CN111518257B - Water-based polyurethane shoe adhesive and preparation method thereof - Google Patents
Water-based polyurethane shoe adhesive and preparation method thereof Download PDFInfo
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- CN111518257B CN111518257B CN202010478814.1A CN202010478814A CN111518257B CN 111518257 B CN111518257 B CN 111518257B CN 202010478814 A CN202010478814 A CN 202010478814A CN 111518257 B CN111518257 B CN 111518257B
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Abstract
The invention belongs to the technical field of polyurethane adhesives, and particularly relates to a water-based polyurethane shoe adhesive and a preparation method thereof. The waterborne polyurethane shoe adhesive comprises isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, sulfonated polyether polyol, 1, 6-hexanediol adipate, dibutyltin dilaurate, ethylenediamine, trehalose, sodium dodecyl benzene sulfonate, 1, 4-butanediol, dimethylol butyric acid and butanone. The waterborne polyurethane shoe adhesive prepared by the invention has the characteristics of high solid content, low viscosity, high bonding strength, good water resistance and no pollution. The preparation method of the waterborne polyurethane shoe adhesive has the advantages of simple process, convenient operation, easy recovery and treatment of the solvent and cost saving.
Description
Technical Field
The invention belongs to the field of polyurethane adhesives, and particularly relates to a water-based polyurethane shoe adhesive and a preparation method thereof.
Background
The shoe making industry in China mainly adopts solvent adhesives to bond shoe materials, and the traditional adhesives contain Volatile Organic Compounds (VOCs) and harmful gas pollutants (HAPs), and have the problems of environmental pollution, potential safety hazard and the like. As a new generation of environment-friendly products, the waterborne polyurethane has the advantages of small smell, no combustion, no environmental pollution, convenient construction and the like, and has become a key research direction for replacing solvent-based adhesives. The polyurethane adhesive is an adhesive containing a urethane group (-NHCOO-) or an isocyanate group (-NCO) in the molecular chain. The polyurethane adhesive has the characteristics of wide raw material selection range, strong molecular designability, good adhesion performance to a plurality of materials and the like.
In the prior art, the solid content of the waterborne polyurethane adhesive for shoes is controlled to be about 50 percent, and the viscosity is higher. The solid content is improved, the drying speed of the waterborne polyurethane adhesive for shoes can be increased, the production efficiency is improved, and meanwhile, the heat required by drying is reduced, and the energy is saved. After the solid content exceeds 60%, the viscosity rapidly rises along with the increase of the solid content, and the high viscosity easily causes poor fluidity, so that the discontinuous condition of an adhesive film is easily caused, and further the leveling property and the gluing amount are influenced, therefore, the problem of searching the waterborne polyurethane adhesive for shoes, which has high solid content, low viscosity and high bonding strength, is the subject of research by the technicians in the field.
Disclosure of Invention
The invention provides a water-based polyurethane shoe adhesive and a preparation method thereof on the basis of overcoming the prior art. The preparation method of the waterborne polyurethane shoe adhesive has the advantages of simple process, convenient operation, easy recovery and treatment of the solvent and cost saving; the prepared waterborne polyurethane shoe adhesive has the characteristics of high solid content, low viscosity, high bonding strength, good water resistance and no pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the water-based polyurethane shoe adhesive comprises the following raw materials in parts by weight: 30-50 parts of isophorone-diisocyanate, 20-40 parts of 4,4' -dicyclohexylmethane diisocyanate, 10-25 parts of sulfonated polyether polyol, 5-15 parts of 1, 6-hexanediol adipate, 0.5-3 parts of dibutyltin dilaurate, 1-5 parts of trehalose, 0.5-5 parts of sodium dodecyl benzene sulfonate, 2-8 parts of 1, 4-butanediol, 1-5 parts of dimethylolbutyric acid, 4-8 parts of butanone and 1-3 parts of ethylenediamine.
