CN104974702A - Nanometer waterborne polyurethane adhesive and preparation method therefor - Google Patents
Nanometer waterborne polyurethane adhesive and preparation method therefor Download PDFInfo
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- CN104974702A CN104974702A CN201510349110.3A CN201510349110A CN104974702A CN 104974702 A CN104974702 A CN 104974702A CN 201510349110 A CN201510349110 A CN 201510349110A CN 104974702 A CN104974702 A CN 104974702A
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Abstract
The invention discloses a nanometer waterborne polyurethane adhesive and a preparation method therefor. The nanometer waterborne polyurethane adhesive comprises the following components in parts by weight: 20-30 parts of polycaprolactone diol, 10-15 parts of isophorone diisocyanate, 2-6 parts of polyether triol, 3-6 parts of dibutyl phthalate, 0.2-0.8 part of dibutyltin dilaurate, 0.1-0.3 part of ethylene glycol monomethyl acetate, 0.3-0.9 part of trimethylolpropane trimester, 0.2-0.5 part of ethoxy lauryl alcohol, 0.3-0.7 part of lysine-di-isocyanate, 5-10 parts of polyhydric alcohols, 1-4 parts of polyamine, 1-3 parts of sodium alkyl benzene sulfonate, 2-5 parts of sodium dodecyl benzene sulfonate, 1-2 parts of curing agent and 20-40 parts of water. A sulfonate radical hydrophilic chain extender is adopted in the adhesive, the water resistance is improved, the cross-linking agents such as polyhydric alcohols and polyamine are added in a polyurethane system, and the adhesive strength of the adhesive is improved.
Description
Technical field
The invention belongs to technology of fine chemicals, be specifically related to a kind of nano aqueous adhesive for polyurethane and preparation method thereof.
Background technology
China is shoemaking country maximum in the world, the annual production of current gluing footwear is more than 2,000,000,000 pairs, in footwear production, the overwhelming majority (95%) uses neoprene sizing agent, its tack is good, can cold bonding, cheap, but its plasticizer-resistant poor permeability, poor with material binding to novel footwear such as PU leather, thermoplastic elastomer, soft pvcs, what this product was more fatal is that it adopts benzene-like compounds to make solvent, not only poisonous, and inflammable, be not suitable with the requirement of shoe-making industry development.The graft neoprene adhesives of the not containing benezene solvent of current third generation adhesives for shoes, lowly poisons formula although have employed, and wherein a large amount of organic solvent still can damage human body and ecotope.Along with the enhancing in the appearance of organic volatile standard and people's environmental consciousness, take advantage of a situation based on the forth generation adhesives for shoes of aq. type and no-solvent type.No matter from domestic or state is external, research and develop the water-based adhesives for shoes that can compare favourably with solvent-based adhesive become shoe-making field can the important symbol of Sustainable development.Do not use or use the organic solvent of seldom amount in Aqueous Polyurethane Adhesives production process, decrease environmental pollution, reduce the generation of potential safety hazard between work car and workman's occupational illness, therefore its development & application gets more and more people's extensive concerning simultaneously.
Adhesives for shoes generally should have good snappiness and impact resistance, and tack is strong, has good wetting property to multiple footwear material (leather, synthetic leather and rubber etc.); Because be exposed to open air, shoes-used glue also should have superior resistance to low temperature and water resistance, i.e. weathering resistance; In addition, sizing agent also should be tried one's best, and soon, this just requires that it has high solids content and low curing performance to rate of drying at normal temperatures.In addition, glue-applying technique also should be tried one's best simple and fast, convenient operation.Aqueous Polyurethane Adhesives outward appearance is generally substantially all oyster white even translucent, also not easily find even if having to remain in a little beyond non-adhering side, the needs of the light color that applicable requirement is higher or even white leather shoes or sports shoes production, but because price is partially expensive, at present mainly for the production of high-grade footwear and outlet footwear.The defect that adhesives for shoes also also exists self made by urethane.Because the volatilization of water is compared to the volatilization of organic solvent, need the time more grown, this will inevitably increase the thermal energy consumption of Aqueous Polyurethane Adhesives in application and construction process.Because the material of shoemaking often shows hydrophobicity, and adhesive for polyurethane is wetting ability, and the physisorption that both difficult consistencies make cohesive strength natively not make us good is very little especially.This defect have impact on its widespread use to a great extent.
