CN1167803A - Process for producing adhesive for polyurethane shoes by solution method - Google Patents
Process for producing adhesive for polyurethane shoes by solution method Download PDFInfo
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- CN1167803A CN1167803A CN 97109045 CN97109045A CN1167803A CN 1167803 A CN1167803 A CN 1167803A CN 97109045 CN97109045 CN 97109045 CN 97109045 A CN97109045 A CN 97109045A CN 1167803 A CN1167803 A CN 1167803A
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- solution method
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- producing adhesive
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Abstract
A solution method for producing polyurethane binder for making shoes includes synthesizing polyester at lower temp and synthesizing polyurethane binder by polymerization of polyester and 4, 4'-diphenyl methane diisocyanate (MDI) in toluene solvent, and features easy operation, low cost and high quality of product.
Description
The invention belongs to the tackiness agent production technique, be specifically related to produce the technology of urethane shoes-used glue with solution polymerization process.
At present, the shoes-used glue of selling on the domestic market mainly contains neoprene latex, grafted CR adhesive and polyurethane adhesive.Neoprene type tackiness agent uses the toxicity problem of solution to cause people's great attention, and it is in weathering resistance in addition, and the aspects such as suitability that anti-flexibility reaches New Type Material exist not enough.Replaced by polyurethane tackifier gradually at present.The polyurethane adhesive synthetic method mainly contains substance law.The substance law building-up reactions is wayward, and molecular weight is inhomogeneous.Therefore circulation ratio is not so good.Because of its product is a pellet, need secondary processing to join glue during use.Domestic production urethane shoes-used glue mainly is to refer to or work in-process (pellet) are joined glue from external import tree.Therefore, the product price height is difficult for being accepted by one factory.Produce the urethane shoes-used glue with solution method,, do not see relevant bibliographical information as yet to form stable suitability for industrialized production.
It is synthetic to the objective of the invention is to propose a kind of polyester that comprises, the novel process of the stable suitability for industrialized production urethane shoes-used glue of solution method synthesis of polyurethane glue.
Process technology scheme of the present invention is: polyester is synthetic at a lower temperature, its technology: hexanodioic acid and butyleneglycol are under the effect of catalyzer, in 130～200 ℃ reactor, at acid number (behind the 4mgKOH/g, be decompressed to 0.01MPa and kept 0.5～1 hour, make synthetics acid number (0.8mgKOH/g, hydroxyl value is 45～60mgKOH/g, cooling, discharging.The urethane glue is by polyester and 4,4 '-diphenylmethanediisocyanate polymerization reaction take place in solvent toluene forms, its technology: toluene, polyester and 4, the two isocyanide ester acid (MDI) of 4 '-ditan are under the effect of catalyzer, in 80～100 ℃ reactor, react after 1～2 hour, add chainextender, continue reaction 1～2 hour, add butanone and ethyl acetate and stir cooling discharging.
This technology is convenient easy to operate, and production cost is low, and quality product reaches international like product level.Be widely used in various one factories.
Accompanying drawing solution method urethane synthesis process flow diagram
Embodiment: as figure, by the technological process in the technical scheme, catalyzer adopted hydrated stannous chloride during polyester was synthetic, each substance weight ratio is: hexanodioic acid: butyleneglycol: hydrated stannous chloride=438: 305.5～310.9: 0.05～0.1, specifically: hexanodioic acid 438kg, butyleneglycol 309kg, hydrated stannous chloride 0.05～0.1kg, synthesizing polyester.Catalyzer adopted dibutyl tin dilaurate during urethane was synthetic, chainextender adopts butyleneglycol, each material mole ratio is: polyester: 4,4 '-diphenylmethanediisocyanate (MDI): chainextender (butyleneglycol)=1: 1.5: 0.5, concrete polyester 1mol, 4,4 '-diphenylmethanediisocyanate (MDI) 1.5mol, butyleneglycol 0.5mol, wherein wt: contain solid thing: (toluene+butanone+ethyl acetate)=15%: 85%, toluene: butanone: ethyl acetate (weight)=4.5: 4.5: 1.
Be compared as follows table by above technology products obtained therefrom performance and external like product
| Stripping strength | Solid content | Outward appearance | Viscosity | ||||||||||||
| Corium and corium | Corium and rubber | Corium and pvc | Pu and pu | Pvc and pu | This product | Import | This product | Import | This product | ||||||
| This product | Import | This product | Import | This product | Import | This product | Import | This product | Import | ||||||
| Measured data | 4.0 | 4.0 | 2.6 | 2.8 | 3.3 | 1.9 | 3.8 | 4.4 | 2.7 | 3.3 | 14.3 | 15.7 | Water white transparency | Oyster white | 2.2 |
| Measure unit | KN/m | KN/m | KN/m | KN/m | KN/m | KN/m | KN/m | KN/m | KN/m | KN/m | ％ | ％ | PaS | ||
| Remarks | Disconnected by sticking material | Disconnected by sticking material | |||||||||||||
Thus, the polyurethane shoe of explained hereafter of the present invention can reach the performance of international like product with colloidality, and need not secondary and join glue, and its cost price is all fallen in external product, is suitable for the domestic market needs.
