CN1955245A - Preparation method of polyurethane adhesive without containing 'tribenzene' solvent - Google Patents
Preparation method of polyurethane adhesive without containing 'tribenzene' solvent Download PDFInfo
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- CN1955245A CN1955245A CN 200510113972 CN200510113972A CN1955245A CN 1955245 A CN1955245 A CN 1955245A CN 200510113972 CN200510113972 CN 200510113972 CN 200510113972 A CN200510113972 A CN 200510113972A CN 1955245 A CN1955245 A CN 1955245A
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Abstract
This invention provies to a polyurethane tackifier without benzene, toluene, xylene and its preparation, and it relates to chemistry field, especially relates to a shoes-making bonding agent. This polyurethane tackifier is prepared from polyester polyalcohol with high efficiency. It polymerizes with isocyanate and chain extender dihydric alcohol under accelerant, and ripening is conducted under 150-180deg.C for 25-40min, and then dissolved. This preparation has lots of merits, such as simple, short reaction time, stable quality, none-yellowing, without benzene, toluene, xylene, cheap and so on. Its quality has reached the best level in our country.
Description
Technical field
The present invention relates to chemical field, particularly relate to the tackiness agent that a kind of shoemaking is used.
Background technology
Polyurethane adhesive not only has the such broad applicability of chloroprene rubber adhesive agent and excellent elasticity, flexibility and flexible resistance, and has water-fast, grease resistance and the resistance toheat better than the latter.70% uses chloroprene rubber adhesive agent in present China shoemaking industry, and the polyurethane adhesive consumption accounts for 30%, and mainly relies on import.But the good cold bonding of chloroprene rubber adhesive agent tack, low price etc. are its advantages, but its not plasticizer-resistant infiltration is poor with material adhesive to novel footwear such as soft pvc, thermoplastic elastomer, PU leather, the requirement of incompatibility shoemaking industry development.External trend is to be replaced by polyurethane adhesive gradually.The shoes-used glue of Europe, the United States 80%～90% is captured by polyurethane adhesive at present.Domestic also must be such trend, and China's polyurethane adhesive is started late, and quality is stable inadequately, yellowing easily, and price is higher, much produces house so far and still adopts the polyurethane adhesive that contains " triphen " solvent, serious environment pollution, infringement people's physical and mental health.
Summary of the invention
Purpose of the present invention is exactly the shortcoming that contains the polyurethane adhesive of " triphen " solvent in order to overcome, through great efforts, succeeded in developing the polyurethane adhesive that does not contain " triphen " (benzene,toluene,xylene) solvent, a kind of method from polyester polyol efficient production polyurethane adhesive promptly is provided, it is about polyester polyol and isocyanic ester in the presence of catalyzer, polyreactions such as chainextender dibasic alcohol are then carried out slaking, are dissolved as the preparation method of feature.
Polyester polyol can be from poly-hexanodioic acid-1,4-butyleneglycol (PBA molecular weight: 2000), poly-adipate glycol (PEA), poly-adipate glycol-propylene glycol, poly-hexanodioic acid glycol ether (PDA), poly-adipate glycol-glycol ether, poly-adipate glycol--1, choose any one kind of them in the 4-butyleneglycol.
Isocyanic ester can be tolylene diisocyanate (TDI), ditan 4,4 '-vulcabond (MDI), polymethylene multi-phenenyl isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI), a kind of in the tetramethylxylylene diisocyanate (TMXDI) etc.
The chainextender dibasic alcohol can be 1,4-butyleneglycol (BDO), 2,3-butyleneglycol, glycol ether, glycerine, TriMethylolPropane(TMP), a kind of in the sorbyl alcohol etc.
Catalyzer can be a tetramethyl butane diamine, triethylenediamine, dibutyl tin dilaurate, a kind of in the stannous octoate etc.
The consumption of each component is during polyreaction: 100 parts polyester polyol, 8～9 parts vulcabond, 0～13 part chainextender dibasic alcohol, 0.05～0.1 part catalyzer.
Described curing temperature is 150～180 ℃, is preferably 170～180 ℃; And the curing time can be 25～40 minutes, is preferably 35～40 minutes.
Solvent during urethane colloidal sol can be one or both in acetone, butanone, pimelinketone, tetrahydrofuran (THF), dioxane, dimethyl formamide, the ethyl acetate etc., is preferably the mixture of acetone and ethyl acetate.
Polyurethane adhesive of the present invention detects with result on trial as follows through Putian Hua Feng footwear industry company limited test cabinet:
Viscosity: 1650 (mps/14 ℃);
Non-volatile content: 15.5%;
Initial stage thermotolerance (60 ℃ * 10 minutes): qualified;
Stripping strength (VN/MM, POC/ rubber): 4.7 (material damages);
Normal temperature complications: be as good as shape 60000 times;
Aging: nothing was come unglued in 48 hours;
Bonding pulling force (〉=2.5): 2.58;
Test report shows that quality has reached the level of domestic best product.