Further, the feed comprises the following raw materials in parts by weight: 35-45 parts of isophorone-diisocyanate, 25-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 15-20 parts of sulfonated polyether polyol, 8-12 parts of 1, 6-hexanediol adipate, 1-2 parts of dibutyltin dilaurate, 2-5 parts of trehalose, 0.5-2 parts of sodium dodecyl benzene sulfonate, 2-5 parts of 1, 4-butanediol, 1-3 parts of dimethylolbutyric acid, 5-7 parts of butanone and 1-3 parts of ethylenediamine.
Further, the sulfonated polyether polyol is preferably a sulfonated polyether polyol having a molecular weight of 3000; the poly (1, 6-hexanediol adipate) is preferably a poly (1, 6-hexanediol adipate) with a molecular weight of 2000.
On the other hand, the preparation method of the water-based polyurethane shoe glue comprises the following steps:
(1) adding sulfonated polyether polyol and 1, 6-hexanediol adipate into a polymerization reactor, heating to 110-120 ℃, distilling under reduced pressure to remove water for 1-2 h, cooling to 60-70 ℃ after water removal is finished, adding isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, dibutyltin dilaurate and trehalose, heating to 80-100 ℃, and reacting for 2-3 h;
(2) cooling the reaction product obtained in the step (1) to 60-70 ℃, adding butanone, stirring for 10min, adding 1, 4-butanediol and dimethylolbutyric acid, heating to 80-90 ℃, and preserving heat for 1-2 h;
(3) cooling the reaction product obtained in the step (2) to 30-40 ℃, adding sodium dodecyl benzene sulfonate, stirring at a high speed and shearing to obtain an emulsion, adding ethylenediamine into the obtained emulsion, and continuing stirring and chain extension for 30-40 min;
(4) and (4) heating the reaction product obtained in the step (3) to 60-70 ℃, and removing the solvent through reduced pressure distillation to obtain the waterborne polyurethane shoe adhesive.
Further, the step (4) further comprises adding a defoaming agent and a thickening agent into the reaction solution after the solvent is removed by distillation under reduced pressure.
Further, the defoaming agent is any one of aqueous defoaming agents Afcona 2501, Afcona 2502 or Afcona 2524; the thickener is any one of SHEUR or LHEUR.
The invention has the following positive effects:
1. according to the invention, the sulfonated polyether polyol and the poly adipic acid 1,6 hexanediol ester are used as main solid matter sources, and the particle size of polyurethane can be increased by using the sulfonated polyether polyol and the poly adipic acid 1,6 hexanediol ester, so that the solid content is increased, and the increase of the solid content is beneficial to the increase of the bonding strength.
2. The invention selects the trehalose as the internal crosslinking agent, which not only can increase the particle size of the polyurethane, but also can widen the particle size distribution of the polyurethane and make the distribution uniform. The trehalose has cross-linking and chain extension effects, so that the molecular weight of the generated polyurethane is increased, molecular chains are mutually entangled, the particle size is increased, and on the other hand, the trehalose has higher rigidity, and more hydrophobic hard segment structures are formed in the polyurethane after participating in the reaction, so that the average particle size of the emulsion is increased, and the bonding strength, the water resistance and the mechanical strength of the adhesive film are greatly improved.
3. According to the invention, 1, 4-butanediol is used as a micromolecule chain extender, the sulfonic acid type chain extender dimethylolbutyric acid is used as a hydrophilic chain extender, and the hydrophilic groups such as carboxyl, hydroxyl and the like are contained, so that the hydration layer can be thinned, the fluidity of the emulsion is enhanced, and the viscosity of the polyurethane is reduced to a certain extent.
4. The preparation method has simple process, convenient operation and easy solvent recovery treatment, and the obtained product is applied to the shoe making industry, and has the advantages of great convenience for construction in the production process of glued shoes due to high solid content, low viscosity, high bonding strength and good water resistance, and the gluing amount of shoe materials can be reduced, thereby not only ensuring the quality, but also saving the cost.
Detailed Description
The present invention is further described in the following examples, which should not be construed as limiting the scope of the invention, but rather as providing the following examples which are set forth to illustrate and not limit the scope of the invention.
