroxy-terminated polymer and with thing and isocyanic ester or itself and with thing reaction prepolymer (or semi prepolymer) again with and with chainextender reaction generation polyurethane elastomer glue stock.
- 2, according to the manufacture method of the polyurethane elastomer glue stock of indication in the claim 1, after it is characterized in that using common process equipment with poly-adipate glycol propylene glycol ester of a certain proportion of terminal hydroxy group and hydroxy-terminated polybutadienes mixing, under the certain temperature condition, carry out vacuum hydro-extraction, lower the temperature then and remove vacuum, when stirring, add vulcabond, and make temperature progressively rise to behind the certain value insulation reaction 1.5-3 hour, just make prepolymer (or semi prepolymer).Again with the prepolymer produced under the certain temperature condition, vacuumize and remove contained air, to 2 of preheating then, 4-diamino-3,5-diformazan sulfenyl toluene and N, two (2-hydroxypropyl) aniline etc. of N-add to rapidly in the prepolymer, after the high degree of agitation it are poured in the mold heat, promptly make the elastomer glue stock test piece after the vulcanizing press sulfuration and the demoulding.
- 3, according to the manufacture method of claim 1 and 2 described elastic polyurethane sizing materials, it is characterized in that hydroxyl telechelic polyester (or polyethers) backbone molecule amount is 1000-2000, hydroxy functionality is 2-2.2; The molecular weight of hydroxy-terminated polybutadienes is 1800-4000, and hydroxy functionality is 2-2.39.Hydroxyl telechelic polyester (or polyethers) is 40-90/60-10 with weight ratio also with hydroxy-terminated polybutadienes.
- 4, the manufacture method of polyurethane elastomer glue stock according to claim 1 is characterized in that and is by 2 with chainextender, 4-diamino-3, and 5-diformazan sulfenyl toluene and N, compositions such as two (2-hydroxypropyl) aniline of N-, its equivalence ratio is 1-3/2-0.5.
- 5, the manufacture method of polyurethane elastomer glue stock according to claim 1, it is characterized in that by prepolymer (or semi prepolymer) with and during with chainextender reaction system polyurethane elastomer glue stock, and be 0.8-0.95/1 with the equivalence ratio of chainextender and prepolymer (or semi prepolymer).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110408 CN1092783A (en) | 1994-01-11 | 1994-01-11 | The manufacture method of polyurethane elastomer glue stock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110408 CN1092783A (en) | 1994-01-11 | 1994-01-11 | The manufacture method of polyurethane elastomer glue stock |
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| CN1092783A true CN1092783A (en) | 1994-09-28 |
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| CN 94110408 Pending CN1092783A (en) | 1994-01-11 | 1994-01-11 | The manufacture method of polyurethane elastomer glue stock |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051497C (en) * | 1996-03-20 | 2000-04-19 | 崔福成 | Non-inflated tyre and its production method |
| CN1325246C (en) * | 2003-10-31 | 2007-07-11 | 杭州悍马轮胎科技有限公司 | Green tyre in composite structure between wheel track of polyurethane and tyre core of rubber, and fabricating method |
| CN101070370B (en) * | 2007-05-25 | 2010-04-14 | 张勇 | Process for polyurethane crosslinking agent for melting spandex fiber |
| CN101130597B (en) * | 2007-09-29 | 2011-06-01 | 山东东大一诺威聚氨酯有限公司 | Synthesis method of solvent resistant solvent type urethane elastomer |
| CN102643409A (en) * | 2012-03-23 | 2012-08-22 | 中国海洋石油总公司 | Polyurethane gel for marine exploration streamer and preparation method for same |
| CN103467975A (en) * | 2013-09-12 | 2013-12-25 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| CN105934457A (en) * | 2013-11-26 | 2016-09-07 | 巴斯夫欧洲公司 | Polyurethane elastomeric composition and method of preparing the same |
| CN106274014A (en) * | 2016-08-25 | 2017-01-04 | 山西佰得拓普工贸有限公司 | Polyurethane elastomer and rubber combined technique |
