CN101845133A - Method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion - Google Patents
Method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion Download PDFInfo
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Abstract
The invention discloses a method for preparing natural polyhydroxy compound modified aqueous polyurethane emulsion, which comprises the following steps of: adding polyglycol into a dry reactor, heating the reactor to melt the polyglycol in the reactor, and adding diisocyanate into the reactor to perform polymerization reaction; adding a chain extender into the reactor to prepare a polyurethane prepolymer; adding a natural polyhydroxy compound and a hydrophilic chain extender into the reactor to perform reaction for certain time, then cooling a reaction system, and adding organic alkali into the reactor to adjust the pH value of the reaction system; and adding deionized water into the reactor with high-speed stirring to obtain the natural polyhydroxy compound modified aqueous polyurethane emulsion. Because of the adoption of natural polyhydroxy compound modified aqueous polyurethane, the product has good comprehensive performance, has the characteristics of environment friendliness, no toxicity, no harm, safe transportation and the like, and belongs to an environment-friendly polyurethane product. The natural polyhydroxy compound modified aqueous polyurethane can overcome the defects that the traditional aqueous polyurethane has low room-temperature curing speed, poor water resistance and the like.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion.
Background technology
Along with human life quality's raising, environmental regulation is also more and more stricter, and various environmental regulations all have strict restriction to the quantity discharged of volatile organic compounds (VOC), the content of hazardous solvent.Aqueous polyurethane is dispersion medium with water, have low toxicity, advantage such as nonflammable, free from environmental pollution, energy-conservation, safe and reliable, therefore aqueous polyurethane is covered with paint, lacquer, colour wash, etc. and field such as printing ink has obtained to use widely at coating, tackiness agent, textile finishing, leather, synthetic leather in recent years.But with respect to solvent borne polyurethane, aqueous polyurethane has been owing to introduced hydrophilic radicals such as carboxyl, hydroxyl in molecular structure, often has water-fast, solvent resistance and the relatively poor shortcoming of mechanical property.
Cross-linking modified is that form by chemical bond is linked at the polyurethane macromolecular of line style together, form to have cancellated urethane resin, and be to change thermoplastic urethane resin into thermosetting resin more effective a kind of approach.Aqueous polyurethane after crosslinked is filmed and can be shown good water-fast, solvent resistance.
Summary of the invention
The objective of the invention is to overcome that existing aqueous polyurethane is water-fast, solvent resistance and the relatively poor shortcoming of mechanical property, provide a kind of with low cost, technology is simple, the preparation method of eco-friendly natural polyhydroxy compound modified aqueous polyurethane emulsion.
For achieving the above object, the technical solution used in the present invention is:
1) at first polyglycol is joined in the dry reactor, after heating the polyglycol fusion that makes in the reactor, vulcabond is joined in the reactor and carry out polyreaction at 70-90 ℃, wherein vulcabond is 2-4 with the ratio of the amount of substance of polyglycol: 1, and the reaction times is 1-5h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 1-4h, and wherein 1, the 4-butyleneglycol is 0.3-1.2 with the ratio of the amount of substance of polyglycol: 1;
3) add natural polyhydroxy compound and hydrophilic chain extender again in the reactor at 60-80 ℃ of reaction 2-5h, wherein vulcabond is 8-35 with the ratio of the amount of substance of natural polyhydroxy compound: 1, and vulcabond is 2.5-5 with the ratio of the amount of substance of hydrophilic chain extender: 1;
4) be cooled to 15～35 ℃, adding organic bases conditioned reaction system pH is 7-8, and the adding temperature is 0～40 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Polyglycol of the present invention is polyether Glycols or polyester diol, and polyether Glycols and polyester diol number average relative molecular mass be respectively 1000 or 2000, and polyether Glycols is polyoxypropyleneglycol or PTMG dibasic alcohol; Polyester diol is polycaprolactone dibasic alcohol, PCDL or poly adipate succinic acid ester dibasic alcohol;
Vulcabond is isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate;
Natural polyhydroxy compound is sucrose, glucose, Xylitol or sorbyl alcohol;
Hydrophilic chain extender has sulfonate type and carboxylic acid type two classes, and the sulfonate type chainextender is a quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate or 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium; The carboxylic acid type chainextender is dimethylol propionic acid or dimethylolpropionic acid;
Organic bases is Trimethylamine 99, triethylamine or trolamine.
