CN102838963B - Preparation method of high-temperature anti-yellowing polyurethane adhesive size - Google Patents
Preparation method of high-temperature anti-yellowing polyurethane adhesive size Download PDFInfo
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- CN102838963B CN102838963B CN201210346462XA CN201210346462A CN102838963B CN 102838963 B CN102838963 B CN 102838963B CN 201210346462X A CN201210346462X A CN 201210346462XA CN 201210346462 A CN201210346462 A CN 201210346462A CN 102838963 B CN102838963 B CN 102838963B
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Abstract
The invention relates to a preparation method of a high-temperature anti-yellowing polyurethane adhesive size, which belongs to the technical field of adhesive sizes. The preparation method comprises the following steps of: firstly adding solvent in to reaction equipment; then adding two or more different types of polyisocyanates and polyols oligomer; heating to be 55-65 DEG C under the protection of nitrogen; adding organic bismuth catalyst to react for 1-3h; then adding chain extenders, heating to be 70-85 DEG C under the protection of the nitrogen, and reacting for 2-3h to obtain a polyurethane prepolymer; adding solvent to regulate the prepolymer to achieve expectant solid content; and simultaneously, cooling the prepolymer to be 55-65 DEG C, adding heat-resistant and antiaging agent being 0.5 percent of the total of the polyurethane prepolymer into the polyurethane prepolymer, and stirring for 10-20min to discharge, wherein the mass ratio of the solvent, the polyisocyanates, the polyols oligomer, the chain extenders and the organic bismuth catalyst is 200-500:30-40:100:5-15:0.01-0.02. Compared with the prior art, the preparation method of the high-temperature anti-yellowing polyurethane adhesive size has the characteristics of anti-yellowing property, good adhesion property, low production cost and the like.
Description
Technical field:
The present invention relates to the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature slurry, belong to the adhesive technology field.
Technical background:
Urethane is mainly to close by the polyisocyanates such as vulcabond and low molecular weight polycaprolactone the superpolymer that dibasic alcohol is polymerized, due to the carbamate groups with strong polarity, simultaneously between macromole, have hydrogen bond, thereby polyurethane material have high strength, wear-resisting, anti-solvent, the characteristics such as ageing-resistant, water-fast.In addition, type and the structure that changes polyol, molecular weight etc. by changing polyisocyanates, can change the performance of polyurethane material in a big way.Polyurethane material is widely used in fields such as synthetic leather, leather, wrapping material, synthon, products with adhesive now.
The polyurethane adhesive used in existing market is very extensive, but there are many weak points, common dual-component polyurethane adhesive is unsuitable excess Temperature in heating cure, hot setting highlights the tint permanence of product, destroyed the outward appearance of finished product, but solidify at low temperatures, can make the isocyanate-based curing agent of tackiness agent crosslinked not exclusively, thereby the performance of tackiness agent is had a greatly reduced quality, and the isocyanate group of isocyanate-based curing agent very easily reacts with airborne moisture in 60 ℃～80 ℃ solidify, make it lose reactive behavior and reactivity worth, reduced the performance of tackiness agent, improved production cost.How to shield the activity of the group of easy generation xanthochromia, make it when high temperature, be in the torpescence state, thereby the product bridging property is improved greatly, avoided the interference of moisture to solidifying agent, reduce the usage quantity of solidifying agent, reduce production costs, also must guarantee simultaneously the bonding effect of product and the scope of application, become the direction of current research.
Summary of the invention:
Purpose of the present invention solves the activity that how to shield the group of easy generation xanthochromia in prior art just, make it when high temperature, be in the torpescence state, thereby the product bridging property is improved greatly, avoided the interference of moisture to solidifying agent, the usage quantity that has reduced solidifying agent has reduced the method for production cost, by using two or more isocyanic ester, the activity difference of reaction, changed the state of molecular structure, make the force of cohesion of product that variation occur, thereby improved the bonding effect of product and the scope of application.
