CN101717486B - Degradable aqueous polyurethane dispersion and preparation method thereof - Google Patents
Degradable aqueous polyurethane dispersion and preparation method thereof Download PDFInfo
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- CN101717486B CN101717486B CN 200910199893 CN200910199893A CN101717486B CN 101717486 B CN101717486 B CN 101717486B CN 200910199893 CN200910199893 CN 200910199893 CN 200910199893 A CN200910199893 A CN 200910199893A CN 101717486 B CN101717486 B CN 101717486B
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Abstract
The invention relates to degradable aqueous polyurethane dispersion and a preparation method thereof. The dispersion comprises the following components in part by weight: 10 to 30 parts of polyol, 15 to 25 parts of diisocyanate, 3 to 8 parts of hydrophilic chain-extender, 1 to 3 parts of collagen, 3 to 5 parts of neutralizer, 45 to 55 parts of acetone, and 140 to 180 parts of deionized water. The method comprises the following steps: dehydrating the polyol under reduced pressure; adding the diisocyanate, the hydrophilic chain-extender, the collagen and the acetone into the polyol; reacting the mixture until the isocyano amount reaches a theoretical value; adding the neutralizer and the deionized water into the solution after the solution is cooled; and distilling the product to obtain the degradable aqueous polyurethane dispersion. Compared with the prior art, the degradable aqueous polyurethane dispersion has the advantages of reasonable synthesis route, simple operation, high product stability, high water resistance, good degradability and sanitary performance, and can be used for package paint of foods, medicaments, cigarettes and other products.
Description
Technical field
The present invention relates to a kind of polyurethane aqueous dispersion body and preparation method thereof, especially relate to a kind of degradable aqueous polyurethane dispersion and preparation method thereof.
Background technology
During polyurethane material is widely used in producing, lives with advantages such as its excellent mechanical strength, snappiness, wear resistance, biocompatibilities.The development of aqueous polyurethane has solved design safety and healthy problem that solvent application is brought, but the offal treatment problem of the application products of large weight polyurethane becomes increasingly conspicuous.Thereby degradation material is complied with environmental requirement, must be the important directions of future development.
Summary of the invention
Purpose of the present invention is exactly that a kind of eco-friendly, degradable, degradable aqueous polyurethane dispersion that safety performance is good and preparation method thereof is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of degradable aqueous polyurethane dispersion is characterized in that, this dispersion comprises following component and weight part content:
Polymer polyatomic alcohol 10-30;
Vulcabond 15-25;
Hydrophilic chain extender 3-8;
Collagen protein 1-3;
Neutralizing agent 3-5;
Acetone 45-55;
Deionized water 140-180.
Described polymer polyatomic alcohol comprises one or more in polycarbonate diol, polytetramethylene ether diol, polycaprolactone, Viscotrol C or the soybean oil.
Described vulcabond comprises one or more in '-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate.
Described hydrophilic chain extender comprises one or more of dimethylol propionic acid, dimethylolpropionic acid or second diamino ethyl sulfonic acid sodium.
Described collagen protein comprises animal raw hide or bombyx mori silk fibroin.
Described neutralizing agent comprises triethylamine, tri-n-butylamine, potassium hydroxide or N methyldiethanol amine.
A kind of preparation method of degradable aqueous polyurethane dispersion is characterized in that, the method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Polymer polyatomic alcohol 10-30,
Vulcabond 15-25,
Hydrophilic chain extender 3-8,
Collagen protein 1-3,
Neutralizing agent 3-5,
Acetone 45-55,
Deionized water 140-180;
(2) with polymer polyatomic alcohol at 110-130 ℃ of lower decompression dehydration 1-2h, then be cooled to 60-70 ℃, add vulcabond and be warming up to again 80-100 ℃, react to the isocyano amount of solution and reach theoretical value;
(3) product that obtains to step (2) adds hydrophilic chain extender, reacts to solution isocyano amount and reaches theoretical value;
(4) product that obtains to step (3) adds collagen protein and acetone, reacts under the acetone reflux temperature to the isocyano amount of solution and reaches theoretical value;
(5) product that step (4) is obtained is cooled to 25-40 ℃, adds neutralizing agent, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 1500-3000rpm, dispersed with stirring 0.5-1h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
The theoretical value of described solution isocyano amount is 1-7% (wt%).
The reflux temperature of described acetone is 50-56 ℃.