Summary of the invention
The invention provides a kind of nano aqueous adhesive for polyurethane and preparation method thereof, adopt sulfonate radical class hydrophilic chain extender in sizing agent, improve water tolerance, in polyurethane system, add internal crosslinker polyvalent alcohol and polyamine, improve the cohesive strength of tackiness agent.
To achieve these goals, the technique means that the present invention takes is:
Nano aqueous adhesive for polyurethane, component and each constituent mass number as follows: polycaprolactone diols 20 ~ 30 parts, isophorone diisocyanate 10 ~ 15 parts, trihydroxy-polyethers 2 ~ 6 parts, dibutyl phthalate 3 ~ 6 parts, dibutyl tin laurate 0.2 ~ 0.8 part, ethylene glycol ether ester 0.1 ~ 0.3 part, trimethylolpropane triester 0.3 ~ 0.9 part, hydroxyethyl dodecyl alcohol 0.2 ~ 0.5 part, lysinediisocyanate 0.3 ~ 0.7 part, polyvalent alcohol 5 ~ 10 parts, polyamine 1 ~ 4 part, sodium alkyl benzene sulfonate 1 ~ 3 part, Sodium dodecylbenzene sulfonate 2 ~ 5 parts, 1 ~ 2 part, solidifying agent, 20 ~ 40 parts, water.
Described solidifying agent is benzoyl peroxide or water-based isocyanate.
Described polyvalent alcohol is glycerol or butyleneglycol.
Described polyamine is triethylamine.
Described nano aqueous adhesive for polyurethane, component and each constituent mass number as follows: polycaprolactone diols 25 parts, isophorone diisocyanate 12.5 parts, trihydroxy-polyethers 4 parts, dibutyl phthalate 4.5 parts, dibutyl tin laurate 0.5 part, ethylene glycol ether ester 0.2 part, trimethylolpropane triester 0.6 part, hydroxyethyl dodecyl alcohol 0.35 part, lysinediisocyanate 0.5 part, polyvalent alcohol 8 parts, polyamine 2.5 parts, sodium alkyl benzene sulfonate 2 parts, Sodium dodecylbenzene sulfonate 3.5 parts, 1.5 parts, solidifying agent, 30 parts, water.
The preparation method of described nano aqueous adhesive for polyurethane, comprises the steps:
1), under nitrogen protection, isophorone diisocyanate and polycaprolactone diols are joined in four-hole boiling flask, drip dibutyl tin laurate, with the rotating speed stirring reaction 1 ~ 3h of 60 ~ 90rpm with the speed of 1 ~ 3mL/min;
2) add trihydroxy-polyethers, dibutyl phthalate, ethylene glycol ether ester, trimethylolpropane triester, hydroxyethyl dodecyl alcohol, lysinediisocyanate and polyvalent alcohol to stir, add polyamine neutralization reaction 20 ~ 60min;
3) sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are dissolved in water, are then added drop-wise to step 2) solution in carry out chain extending reaction, reaction times 20 ~ 50min, dropping process stirs simultaneously;
4) add solidifying agent, stir 10 ~ 30min with the rotating speed of 320 ~ 400rpm, obtain nano aqueous adhesive for polyurethane.
In step 1), rate of addition is 2mL/min.
Step 2) middle neutralization reaction 40min.
Step 4) medium speed is 380rpm, stirs 20min.
Sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are hydrophilic chain extender, sulfonate radical is stronger than the wetting ability of carboxylate radical, ensureing under the prerequisite that wetting ability requires, reduce total hydrophilic radical content, thus improve the water tolerance of sizing agent, in polyurethane system, add internal crosslinker polyvalent alcohol, polyamine etc., adding of linking agent makes script urethane formation cross-linked structure to a certain degree linearly, thus can improve the cohesive strength of tackiness agent.