In order to achieve the above object, the preparation method of the anti-yellowing change polyurethane adhesive of this high temperature of the present invention slurry is achieved in that
In conversion unit, at first add solvent, and then add two or more dissimilar polyisocyanates and oligomer polyol, under the protection of nitrogen, be warming up to 55～65 ℃, add organo-bismuth class catalyst reaction 1～3h, then adding chainextender is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 2～3h, obtain base polyurethane prepolymer for use as, add solvent to adjust the solid content that performed polymer reaches expection, simultaneously performed polymer is cooled to 55～65 ℃ and account for the high temperature resistant antiaging agent of base polyurethane prepolymer for use as total amount 0.5% to adding in this base polyurethane prepolymer for use as, discharging after stirring 10～20min, wherein the mass ratio of solvent, polyisocyanates, oligomer polyol, chainextender and organo-bismuth class catalyzer is: 200～500: 30～40: 100: 5～15: 0.01～0.02.
Further, described dissimilar polyisocyanates is:
Aromatic polyisocyanate is: tolylene diisocyanate, ditan-4,4 '-vulcabond, the many vulcabond of polymethylene polyphenyl, liquefaction ditan-4,4 '-vulcabond, tetramethylxylylene diisocyanate or naphthalene-1, the 5-vulcabond;
The fats polyisocyanates is: hexamethylene diisocyanate or isophorone diisocyanate;
Alicyclic ring class polyisocyanates is: Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
Further, described oligomer polyol is polyester polyol or polyether glycol.
Further, described chainextender is ethylene glycol, glycol ether, BDO, 1,3 butylene glycol, 1, and one or more in 6-hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), glycerine, sorbyl alcohol, tetramethylolmethane are composite.
Further, described high temperature resistant antiaging agent is 2,6-ditertbutylparacresol, 4, tertiary octyl group-the pentanoic of 4-bis-, tetramethylene β-propionic acid pentaerythritol ester, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) one or more in phenyl-5 chlorinated benzotriazole, carbodiimide are composite.
Further, described solvent is composite or two or more composite of in DMF, butanone, acetone, pimelinketone, vinyl acetic monomer, methylcarbonate, ritalin, N-BUTYL ACETATE, toluene, dimethylbenzene two kinds.
Further, described polyester polyol is polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-Isosorbide-5-Nitrae butanediol ester glycol, polycarbonate diol or polycaprolactone glycol; Described polyether glycol is polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
During use, by the prepared slurry of the present invention with take-NCO is mixed to get dual-component polyurethane adhesive as the polyisocyanate curing agent of end-blocking.
The characteristics such as compared with the prior art the present invention has anti-xanthochromia, bond properties is good, and production cost is low.
Embodiment
Below in conjunction with embodiment and reference examples, essence of the present invention and feature are described, example, only be used to explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1: the 200g dimethyl formamide is put in reaction vessel, and then the polyoxypropyleneglycol that the 100g molecular weight is 2000 is put in reaction vessel, start the agitator of reaction vessel, and then the mixture 40g of tolylene diisocyanate and isophorone diisocyanate is dropped into, under the protection of nitrogen, be warming up to 60 ℃ of left and right, add 1～2 of organic Bi catalyzer (approximately 0.5～1 gram) reaction 2h, then adding glycol chain extender 10g is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 3h obtains base polyurethane prepolymer for use as, add the dimethyl formamide of 150 gram left and right to adjust solid content to 30% ± 1, performed polymer is cooled to 60 ℃ of left and right, in this base polyurethane prepolymer for use as, add the high temperature resistant antiaging agent of 0.75g, cooling discharge after stirring 10～20min.
Embodiment 2. puts into the 200g dimethyl formamide in reaction vessel, and then the polyester glycol that the 100g molecular weight is 1500 is put in reaction vessel, start the agitator of reaction vessel, and then the mixture 35g of tolylene diisocyanate and hexamethylene diisocyanate is dropped into, under the protection of nitrogen, be warming up to 60 ℃ of left and right, add 1～2 of organic Bi catalyzer (approximately 0.5～1 gram) reaction 2h, then adding chainextender 1.4-butyleneglycol 13.06g is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 3h obtains base polyurethane prepolymer for use as, add the dimethyl formamide of 145.5 gram left and right to adjust solid content to 30% ± 1, performed polymer is cooled to 60 ℃ of left and right, in this base polyurethane prepolymer for use as, add the high temperature resistant antiaging agent of 0.75g, cooling discharge after stirring 10～20min.