The present invention utilizes natural materials that aqueous polyurethane is carried out modification, can obtain the complete environment-protecting polyurethane material of excellent combination property.Hydroxyl can be introduced polyurethane backbone when utilizing natural polyhydroxy compound and polyurethane reaction, make it to form complicated cross-linked structure, prepared aqueous polyurethane will keep the characteristic of environment-friendly material, and it is slow to improve traditional water based polyurethane self-vulcanizing speed, poor water resistance, shortcoming such as initial bonding strength is low.And do not need to add hazardous solvent in the whole preparation process, and so both eliminated pollution and infringement to environment and operator, also improved the effect of product; Simultaneously, can be by regulating vulcabond and the kind of polyglycol and the product that relative molecular mass obtains expecting.
Embodiment
Embodiment 1,
1) at first the polycaprolactone dibasic alcohol is joined in the dry reactor, after heating the polycaprolactone dibasic alcohol fusion that makes in the reactor, again isophorone diisocyanate is joined in the reactor and carry out polyreaction at 70 ℃, wherein isophorone diisocyanate is 2: 1 with the ratio of the amount of substance of polycaprolactone dibasic alcohol, and the reaction times is 5h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 2h, and wherein 1, the 4-butyleneglycol is 0.3: 1 with the ratio of the amount of substance of polycaprolactone dibasic alcohol;
3) add sucrose and hydrophilic chain extender dimethylol propionic acid again in the reactor at 60 ℃ of reaction 5h, wherein isophorone diisocyanate is 25: 1 with the ratio of the amount of substance of sucrose, and isophorone diisocyanate is 4.4: 1 with the ratio of the amount of substance of dimethylol propionic acid;
4) be cooled to 15 ℃, adding triethylamine conditioned reaction system pH is 7, and the adding temperature is 10 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Embodiment 2,
1) at first the PTMG dibasic alcohol is joined in the dry reactor, after heating the PTMG dibasic alcohol fusion that makes in the reactor, again hexamethylene diisocyanate is joined in the reactor and carry out polyreaction at 90 ℃, wherein hexamethylene diisocyanate is 4: 1 with the ratio of the amount of substance of PTMG dibasic alcohol, and the reaction times is 1h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 3h, and wherein 1, the 4-butyleneglycol is 1.2: 1 with the ratio of the amount of substance of PTMG dibasic alcohol;
3) add glucose and hydrophilic chain extender dimethylolpropionic acid again in the reactor at 70 ℃ of reaction 3.5h, wherein hexamethylene diisocyanate is 35: 1 with the ratio of the amount of substance of glucose, and hexamethylene diisocyanate is 2.5: 1 with the ratio of the amount of substance of dimethylolpropionic acid;
4) be cooled to 30 ℃, adding Trimethylamine 99 conditioned reaction system pH is 7.5, and the adding temperature is 0 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Embodiment 3,
1) at first polyoxypropyleneglycol is joined in the dry reactor, after heating the polyoxypropyleneglycol fusion that makes in the reactor, again tolylene diisocyanate is joined in the reactor and carry out polyreaction at 80 ℃, wherein tolylene diisocyanate is 3: 1 with the ratio of the amount of substance of polyoxypropyleneglycol, and the reaction times is 3h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 1h, and wherein 1, the 4-butyleneglycol is 0.7: 1 with the ratio of the amount of substance of polyoxypropyleneglycol;
3) add Xylitol and hydrophilic chain extender quadrol base ethyl sulfonic acid sodium again in the reactor at 65 ℃ of reaction 4h, wherein tolylene diisocyanate is 30: 1 with the ratio of the amount of substance of Xylitol, and tolylene diisocyanate is 3.9: 1 with the ratio of the amount of substance of quadrol base ethyl sulfonic acid sodium;
4) be cooled to 25 ℃, adding trolamine conditioned reaction system pH is 7.5, and the adding temperature is 40 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Embodiment 4,
1) at first PCDL is joined in the dry reactor, after heating the PCDL fusion that makes in the reactor, again diphenylmethanediisocyanate is joined in the reactor and carry out polyreaction at 85 ℃, wherein diphenylmethanediisocyanate is 2.7: 1 with the ratio of the amount of substance of PCDL, and the reaction times is 2.5h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 3h, and wherein 1, the 4-butyleneglycol is 0.45: 1 with the ratio of the amount of substance of PCDL;