Polyurethane adhesive preparation method's of the present invention characteristics are: 1) technology is easy, and the reaction times is short; 2) steady quality, not yellowing; 3) do not contain " triphen " noxious solvent; 4) low price.
Embodiment
Following example is to more specifically explanation of the present invention, but the present invention does not limit following these examples.
Embodiment 1: will gather hexanodioic acid-1 earlier, (the PBA molecular weight: 2000) 200 grams place the 1000ml three-necked bottle to the 4-butyleneglycol, 140 ℃ of following vacuum hydro-extractions 15 minutes, be cooled to 60 ℃, add 1, hexamethylene-diisocyanate (HDI) 16.8 grams, dibutyl tin dilaurate 0.11 gram, stir after 3～5 minutes, 175～180 ℃ of following slakings 40 minutes, be cooled to 60 ℃, be dissolved in the mixed solution of 75 (weight) % acetone and 25 (weight) % butanone, make the polyurethane adhesive of solid content 18 (weight) %, viscosity: 1850 (mps/14 ℃).
Embodiment 2: take by weighing the poly-hexanodioic acid-1 of 1000 grams after the vacuum hydro-extractions, the 4-butyleneglycol adds 1,4-butyleneglycol 122 grams, hexamethylene diisocyanate (HDI) 88 grams, dibutyl tin dilaurate 0.55 gram, stir after 5 minutes, 170 ℃ of following slakings 40 minutes, be cooled to 60 ℃, be dissolved in the mixed solution of 80 (weight) % acetone and 20 (weight) % butanone, make the polyurethane adhesive of solid content 15 (weight) %, viscosity: 1650 (mps/14 ℃).
Claims (9)
1. preparation method who does not contain the polyurethane adhesive of " triphen " solvent, it is characterized in that: this method be adopt polyester polyol in the presence of catalyzer with isocyanic ester, the chainextender dibasic alcohol carries out polyreaction, then carried out slaking 25～40 minutes, again the dissolved preparation method at 150～180 ℃.
2. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1, it is characterized in that: described polyester polyol is poly-hexanodioic acid-1, the 4-butyleneglycol (2000), poly-adipate glycol (PEA), poly-adipate glycol-propylene glycol, poly-hexanodioic acid glycol ether (PDA), poly-adipate glycol-glycol ether, poly-adipate glycol PBA molecular weight:--1, a kind of in the 4-butyleneglycol.
3. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1, it is characterized in that: described isocyanic ester is tolylene diisocyanate (TDI), ditan 4,4 '-vulcabond (MDI), polymethylene multi-phenenyl isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI), a kind of in the tetramethylxylylene diisocyanate (TMXDI).
4. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1, it is characterized in that: described chainextender dibasic alcohol is 1,4-butyleneglycol (BDO), 2, a kind of in 3-butyleneglycol, glycol ether, glycerine, TriMethylolPropane(TMP), the sorbyl alcohol.
5. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1 is characterized in that: described catalyzer is a kind of in tetramethyl butane diamine, triethylenediamine, dibutyl tin dilaurate, the stannous octoate.
6. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1 is characterized in that: described curing temperature is 170～180 ℃.
7. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1 is characterized in that: the described curing time is 35～40 minutes.
8. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 1 is characterized in that: described dissolution solvent is one or both in acetone, butanone, pimelinketone, tetrahydrofuran (THF), dioxane, dimethyl formamide, the ethyl acetate.