Embodiment 3. puts into the 200g dimethyl formamide in reaction vessel, and then the polyester glycol that the 100g molecular weight is 1500 is put in reaction vessel, start the agitator of reaction vessel, and then the mixture 35g of tolylene diisocyanate and hexamethylene diisocyanate is dropped into, under the protection of nitrogen, be warming up to 60 ℃ of left and right, add 1～2 of organic Bi catalyzer (approximately 0.5～1 gram) reaction 2h, then adding glycol chain extender 9g is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 3h obtains base polyurethane prepolymer for use as, add the dimethyl formamide of 136 gram left and right to adjust solid content to 30% ± 1, performed polymer is cooled to 60 ℃ of left and right, in this base polyurethane prepolymer for use as, add the high temperature resistant antiaging agent of 0.75g, cooling discharge after stirring 10～20min.
Embodiment 4. puts into the 200g dimethyl formamide in reaction vessel, and then the polyoxypropyleneglycol that the 100g molecular weight is 1000 is put in reaction vessel, start the agitator of reaction vessel, and then by ditan-4, 4 '-mixture of vulcabond and hexamethylene diisocyanate drops into 36.37g, under the protection of nitrogen, be warming up to 60 ℃ of left and right, add 1～2 of organic Bi catalyzer (approximately 0.5～1 gram) reaction 2h, then adding glycol chain extender 5g is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 3h obtains base polyurethane prepolymer for use as, add the dimethyl formamide of 130 gram left and right to adjust solid content to 30% ± 1, performed polymer is cooled to 60 ℃ of left and right, in this base polyurethane prepolymer for use as, add the high temperature resistant antiaging agent of 0.75g, cooling discharge after stirring 10～20min.
Embodiment 5. puts into the 200g dimethyl formamide in reaction vessel, and then the polyester glycol that the 100g molecular weight is 3000 is put in reaction vessel, start the agitator of reaction vessel, and then by ditan-4, 4 '-mixture of vulcabond and isophorone diisocyanate drops into 30g, under the protection of nitrogen, be warming up to 60 ℃ of left and right, add 1～2 of organic Bi catalyzer (approximately 0.5～1 gram) reaction 2h, then adding glycol chain extender 10.38g is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 3h obtains base polyurethane prepolymer for use as, add the dimethyl formamide of 128 gram left and right to adjust solid content to 30% ± 1, performed polymer is cooled to 60 ℃ of left and right, in this base polyurethane prepolymer for use as, add the high temperature resistant antiaging agent of 0.75g, cooling discharge after stirring 10～20min.
The foregoing is only part embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. the preparation method of the anti-yellowing change polyurethane adhesive of a high temperature slurry is characterized in that according to following steps:
In conversion unit, at first add solvent, and then add two or more dissimilar polyisocyanates and oligomer polyol, under the protection of nitrogen, be warming up to 55～65 ℃, add organo-bismuth class catalyst reaction 1～3h, then adding chainextender is being warming up under the protection of nitrogen under 70 ℃～85 ℃ again, reaction 2～3h, obtain base polyurethane prepolymer for use as, add solvent to adjust the solid content that performed polymer reaches expection, simultaneously performed polymer is cooled to 55～65 ℃ and account for the high temperature resistant antiaging agent of base polyurethane prepolymer for use as total amount 0.5% to adding in this base polyurethane prepolymer for use as, discharging after stirring 10～20min, wherein the mass ratio of solvent, polyisocyanates, oligomer polyol, chainextender and organo-bismuth class catalyzer is: 200～500: 30～40: 100: 5～15: 0.01～0.02.
2. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 1 slurry is characterized in that described dissimilar polyisocyanates is:
Aromatic polyisocyanate is: tolylene diisocyanate, ditan-4,4 '-vulcabond, the many vulcabond of polymethylene polyphenyl, liquefaction ditan-4,4 '-vulcabond, tetramethylxylylene diisocyanate or naphthalene-1, the 5-vulcabond;
The fats polyisocyanates is: hexamethylene diisocyanate or isophorone diisocyanate;
Alicyclic ring class polyisocyanates is: Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
3. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 1 slurry, is characterized in that described oligomer polyol is polyester polyol or polyether glycol.
4. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 1 slurry, it is characterized in that described chainextender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 1,3-butyleneglycol, 1, one or more in 6-hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), glycerine, sorbyl alcohol, tetramethylolmethane are composite.
5. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 1 slurry, it is characterized in that described high temperature resistant antiaging agent is 2,6-ditertbutylparacresol, 4, tertiary octyl group-the pentanoic of 4-bis-, tetramethylene β-propionic acid pentaerythritol ester, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) one or more in phenyl-5-chlorinated benzotriazole, carbodiimide are composite.
6. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 1 slurry, it is characterized in that described solvent is composite or two or more composite of in DMF, butanone, acetone, pimelinketone, vinyl acetic monomer, methylcarbonate, ritalin, N-BUTYL ACETATE, toluene, dimethylbenzene two kinds.
7. the preparation method of the anti-yellowing change polyurethane adhesive of a kind of high temperature according to claim 3 slurry, it is characterized in that described polyester polyol is polyethylene glycol adipate glycol, poly-hexanodioic acid glycol ether esterdiol, poly-hexanodioic acid-BDO esterdiol, polycarbonate diol or polycaprolactone glycol; Described polyether glycol is polyoxypropyleneglycol, polyoxytrimethylene triol, polytetrahydrofuran diol or tetrahydrofuran (THF)-propylene oxide copolymerization glycol.
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| CN104232004B (en) * | 2014-09-26 | 2017-05-17 | 南京汇鑫光电材料有限公司 | Polyurethane pressure-sensitive adhesive composition and preparation method and application thereof |
| CN104830264B (en) * | 2015-05-22 | 2018-06-05 | 佛山市高明恒祥化工树脂有限公司 | A kind of solvent-borne type hydrolysis resists cold, and fusing point is low to crystallize fast polyurethane hot melt manufacturing method |
| CN106700884A (en) * | 2016-12-01 | 2017-05-24 | 迪马新材料科技（苏州）有限公司 | PUR adhesive and preparation method |
| CN106832186A (en) * | 2017-01-06 | 2017-06-13 | 陕西科技大学 | One kind mixing diisocyanate type urethane and preparation method thereof |
| CN106928422A (en) * | 2017-04-28 | 2017-07-07 | 广东工业大学 | A kind of resisting high-temperature yellowing polyurethane and preparation method thereof |
| CN107189029B (en) * | 2017-06-09 | 2019-10-18 | 肇庆市华莱特复合新型材料有限公司 | A kind of Weak solvent system PU resin and preparation method thereof |
| CN107718812A (en) * | 2017-08-24 | 2018-02-23 | 浙江米欧制带股份有限公司 | Polyurethane foodweb and its manufacture method |
| CN108641657A (en) * | 2018-04-28 | 2018-10-12 | 安徽富煌门窗幕墙有限公司 | A kind of polyurethane bicomponent window angle glue |
| CN109628051B (en) * | 2018-12-26 | 2021-05-07 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant three-component polyurethane adhesive and preparation method thereof |
| CN110951038B (en) * | 2019-05-14 | 2022-02-08 | 天津科技大学 | Novel polyurethane film and preparation thereof |
| CN111019161A (en) * | 2019-12-31 | 2020-04-17 | 广东绿洲化工有限公司 | Preparation method of polyurethane powder |
| CN111172806A (en) * | 2020-01-17 | 2020-05-19 | 成都迪泰化工有限公司 | Anti-yellowing UPE transparent primer, preparation method and application thereof in paper paint spraying |
| CN112831306A (en) * | 2021-01-27 | 2021-05-25 | 南宝树脂（佛山）有限公司 | Anti-yellowing aqueous adhesive and preparation method and application thereof |
| CN116042076A (en) * | 2023-01-18 | 2023-05-02 | 南京科工煤炭科学技术研究有限公司 | Low-thermal-resistance quick-setting roadway spraying foaming sealing material and preparation method thereof |
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| CN1200064C (en) * | 2002-04-28 | 2005-05-04 | 林润强 | Solution process of synthesizing polyurethane glue |
| CN101914285A (en) * | 2010-09-06 | 2010-12-15 | 中国科学院嘉兴绿色化学工程中心 | Environmental-friendly polyurethane slurry and application |
| CN102443131B (en) * | 2011-09-19 | 2013-10-30 | 烟台市福山区化学工业研究所有限公司 | Non-yellowing polyurethane slurry for hasp, and preparation method thereof |
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