| CN106753157A (en) * | 2017-01-17 | 2017-05-31 | 深圳市力信陆南橡塑五金有限公司 | A kind of excellent power glue performed polymer of fire-resistant antistatic polyurethane and preparation method thereof |
| CN107266658A (en) * | 2017-07-05 | 2017-10-20 | 苏州大学 | The polyurethane elastomer of a kind of main chain containing ferrocene and preparation method thereof |
| CN109134822A (en) * | 2018-07-24 | 2019-01-04 | 大连中海达科技有限公司 | It is a kind of can ultraviolet light cross-linking thermoplastic polyurethane elastomer synthetic method |
| CN109705303A (en) * | 2019-01-16 | 2019-05-03 | 荆晓东 | Spherical tire method for preparing polyurethane elastic body |
| CN109988417A (en) * | 2019-04-03 | 2019-07-09 | 郑州华普密封材料有限公司 | A kind of anti-puncture sealant material of patch type vacuum tyre and preparation method thereof |
| CN110506065A (en) * | 2017-04-12 | 2019-11-26 | 巴斯夫欧洲公司 | Thermoplastic polyurethane and composite article |
-
1994
- 1994-01-11 CN CN 94110408 patent/CN1092783A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051497C (en) * | 1996-03-20 | 2000-04-19 | 崔福成 | Non-inflated tyre and its production method |
| CN1325246C (en) * | 2003-10-31 | 2007-07-11 | 杭州悍马轮胎科技有限公司 | Green tyre in composite structure between wheel track of polyurethane and tyre core of rubber, and fabricating method |
| CN101070370B (en) * | 2007-05-25 | 2010-04-14 | 张勇 | Process for polyurethane crosslinking agent for melting spandex fiber |
| CN101130597B (en) * | 2007-09-29 | 2011-06-01 | 山东东大一诺威聚氨酯有限公司 | Synthesis method of solvent resistant solvent type urethane elastomer |
| CN102643409A (en) * | 2012-03-23 | 2012-08-22 | 中国海洋石油总公司 | Polyurethane gel for marine exploration streamer and preparation method for same |
| CN102643409B (en) * | 2012-03-23 | 2013-09-18 | 中国海洋石油总公司 | Polyurethane gel for marine exploration streamer and preparation method for same |
| CN103467975A (en) * | 2013-09-12 | 2013-12-25 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| CN103467975B (en) * | 2013-09-12 | 2015-04-01 | 山东永泰化工有限公司 | Butyl hydroxy type polyurethane composite tire rubber material and preparation method thereof |
| US10450470B2 (en) | 2013-11-26 | 2019-10-22 | Basf Se | Polyurethane elastomeric composition and method of preparing the same |
| CN105934457A (en) * | 2013-11-26 | 2016-09-07 | 巴斯夫欧洲公司 | Polyurethane elastomeric composition and method of preparing the same |
| CN106274014A (en) * | 2016-08-25 | 2017-01-04 | 山西佰得拓普工贸有限公司 | Polyurethane elastomer and rubber combined technique |
| CN106753157A (en) * | 2017-01-17 | 2017-05-31 | 深圳市力信陆南橡塑五金有限公司 | A kind of excellent power glue performed polymer of fire-resistant antistatic polyurethane and preparation method thereof |
| CN110506065B (en) * | 2017-04-12 | 2023-01-24 | 巴斯夫欧洲公司 | Thermoplastic polyurethane and composite article |
| US11312816B2 (en) | 2017-04-12 | 2022-04-26 | Basf Se | Thermoplastic polyurethane and composite article |
| CN110506065A (en) * | 2017-04-12 | 2019-11-26 | 巴斯夫欧洲公司 | Thermoplastic polyurethane and composite article |
| CN107266658B (en) * | 2017-07-05 | 2020-02-11 | 苏州大学 | Polyurethane elastomer with main chain containing ferrocene and preparation method thereof |
| CN107266658A (en) * | 2017-07-05 | 2017-10-20 | 苏州大学 | The polyurethane elastomer of a kind of main chain containing ferrocene and preparation method thereof |
| CN109134822A (en) * | 2018-07-24 | 2019-01-04 | 大连中海达科技有限公司 | It is a kind of can ultraviolet light cross-linking thermoplastic polyurethane elastomer synthetic method |
| CN109134822B (en) * | 2018-07-24 | 2021-06-25 | 大连中海达科技有限公司 | Synthesis method of thermoplastic polyurethane elastomer capable of being crosslinked by ultraviolet light |
| CN109705303A (en) * | 2019-01-16 | 2019-05-03 | 荆晓东 | Spherical tire method for preparing polyurethane elastic body |
| CN109988417B (en) * | 2019-04-03 | 2021-04-20 | 郑州华普密封材料有限公司 | Patch type vacuum tire puncture-proof sealing layer material and preparation method thereof |
| CN109988417A (en) * | 2019-04-03 | 2019-07-09 | 郑州华普密封材料有限公司 | A kind of anti-puncture sealant material of patch type vacuum tyre and preparation method thereof |
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