Beneficial effect:
The invention provides a kind of nano aqueous adhesive for polyurethane and preparation method thereof, adopt sulfonate radical class hydrophilic chain extender in sizing agent, improve water tolerance, in polyurethane system, add internal crosslinker polyvalent alcohol and polyamine, improve the cohesive strength of tackiness agent.
Embodiment
Embodiment 1
Nano aqueous adhesive for polyurethane, component and each constituent mass number as follows: polycaprolactone diols 20 parts, isophorone diisocyanate 10 parts, trihydroxy-polyethers 2 parts, dibutyl phthalate 3 parts, dibutyl tin laurate 0.2 part, ethylene glycol ether ester 0.1 part, trimethylolpropane triester 0.3 part, hydroxyethyl dodecyl alcohol 0.2 part, lysinediisocyanate 0.3 part, glycerol 5 parts, triethylamine 1 part, sodium alkyl benzene sulfonate 1 part, Sodium dodecylbenzene sulfonate 2 parts, solidifying agent benzoyl peroxide 1 part, 20 parts, water.
Preparation method, comprises the steps:
1), under nitrogen protection, isophorone diisocyanate and polycaprolactone diols are joined in four-hole boiling flask, drip dibutyl tin laurate, with the rotating speed stirring reaction 2h of 70rpm with the speed of 2mL/min;
2) add trihydroxy-polyethers, dibutyl phthalate, ethylene glycol ether ester, trimethylolpropane triester, hydroxyethyl dodecyl alcohol, lysinediisocyanate and polyvalent alcohol to stir, add polyamine neutralization reaction 40min;
3) sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are dissolved in water, are then added drop-wise to step 2) solution in carry out chain extending reaction, reaction times 35min, dropping process stirs simultaneously;
4) add solidifying agent, stir 20min with the rotating speed of 380rpm, obtain nano aqueous adhesive for polyurethane.
Embodiment 2
Nano aqueous adhesive for polyurethane, component and each constituent mass number as follows: polycaprolactone diols 30 parts, isophorone diisocyanate 15 parts, trihydroxy-polyethers 6 parts, dibutyl phthalate 6 parts, dibutyl tin laurate 0.8 part, ethylene glycol ether ester 0.3 part, trimethylolpropane triester 0.9 part, hydroxyethyl dodecyl alcohol 0.5 part, lysinediisocyanate 0.7 part, glycerol 10 parts, triethylamine 4 parts, sodium alkyl benzene sulfonate 3 parts, Sodium dodecylbenzene sulfonate 5 parts, solidifying agent benzoyl peroxide 2 parts, 40 parts, water.
Preparation method, comprises the steps:
1), under nitrogen protection, isophorone diisocyanate and polycaprolactone diols are joined in four-hole boiling flask, drip dibutyl tin laurate, with the rotating speed stirring reaction 2h of 70rpm with the speed of 2mL/min;
2) add trihydroxy-polyethers, dibutyl phthalate, ethylene glycol ether ester, trimethylolpropane triester, hydroxyethyl dodecyl alcohol, lysinediisocyanate and polyvalent alcohol to stir, add polyamine neutralization reaction 40min;
3) sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are dissolved in water, are then added drop-wise to step 2) solution in carry out chain extending reaction, reaction times 35min, dropping process stirs simultaneously;
4) add solidifying agent, stir 20min with the rotating speed of 380rpm, obtain nano aqueous adhesive for polyurethane.
Embodiment 3
Nano aqueous adhesive for polyurethane, component and each constituent mass number as follows: polycaprolactone diols 25 parts, isophorone diisocyanate 12.5 parts, trihydroxy-polyethers 4 parts, dibutyl phthalate 4.5 parts, dibutyl tin laurate 0.5 part, ethylene glycol ether ester 0.2 part, trimethylolpropane triester 0.6 part, hydroxyethyl dodecyl alcohol 0.35 part, lysinediisocyanate 0.5 part, butyleneglycol 8 parts, triethylamine 2.5 parts, sodium alkyl benzene sulfonate 2 parts, Sodium dodecylbenzene sulfonate 3.5 parts, water-based isocyanate 1.5 parts, 30 parts, water.