Example 1
The waterborne polyurethane shoe adhesive comprises the following raw materials in parts by weight:
a preparation method of water-based polyurethane shoe glue comprises the following steps:
adding sulfonated polyether polyol and 1, 6-hexanediol adipate into a polymerization reactor according to the component ratio, heating to 120 ℃, carrying out reduced pressure distillation to remove water for 2 hours, cooling to 65 ℃ after the water removal is finished, adding isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, dibutyltin dilaurate and trehalose, heating to 90 ℃, and reacting for 2 hours; then cooling the reaction product to 70 ℃, adding butanone, stirring for 10min, adding 1, 4-butanediol and dimethylolbutyric acid, heating to 90 ℃, and preserving heat for 1 h; cooling the reaction product to 35 ℃, adding sodium dodecyl benzene sulfonate and deionized water, shearing in a high-speed shearing stirrer at the rotating speed of 5000r/min to obtain emulsion, adding ethylenediamine, and continuing stirring and chain extension for 40 min; and finally, heating to 70 ℃, and removing the solvent by reduced pressure distillation to obtain the waterborne polyurethane shoe adhesive.
Example 2
The waterborne polyurethane shoe adhesive comprises the following raw materials in parts by weight:
a preparation method of water-based polyurethane shoe glue comprises the following steps:
adding sulfonated polyether polyol and 1, 6-hexanediol adipate into a polymerization reactor according to the component ratio, heating to 110 ℃, carrying out reduced pressure distillation to remove water for 2 hours, cooling to 60 ℃ after the water removal is finished, adding isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, dibutyltin dilaurate and trehalose, heating to 80 ℃, and reacting for 2 hours; then cooling the reaction product to 60 ℃, adding butanone, stirring for 10min, adding 1, 4-butanediol and dimethylolbutyric acid, heating to 80 ℃, and preserving heat for 1 h; cooling the reaction product to 30 ℃, adding sodium dodecyl benzene sulfonate and deionized water, shearing to obtain emulsion under the condition that the rotating speed in a high-speed shearing stirrer is 4500r/min, adding ethylenediamine, and continuing stirring and chain extension for 40 min; and finally, heating to 70 ℃, and removing the solvent by reduced pressure distillation to obtain the waterborne polyurethane shoe adhesive.
Example 3
The waterborne polyurethane shoe adhesive comprises the following raw materials in parts by weight:
a preparation method of water-based polyurethane shoe glue comprises the following steps:
adding sulfonated polyether polyol and 1, 6-hexanediol adipate into a polymerization reactor according to the component ratio, heating to 120 ℃, carrying out reduced pressure distillation to remove water for 2 hours, cooling to 70 ℃ after the water removal is finished, adding isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, dibutyltin dilaurate and trehalose, heating to 100 ℃, and reacting for 2 hours; then cooling the reaction product to 70 ℃, adding butanone, stirring for 10min, adding 1, 4-butanediol and dimethylolbutyric acid, heating to 90 ℃, and preserving heat for 1 h; cooling the reaction product to 40 ℃, adding sodium dodecyl benzene sulfonate and deionized water, shearing in a high-speed shearing stirrer at the rotating speed of 5000r/min to obtain emulsion, adding ethylenediamine, and continuing stirring and chain extension for 40 min; and finally, heating to 70 ℃, and removing the solvent by reduced pressure distillation to obtain the waterborne polyurethane shoe adhesive.
Comparative example 1
Compared with the example 1, the component is trimethylolpropane to replace the trehalose, and the rest is the same;
comparative example 2
Compared with the example 1, the ingredients do not contain trehalose, and the rest is the same;
comparative example 3
1, 4-butanediol and dimethylolbutyric acid were not contained in the composition as in example 1;
comparative example 4
Compared with the example 1, 4-butanediol is not contained in the components, and the rest is the same;
comparative example 5
As compared with example 1, dimethylolbutyric acid was not contained in the composition, the same holds true;
and (3) performance testing:
the samples of examples 1 to 3 and comparative examples 1 to 5 were subjected to the following tests of the index, and the results are shown in Table 1 below.