3) in reactor, add sorbyl alcohol and hydrophilic chain extender 1 again, 4-butyleneglycol-2-sodium sulfonate is at 75 ℃ of reaction 2h, wherein diphenylmethanediisocyanate is 21: 1 with the ratio of the amount of substance of sorbyl alcohol, diphenylmethanediisocyanate and 1, the ratio of the amount of substance of 4-butyleneglycol-2-sodium sulfonate is 5: 1;
4) be cooled to 18 ℃, adding triethylamine conditioned reaction system pH is 7.8, and the adding temperature is 22 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Embodiment 5,
1) at first the poly adipate succinic acid ester dibasic alcohol is joined in the dry reactor, after heating the poly adipate succinic acid ester dibasic alcohol fusion that makes in the reactor, again isophorone diisocyanate is joined in the reactor and carry out polyreaction at 78 ℃, wherein isophorone diisocyanate is 3.2: 1 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol, and the reaction times is 4h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 4h, and wherein 1, the 4-butyleneglycol is 0.9: 1 with the ratio of the amount of substance of poly adipate succinic acid ester dibasic alcohol;
3) in reactor, add sucrose and hydrophilic chain extender 1 again, 2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium is at 80 ℃ of reaction 5h, wherein isophorone diisocyanate is 8: 1 with the ratio of the amount of substance of sucrose, isophorone diisocyanate and 1, the ratio of the amount of substance of 2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium is 3.7: 1;
4) be cooled to 35 ℃, adding Trimethylamine 99 and triethylamine conditioned reaction system pH is 8, and the adding temperature is 30 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
Claims (6)
1. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion is characterized in that:
1) at first polyglycol is joined in the dry reactor, after heating the polyglycol fusion that makes in the reactor, vulcabond is joined in the reactor and carry out polyreaction at 70-90 ℃, wherein vulcabond is 2-4 with the ratio of the amount of substance of polyglycol: 1, and the reaction times is 1-5h;
2) with chainextender 1, the 4-butyleneglycol adds reactor reaction 1-4h, and wherein 1, the 4-butyleneglycol is 0.3-1.2 with the ratio of the amount of substance of polyglycol: 1;
3) add natural polyhydroxy compound and hydrophilic chain extender again in the reactor at 60-80 ℃ of reaction 2-5h, wherein vulcabond is 8-35 with the ratio of the amount of substance of natural polyhydroxy compound: 1, and vulcabond is 2.5-5 with the ratio of the amount of substance of hydrophilic chain extender: 1;
4) be cooled to 15～35 ℃, adding organic bases conditioned reaction system pH is 7-8, and the adding temperature is 0～40 ℃ a deionized water under the high-speed stirring, has promptly obtained natural polyhydroxy compound modified aqueous polyurethane emulsion.
2. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion according to claim 1, it is characterized in that: described polyglycol is polyether Glycols or polyester diol, and polyether Glycols and polyester diol number average relative molecular mass are respectively 1000 or 2000, and polyether Glycols is polyoxypropyleneglycol or PTMG dibasic alcohol; Polyester diol is polycaprolactone dibasic alcohol, PCDL or poly adipate succinic acid ester dibasic alcohol.
3. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion according to claim 1, it is characterized in that: described vulcabond is isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate.
4. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion according to claim 1, it is characterized in that: described natural polyhydroxy compound is sucrose, glucose, Xylitol or sorbyl alcohol.
5. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion according to claim 1, it is characterized in that: described hydrophilic chain extender has sulfonate type and carboxylic acid type two classes, the sulfonate type chainextender is a quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate or 1,2-dihydroxyl-3-N-morpholinopropanesulfonic acid sodium; The carboxylic acid type chainextender is dimethylol propionic acid or dimethylolpropionic acid.
6. the preparation method of natural polyhydroxy compound modified aqueous polyurethane emulsion according to claim 1, it is characterized in that: described organic bases is Trimethylamine 99, triethylamine or trolamine.