Preparation method, comprises the steps:
1), under nitrogen protection, isophorone diisocyanate and polycaprolactone diols are joined in four-hole boiling flask, drip dibutyl tin laurate, with the rotating speed stirring reaction 2h of 70rpm with the speed of 2mL/min;
2) add trihydroxy-polyethers, dibutyl phthalate, ethylene glycol ether ester, trimethylolpropane triester, hydroxyethyl dodecyl alcohol, lysinediisocyanate and polyvalent alcohol to stir, add polyamine neutralization reaction 40min;
3) sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are dissolved in water, are then added drop-wise to step 2) solution in carry out chain extending reaction, reaction times 35min, dropping process stirs simultaneously;
4) add solidifying agent, stir 20min with the rotating speed of 380rpm, obtain nano aqueous adhesive for polyurethane.
Performance test is carried out to the nano aqueous adhesive for polyurethane of embodiment 1 ~ 3.
The mensuration of solid content: first clean surface ware is weighed, quality is W, then takes W1 sample in watch-glass, and 120 DEG C of dry 3h, are weighed as W2 after being cooled to room temperature, emulsion solid content=(W2-W)/W1 × l00%;
Initial stage peeling force and the stripping strength of tackiness agent is measured according to ISOISO-11644;
Water tolerance measures: water-intake rate can reflect the water tolerance of glued membrane.The glued membrane of preparation quality scope in 0.1-0.5g, its quality is also denoted as W; And then after glued membrane is soaked 24h completely in water, take out and blot with the moisture of filter paper by its surface immediately, claim its quality and be denoted as W1, water-intake rate=(W1-W)/W1 × 100%.Test result is in table 1.
Table 1:
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Solid content/% | 49 | 48 | 57 |
| Tensile strength/MPa | 6.82 | 6.57 | 8.22 |
| Elongation at break/% | 136 | 162 | 194 |
| Water-intake rate/% | 22.5 | 23.1 | 19.3 |
Claims (9)
1. nano aqueous adhesive for polyurethane, it is characterized in that component and each constituent mass number as follows: polycaprolactone diols 20 ~ 30 parts, isophorone diisocyanate 10 ~ 15 parts, trihydroxy-polyethers 2 ~ 6 parts, dibutyl phthalate 3 ~ 6 parts, dibutyl tin laurate 0.2 ~ 0.8 part, ethylene glycol ether ester 0.1 ~ 0.3 part, trimethylolpropane triester 0.3 ~ 0.9 part, hydroxyethyl dodecyl alcohol 0.2 ~ 0.5 part, lysinediisocyanate 0.3 ~ 0.7 part, polyvalent alcohol 5 ~ 10 parts, polyamine 1 ~ 4 part, sodium alkyl benzene sulfonate 1 ~ 3 part, Sodium dodecylbenzene sulfonate 2 ~ 5 parts, 1 ~ 2 part, solidifying agent, 20 ~ 40 parts, water.
2. nano aqueous adhesive for polyurethane according to claim 1, is characterized in that: described solidifying agent is benzoyl peroxide or water-based isocyanate.
3. nano aqueous adhesive for polyurethane according to claim 1, is characterized in that: described polyvalent alcohol is glycerol or butyleneglycol.
4. nano aqueous adhesive for polyurethane according to claim 1, is characterized in that: described polyamine is triethylamine.
5. nano aqueous adhesive for polyurethane according to claim 1, it is characterized in that component and each constituent mass number as follows: polycaprolactone diols 25 parts, isophorone diisocyanate 12.5 parts, trihydroxy-polyethers 4 parts, dibutyl phthalate 4.5 parts, dibutyl tin laurate 0.5 part, ethylene glycol ether ester 0.2 part, trimethylolpropane triester 0.6 part, hydroxyethyl dodecyl alcohol 0.35 part, lysinediisocyanate 0.5 part, polyvalent alcohol 8 parts, polyamine 2.5 parts, sodium alkyl benzene sulfonate 2 parts, Sodium dodecylbenzene sulfonate 3.5 parts, 1.5 parts, solidifying agent, 30 parts, water.