(1) Solid content: weighing 1.0-1.5g of the sample in a weighed weighing bottle, drying to constant weight, and calculating the solid content;
(2) viscosity: measured according to GB/T4851-84;
(3) initial adhesion: as determined in GB/T2791-1995; coating the emulsion on a PU/PVC film for compounding
Drying the films, and testing the T-peel strength;
(4) water resistance: the mixture was placed in 50 ℃ water for 24 hours and then observed.
(5) Heat resistance: cleavage was observed at a temperature of 80 ℃.
Table 1 results of performance testing
From the results in Table 1, it can be seen that the polyurethane shoes prepared in examples 1-3 of the present invention have a gel content of 63% -65%, a viscosity of 180-260 mpa.s, a peel strength of 7.8-8.2N, and good water resistance. And from the results of examples 1 to 3, it can be seen that the polyurethane shoe adhesive prepared in example 1 has the most excellent properties.
Comparative examples 1-2 examined the effect on viscosity when trehalose was used as an internal crosslinker. Comparative example 1 the polyurethane shoe prepared in comparative example 1 had a solid content decreased to 54% and deteriorated heat resistance when trimethylolpropane was used instead of trehalose, while the polyurethane shoe prepared in comparative example 2 had a solid content of only 46% and deteriorated water resistance and heat resistance when no trehalose internal crosslinking agent was included.
Comparative examples 3-5 the effects of 1, 4-butanediol and dimethylolbutanoic acid were examined. Comparative examples 3 to 5 were prepared to have polyurethane shoe adhesives of 780mpa.s, 530mpa.s and 580mpa.s, respectively, and comparative example 3, which did not contain 1, 4-butanediol and dimethylolbutyric acid, had the highest viscosity and deteriorated water resistance and water resistance
Therefore, the results show that the polyurethane shoe glue prepared by the invention has excellent performance, high solid content, low viscosity, strong bonding force, good water resistance and heat resistance.
Claims (6)
1. The water-based polyurethane shoe adhesive is characterized by comprising the following raw materials in parts by weight: 30-50 parts of isophorone-diisocyanate, 20-40 parts of 4,4' -dicyclohexylmethane diisocyanate, 10-25 parts of sulfonated polyether polyol, 5-15 parts of poly (adipic acid-1, 6-hexanediol ester), 0.5-3 parts of dibutyltin dilaurate, 1-5 parts of trehalose, 0.5-5 parts of sodium dodecyl benzene sulfonate, 2-8 parts of 1, 4-butanediol, 1-5 parts of dimethylolbutyric acid, 4-8 parts of butanone and 1-3 parts of ethylenediamine;
the preparation method of the water-based polyurethane shoe adhesive comprises the following steps:
(1) adding sulfonated polyether polyol and poly adipic acid-1, 6-hexanediol into a polymerization reactor, heating to 110-120 ℃, distilling under reduced pressure to remove water for 1-2 h, cooling to 60-70 ℃ after water removal is finished, adding isophorone-diisocyanate, 4' -dicyclohexylmethane diisocyanate, dibutyltin dilaurate and trehalose, heating to 80-100 ℃, and reacting for 2-3 h;
(2) cooling the reaction product obtained in the step (1) to 60-70 ℃, adding butanone, stirring for 10min, adding 1, 4-butanediol and dimethylolbutyric acid, heating to 80-90 ℃, and preserving heat for 1-2 h;
(3) cooling the reaction product obtained in the step (2) to 30-40 ℃, adding sodium dodecyl benzene sulfonate, stirring at a high speed and shearing to obtain an emulsion, adding ethylenediamine into the obtained emulsion, and continuing stirring and chain extension for 30-40 min;
(4) and (4) heating the reaction product obtained in the step (3) to 60-70 ℃, and removing the solvent through reduced pressure distillation to obtain the waterborne polyurethane shoe adhesive.