9. the preparation method who does not contain the polyurethane adhesive of " triphen " solvent as claimed in claim 8 is characterized in that: described dissolution solvent is the mixture of acetone and ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510113972 CN1955245A (en) | 2005-10-24 | 2005-10-24 | Preparation method of polyurethane adhesive without containing 'tribenzene' solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510113972 CN1955245A (en) | 2005-10-24 | 2005-10-24 | Preparation method of polyurethane adhesive without containing 'tribenzene' solvent |
Publications (1)
| Publication Number | Publication Date |
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| CN1955245A true CN1955245A (en) | 2007-05-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510113972 Pending CN1955245A (en) | 2005-10-24 | 2005-10-24 | Preparation method of polyurethane adhesive without containing 'tribenzene' solvent |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059795A (en) * | 2012-12-11 | 2013-04-24 | 宁波豪城合成革有限公司 | Adhesion agent without containing benzene and homologous compounds thereof |
| CN103865467A (en) * | 2014-03-26 | 2014-06-18 | 珠海裕田化工制品有限公司 | Nonyellowing-type high-performance polyurethane adhesive and preparation method thereof |
| CN104388035A (en) * | 2014-12-06 | 2015-03-04 | 赵冯 | Adhesive used for shoemaking |
| CN105297487A (en) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | Washing resistant adhesive and preparation method thereof |
| CN105602511A (en) * | 2016-01-07 | 2016-05-25 | 吉安迅达科技有限公司 | Production formula and production process of environment-friendly low-temperature adhesive |
| CN105602512A (en) * | 2016-03-30 | 2016-05-25 | 光山县博正树脂有限公司 | Environment-friendly PU spraying adhesive and preparation method thereof |
| CN106010418A (en) * | 2016-06-20 | 2016-10-12 | 郑州大学 | Environment-friendly high-strength polyurethane adhesive for wig hair weft glue and preparation method of polyurethane adhesive |
| TWI568817B (en) * | 2015-11-20 | 2017-02-01 | 財團法人工業技術研究院 | Solvent-free adhesive composition |
| CN109554154A (en) * | 2018-12-20 | 2019-04-02 | 泉州禾丰新型化工材料有限公司 | Polyurethane glue and its reaction kettle especially suitable for the production of puffed rice footwear material |
| CN109705791A (en) * | 2018-08-17 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of environment protection modification polyurethane adhesive and preparation method thereof |
| CN110564354A (en) * | 2019-07-25 | 2019-12-13 | 启东东岳化工有限公司 | Polyurethane adhesive with high initial adhesion for roller coating and preparation method thereof |
| WO2020107136A1 (en) * | 2018-11-26 | 2020-06-04 | 福建省晋江泉发骑士鞋业有限公司 | Etpu sole material and preparation method and application thereof |
| CN112409975A (en) * | 2020-09-01 | 2021-02-26 | 重庆韩拓科技有限公司 | Environment-friendly heat-resistant single-component pu and preparation method thereof |
| CN114058315A (en) * | 2021-11-24 | 2022-02-18 | 广东粤港澳大湾区黄埔材料研究院 | Oily polyurethane adhesive and preparation method thereof |
-
2005
- 2005-10-24 CN CN 200510113972 patent/CN1955245A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059795A (en) * | 2012-12-11 | 2013-04-24 | 宁波豪城合成革有限公司 | Adhesion agent without containing benzene and homologous compounds thereof |
| CN103865467A (en) * | 2014-03-26 | 2014-06-18 | 珠海裕田化工制品有限公司 | Nonyellowing-type high-performance polyurethane adhesive and preparation method thereof |
| CN103865467B (en) * | 2014-03-26 | 2018-04-10 | 广东裕田霸力科技股份有限公司 | A kind of high-performance non yellowing type polyaspartic adhesive and preparation method thereof |
| CN104388035A (en) * | 2014-12-06 | 2015-03-04 | 赵冯 | Adhesive used for shoemaking |
| TWI568817B (en) * | 2015-11-20 | 2017-02-01 | 財團法人工業技術研究院 | Solvent-free adhesive composition |
| CN105297487A (en) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | Washing resistant adhesive and preparation method thereof |
| CN105602511A (en) * | 2016-01-07 | 2016-05-25 | 吉安迅达科技有限公司 | Production formula and production process of environment-friendly low-temperature adhesive |
| CN105602512A (en) * | 2016-03-30 | 2016-05-25 | 光山县博正树脂有限公司 | Environment-friendly PU spraying adhesive and preparation method thereof |
| CN106010418A (en) * | 2016-06-20 | 2016-10-12 | 郑州大学 | Environment-friendly high-strength polyurethane adhesive for wig hair weft glue and preparation method of polyurethane adhesive |
| CN106010418B (en) * | 2016-06-20 | 2019-08-23 | 郑州大学 | Environment protection type high-strength wig curtain adhesive polyurethane adhesive and preparation method thereof |
| CN109705791A (en) * | 2018-08-17 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of environment protection modification polyurethane adhesive and preparation method thereof |
| WO2020107136A1 (en) * | 2018-11-26 | 2020-06-04 | 福建省晋江泉发骑士鞋业有限公司 | Etpu sole material and preparation method and application thereof |
| CN109554154A (en) * | 2018-12-20 | 2019-04-02 | 泉州禾丰新型化工材料有限公司 | Polyurethane glue and its reaction kettle especially suitable for the production of puffed rice footwear material |
| CN110564354A (en) * | 2019-07-25 | 2019-12-13 | 启东东岳化工有限公司 | Polyurethane adhesive with high initial adhesion for roller coating and preparation method thereof |
| CN112409975A (en) * | 2020-09-01 | 2021-02-26 | 重庆韩拓科技有限公司 | Environment-friendly heat-resistant single-component pu and preparation method thereof |
| CN114058315A (en) * | 2021-11-24 | 2022-02-18 | 广东粤港澳大湾区黄埔材料研究院 | Oily polyurethane adhesive and preparation method thereof |
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Open date: 20070502 |