6. the preparation method of nano aqueous adhesive for polyurethane described in claim 1, is characterized in that comprising the steps:
1), under nitrogen protection, isophorone diisocyanate and polycaprolactone diols are joined in four-hole boiling flask, drip dibutyl tin laurate, with the rotating speed stirring reaction 1 ~ 3h of 60 ~ 90rpm with the speed of 1 ~ 3mL/min;
2) add trihydroxy-polyethers, dibutyl phthalate, ethylene glycol ether ester, trimethylolpropane triester, hydroxyethyl dodecyl alcohol, lysinediisocyanate and polyvalent alcohol to stir, add polyamine neutralization reaction 20 ~ 60min;
3) sodium alkyl benzene sulfonate and Sodium dodecylbenzene sulfonate are dissolved in water, are then added drop-wise to step 2) solution in carry out chain extending reaction, reaction times 20 ~ 50min, dropping process stirs simultaneously;
4) add solidifying agent, stir 10 ~ 30min with the rotating speed of 320 ~ 400rpm, obtain nano aqueous adhesive for polyurethane.
7. the preparation method of nano aqueous adhesive for polyurethane according to claim 6, is characterized in that: in step 1), rate of addition is 2mL/min.
8. the preparation method of nano aqueous adhesive for polyurethane according to claim 6, is characterized in that: step 2) in neutralization reaction 40min.
9. the preparation method of nano aqueous adhesive for polyurethane according to claim 6, is characterized in that: step 4) medium speed is 380rpm, stirs 20min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510349110.3A CN104974702A (en) | 2015-06-23 | 2015-06-23 | Nanometer waterborne polyurethane adhesive and preparation method therefor |
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| CN201510349110.3A CN104974702A (en) | 2015-06-23 | 2015-06-23 | Nanometer waterborne polyurethane adhesive and preparation method therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237701A (en) * | 2015-11-23 | 2016-01-13 | 施新晴 | Nano water glass-polyester fiber membrane adhesive and preparation method thereof |
| CN106118577A (en) * | 2016-07-04 | 2016-11-16 | 黄淳 | A kind of footwear Bicompenent high solid content polyurethane adhesive and preparation method thereof |
| CN106916272A (en) * | 2016-08-19 | 2017-07-04 | 西北大学 | Material of fragile organic matter historical relic and its preparation method and application is reinforced under a kind of wet environment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051778A (en) * | 2002-07-19 | 2004-02-19 | Dainippon Ink & Chem Inc | Aqueous dispersion of polyurethane resin and water-base adhesive |
| CN103254867A (en) * | 2013-04-26 | 2013-08-21 | 巨石集团有限公司 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
| CN103694941A (en) * | 2013-12-16 | 2014-04-02 | 陕西煤业化工技术研究院有限责任公司 | Waterborne polyurethane adhesive with high solid content and preparation method thereof |
-
2015
- 2015-06-23 CN CN201510349110.3A patent/CN104974702A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051778A (en) * | 2002-07-19 | 2004-02-19 | Dainippon Ink & Chem Inc | Aqueous dispersion of polyurethane resin and water-base adhesive |
| CN103254867A (en) * | 2013-04-26 | 2013-08-21 | 巨石集团有限公司 | Preparation method of sulfonic acid type waterborne polyurethane adhesive |
| CN103694941A (en) * | 2013-12-16 | 2014-04-02 | 陕西煤业化工技术研究院有限责任公司 | Waterborne polyurethane adhesive with high solid content and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237701A (en) * | 2015-11-23 | 2016-01-13 | 施新晴 | Nano water glass-polyester fiber membrane adhesive and preparation method thereof |
| CN106118577A (en) * | 2016-07-04 | 2016-11-16 | 黄淳 | A kind of footwear Bicompenent high solid content polyurethane adhesive and preparation method thereof |
| CN106916272A (en) * | 2016-08-19 | 2017-07-04 | 西北大学 | Material of fragile organic matter historical relic and its preparation method and application is reinforced under a kind of wet environment |
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Application publication date: 20151014 |