2. The water-based polyurethane shoe adhesive of claim 1, which is characterized by comprising the following raw materials in parts by weight: 35-45 parts of isophorone-diisocyanate, 25-35 parts of 4,4' -dicyclohexylmethane diisocyanate, 15-20 parts of sulfonated polyether polyol, 8-12 parts of poly (adipic acid-1, 6-hexanediol ester), 1-2 parts of dibutyltin dilaurate, 2-5 parts of trehalose, 0.5-2 parts of sodium dodecyl benzene sulfonate, 2-5 parts of 1, 4-butanediol, 1-3 parts of dimethylolbutyric acid, 5-7 parts of butanone and 1-3 parts of ethylenediamine.
3. The waterborne polyurethane shoe glue of claim 1, wherein the sulfonated polyether polyol is selected from sulfonated polyether polyols having a molecular weight of 3000; the poly adipic acid-1, 6-hexanediol ester selects poly adipic acid-1, 6-hexanediol ester with molecular weight of 2000.
4. The waterborne polyurethane shoe polish as claimed in claim 1, wherein the rotation speed during high-speed stirring and shearing in step (3) is 4500-5500 r/min.
5. The waterborne polyurethane shoe polish of claim 1, wherein in the preparation method, the step (4) further comprises adding a defoaming agent and a thickening agent into the reaction solution after the solvent is removed by distillation under reduced pressure.
6. The waterborne polyurethane shoe glue of claim 5, wherein the defoaming agent is any one of a waterborne defoaming agent Afcona 2501, Afcona 2502 or Afcona 2524; the thickener is any one of SHEUR or LHEUR.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230189A (en) * | 2008-01-29 | 2008-07-30 | 武汉理工大学 | Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material |
| CN110799617A (en) * | 2017-06-29 | 2020-02-14 | 生态合成股份有限公司 | Adhesive with adhesiveness and use in wood composite products |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6649727B1 (en) * | 2000-07-27 | 2003-11-18 | 3M Innovative Properties Company | Aqueous colloidal dispersions of sulfonated polyurethane ureas and products |
| US7012115B2 (en) * | 2003-07-30 | 2006-03-14 | Asahi Kasei Kabushiki Kaisha | Aqueous urethane polyol and coating composition containing the same |
| JP2010513702A (en) * | 2006-12-19 | 2010-04-30 | ダウ グローバル テクノロジーズ インコーポレイティド | Composition comprising a polyurethane dispersion having a high solids content |
| CN100569887C (en) * | 2007-09-21 | 2009-12-16 | 北京市化学工业研究院 | A kind of method for preparing water polyurethane binder for shoe |
| DE102007062529A1 (en) * | 2007-12-20 | 2009-06-25 | Henkel Ag & Co. Kgaa | 2K PU adhesive for bonding fiber molded parts |
| CA2916047C (en) * | 2013-06-27 | 2020-11-17 | Asahi Kasei Chemicals Corporation | Polyisocyanate composition and method of manufacturing the same, blocked polyisocyanate composition and method of manufacturing the same, resin composition, curable resin composition and hardened material |
| CN104744660B (en) * | 2013-12-31 | 2018-02-02 | 财团法人纺织产业综合研究所 | Aqueous polyurethane resin and its manufacture method and its in the application of synthetic leather |
| CN106221649B (en) * | 2016-08-15 | 2019-03-01 | 汕头市龙湖昌丰化工有限公司 | The Waterborne polyurethane shoe adhesive and preparation method thereof of low viscosity high-adhesive-strength |
| CN109749042B (en) * | 2018-12-06 | 2021-03-30 | 杭州传化精细化工有限公司 | Preparation method of sulfonic acid type aqueous polyurethane dispersion |
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| CN101230189A (en) * | 2008-01-29 | 2008-07-30 | 武汉理工大学 | Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material |
| CN110799617A (en) * | 2017-06-29 | 2020-02-14 | 生态合成股份有限公司 | Adhesive with adhesiveness and use in wood composite products |
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