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Cited By (15)
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| CN102392360A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Fabric coating slurry prepared by modified polyurethane |
| CN102391459A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for modified polyurethane |
| CN102432820A (en) * | 2011-08-25 | 2012-05-02 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing modified environment-friendly polyurethane |
| CN102604036A (en) * | 2012-03-09 | 2012-07-25 | 合肥工业大学 | Method for preparing glucose modified waterborne polyurethane emulsion |
| CN103265678A (en) * | 2013-05-30 | 2013-08-28 | 国家电网公司 | Preparation method of xylitol aroma type polyurethane |
| CN103980791A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Modified water-based organic silicon polyurethane-polyacrylate nano hybrid waterborne coating free from VOC (volatile organic compound) chitosan and preparation method thereof |
| CN104877540A (en) * | 2015-05-06 | 2015-09-02 | 广德加点化工有限公司 | Impact-resistant and tear-resistant water-based paint |
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| CN105367734A (en) * | 2015-11-19 | 2016-03-02 | 太仓市金锚化工有限公司 | High-adhesion aqueous polyurethane adhesive preparation method |
| CN106700016A (en) * | 2016-11-28 | 2017-05-24 | 中国科学院长春应用化学研究所 | Cationic waterborne polyurethane resin, preparation method of cationic waterborne polyurethane resin and waterborne polyurethane adhesive |
| CN106928427A (en) * | 2017-03-03 | 2017-07-07 | 中国科学院长春应用化学研究所 | Carbon dioxide-base cation aqueous polyurethane resin and its preparation method and application |
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| CN102392360A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Fabric coating slurry prepared by modified polyurethane |
| CN102391459A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for modified polyurethane |
| CN102432820A (en) * | 2011-08-25 | 2012-05-02 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing modified environment-friendly polyurethane |
| CN102604036A (en) * | 2012-03-09 | 2012-07-25 | 合肥工业大学 | Method for preparing glucose modified waterborne polyurethane emulsion |
| CN102604036B (en) * | 2012-03-09 | 2013-11-27 | 合肥工业大学 | Method for preparing glucose modified waterborne polyurethane emulsion |
| CN103265678A (en) * | 2013-05-30 | 2013-08-28 | 国家电网公司 | Preparation method of xylitol aroma type polyurethane |
| CN103265678B (en) * | 2013-05-30 | 2016-03-09 | 国家电网公司 | A kind of preparation method of Xylitol aromatic polyurethane |
| CN103980791A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Modified water-based organic silicon polyurethane-polyacrylate nano hybrid waterborne coating free from VOC (volatile organic compound) chitosan and preparation method thereof |
| CN104877534A (en) * | 2015-05-06 | 2015-09-02 | 广德加点化工有限公司 | Waterproof and high-strength water-based paint |
| CN104877540A (en) * | 2015-05-06 | 2015-09-02 | 广德加点化工有限公司 | Impact-resistant and tear-resistant water-based paint |
| CN105367734A (en) * | 2015-11-19 | 2016-03-02 | 太仓市金锚化工有限公司 | High-adhesion aqueous polyurethane adhesive preparation method |
| CN106700016A (en) * | 2016-11-28 | 2017-05-24 | 中国科学院长春应用化学研究所 | Cationic waterborne polyurethane resin, preparation method of cationic waterborne polyurethane resin and waterborne polyurethane adhesive |
| CN106928427A (en) * | 2017-03-03 | 2017-07-07 | 中国科学院长春应用化学研究所 | Carbon dioxide-base cation aqueous polyurethane resin and its preparation method and application |
| CN108003779A (en) * | 2017-12-19 | 2018-05-08 | 江南大学 | A kind of bio-based materials are modified the preparation method of UV solidfication water polyurethane resins |
| CN112341592A (en) * | 2020-09-22 | 2021-02-09 | 长春工业大学 | Preparation method of glucose and sulfonate modified degradable waterborne polyurethane |
| CN112574655A (en) * | 2020-11-28 | 2021-03-30 | 安徽实力环保科技有限公司 | Preparation method of surface coating for glass fiber reinforced plastics with anti-ultraviolet effect |
| CN112574655B (en) * | 2020-11-28 | 2021-12-31 | 安徽实力环保科技有限公司 | Preparation method of surface coating for glass fiber reinforced plastics with anti-ultraviolet effect |
| CN113817132A (en) * | 2020-12-07 | 2021-12-21 | 汉中聚智达远环能科技有限公司 | Preparation method of environment-friendly amine-free special fluorescent polyurethane emulsion protective agent |
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