Claims (6)
1, solution method is produced the polyurethane shoe process for producing adhesive, comprises that polyester is synthetic and the urethane glue is synthetic, it is characterized in that:
A, polyester are synthetic at a lower temperature, its technology: hexanodioic acid and butyleneglycol are under the effect of catalyzer, in 130～200 ℃ reactor, at acid number (behind the 4mgKOH/g, be decompressed to 0.01MPa and kept 0.5～1 hour, make synthetics acid number (0.8mgKOH/g, hydroxyl value is 45～60mgKOH/g, cooling, discharging.
B, urethane glue are by polyester and 4,4 '-diphenylmethanediisocyanate polymerization reaction take place in solvent toluene forms, its technology: toluene, polyester and 4,4 '-'-diphenylmethane diisocyanate in 80～100 ℃ reactor, reacts after 1～2 hour under the effect of catalyzer, add chainextender, continue reaction 1～2 hour, add butanone and acetate and stir cooling discharging.
2,1 solution method is produced the polyurethane shoe process for producing adhesive as claimed in claim, it is characterized in that the synthetic middle catalyzer of polyester is a hydrated stannous chloride.
3,1 solution method is produced the polyurethane shoe process for producing adhesive as claimed in claim, it is characterized in that the synthetic middle catalyzer of urethane is a dibutyl tin dilaurate.
4,1 solution method is produced the polyurethane shoe process for producing adhesive as claimed in claim, it is characterized in that chainextender is a butyleneglycol.
5, solution method is produced the polyurethane shoe process for producing adhesive as claimed in claim 1 or 2, it is characterized in that each substance weight ratio: hexanodioic acid: butyleneglycol: hydrated stannous chloride=438: 305.5～301.9: 0.05～0.1.6, solution method is produced the polyurethane shoe process for producing adhesive according to claim 1, and its feature in each material mole ratio is: polyester: 4, and 4 '-diphenylmethanediisocyanate: butyleneglycol=1: 1.5: 0.5.
7, solution method is produced the polyurethane shoe process for producing adhesive according to claim 1, it is characterized in that ester ammonia ester contains solid thing in synthetic: (toluene+butanone+ethyl acetate) (weight)=15%: 85%; Toluene wherein: butanone: ethyl acetate (weight)=4.5: 4.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109045A CN1095492C (en) | 1997-03-19 | 1997-03-19 | Process for producing adhesive for polyurethane shoes by solution method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109045A CN1095492C (en) | 1997-03-19 | 1997-03-19 | Process for producing adhesive for polyurethane shoes by solution method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167803A true CN1167803A (en) | 1997-12-17 |
| CN1095492C CN1095492C (en) | 2002-12-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97109045A Expired - Fee Related CN1095492C (en) | 1997-03-19 | 1997-03-19 | Process for producing adhesive for polyurethane shoes by solution method |
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| Country | Link |
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| CN (1) | CN1095492C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312248C (en) * | 2004-06-10 | 2007-04-25 | 王福朝 | Adhesive for mouldless renewing and mending tyre and its tool |
| CN101191044A (en) * | 2007-09-30 | 2008-06-04 | 潘成钢 | Water-proof adhesive |
| CN102286262A (en) * | 2011-07-12 | 2011-12-21 | 厦门大学 | Method for preparing polyurethane hot melting transfer print glue |
| CN106520053A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | High-performance adhesive and its preparation method and use |
| CN108517193A (en) * | 2018-03-09 | 2018-09-11 | 旭川化学（昆山）有限公司 | A kind of polyurethane adhesive and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100023A (en) * | 1985-04-01 | 1985-11-10 | 天津大学 | Polyurethane binder and manufacturing process thereof |
| CN1036404C (en) * | 1990-05-22 | 1997-11-12 | 中国兵器工业第五三研究所 | Polyurethane complementary networks adhesive and its making method |
-
1997
- 1997-03-19 CN CN97109045A patent/CN1095492C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312248C (en) * | 2004-06-10 | 2007-04-25 | 王福朝 | Adhesive for mouldless renewing and mending tyre and its tool |
| CN101191044A (en) * | 2007-09-30 | 2008-06-04 | 潘成钢 | Water-proof adhesive |
| CN101191044B (en) * | 2007-09-30 | 2011-06-15 | 潘成钢 | Water-proof adhesive |
| CN102286262A (en) * | 2011-07-12 | 2011-12-21 | 厦门大学 | Method for preparing polyurethane hot melting transfer print glue |
| CN106520053A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院山西煤炭化学研究所 | High-performance adhesive and its preparation method and use |
| CN108517193A (en) * | 2018-03-09 | 2018-09-11 | 旭川化学（昆山）有限公司 | A kind of polyurethane adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1095492C (en) | 2002-12-04 |
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