Compared with prior art, synthetic route of the present invention is reasonable, simple to operate, the product stability that obtains is high, water tolerance is strong, add collagen protein and biological multielement alcohol composition, degradability and the sanitation performance of product have been improved, keep simultaneously the original performance of product not reduce, this product can be used for the package coating of the products such as food, medicine, cigarette.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of degradable aqueous polyurethane dispersion is characterized in that, the method may further comprise the steps:
(1) gets the raw materials ready according to following component and weight part content: 11kg polycaprolactone glycol (molecular weight 2000), 2.5kg soybean oil, 22kg isophorone diisocyanate, 6kg hydrophilic chain extender dimethylol propionic acid, 2kg collagen protein, 4.4kg neutralizing agent triethylamine, 45kg acetone, 150kg deionized water;
(2) with after polycaprolactone glycol and the soybean oil mixing, at 120 ℃ of lower decompression dehydration 1.5h, then be cooled to 60 ℃, add isophorone diisocyanate and be warming up to 90 ℃ again, isocyano (NCO) amount of reacting to solution reaches 6% (wt%);
(3) product that obtains to step (2) adds the hydrophilic chain extender dimethylol propionic acid, reacts to solution isocyano (NCO) amount and reaches 4% (wt%);
(4) product that obtains to step (3) adds collagen protein and acetone, and isocyano (NCO) amount of reacting to solution under 50 ℃ of acetone reflux temperatures reaches 3% (wt%);
(5) product that step (4) is obtained is cooled to 40 ℃, adds the neutralizing agent triethylamine, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 2500rpm, dispersed with stirring 0.5h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
Embodiment 2
A kind of preparation method of degradable aqueous polyurethane dispersion is characterized in that, the method may further comprise the steps:
(1) gets the raw materials ready according to following component and weight part content: 5.5kg polycarbonate diol (molecular weight 1000), 5kg Viscotrol C, 20kg isophorone diisocyanate, 5kg hydrophilic chain extender dimethylol propionic acid, 1kg collagen protein, 3.5kg neutralizing agent triethylamine, 50kg acetone, 140kg deionized water;
(2) polycarbonate diol and Viscotrol C are mixed after, at 120 ℃ of lower decompression dehydration 1.5h, then be cooled to 60 ℃, add isophorone diisocyanate and be warming up to again 90 ℃, react to the NCO amount of solution and reach 7% (wt%);
(3) product that obtains to step (2) adds the hydrophilic chain extender dimethylol propionic acid, reacts to the NCO amount of solution and reaches 6% (wt%);
(4) product that obtains to step (3) adds collagen protein and acetone, reacts under 54 ℃ of acetone reflux temperatures to the NCO amount of solution and reaches 5% (wt%);
(5) product that step (4) is obtained is cooled to 35 ℃, adds the neutralizing agent triethylamine, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 2200rpm, dispersed with stirring 0.5h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
Embodiment 3
(1) gets the raw materials ready according to following component and weight part content: 15kg polycaprolactone glycol (molecular weight 2000), 8kg polycarbonate diol (molecular weight 1000), 18kg tolylene diisocyanate, 6.5kg hydrophilic chain extender dimethylolpropionic acid, 1.5kg collagen protein, 4.0kg neutralizing agent methyldiethanolamine, 48kg acetone, 175kg deionized water;
(2) polycaprolactone glycol and polycarbonate diol are mixed after, at 120 ℃ of lower decompression dehydration 1.5h, then be cooled to 60 ℃, add tolylene diisocyanate and be warming up to again 80 ℃, react to the NCO amount of solution and reach 4% (wt%);
(3) product that obtains to step (2) adds the hydrophilic chain extender dimethylolpropionic acid, reacts to the NCO amount of solution and reaches 2% (wt%);
(4) product that obtains to step (3) adds collagen protein and acetone, reacts under 56 ℃ of acetone reflux temperatures to the NCO amount of solution and reaches 1% (wt%);
(5) product that step (4) is obtained is cooled to 25 ℃, adds the neutralizing agent methyldiethanolamine, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 2000rpm, dispersed with stirring 0.5h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
Embodiment 4
(1) gets the raw materials ready according to following component and weight part content: 10kg polycaprolactone glycol (molecular weight 1000), 15kg tolylene diisocyanate, 3kg hydrophilic chain extender second diamino ethyl sulfonic acid sodium, 1kg collagen protein bombyx mori silk fibroin, 3kg neutralizing agent methyldiethanolamine, 45kg acetone, 140kg deionized water;
(2) with polycaprolactone glycol at 110 ℃ of lower decompression dehydration 1h, then be cooled to 70 ℃, add tolylene diisocyanate and be warming up to again 100 ℃, react to the NCO amount of solution and reach 5% (wt%);
(3) product that obtains to step (2) adds hydrophilic chain extender second diamino ethyl sulfonic acid sodium, reacts to the NCO amount of solution and reaches 4% (wt%);
(4) product that obtains to step (3) adds collagen protein bombyx mori silk fibroin and acetone, reacts under 56 ℃ of acetone reflux temperatures to the NCO amount of solution and reaches 2% (wt%);
(5) product that step (4) is obtained is cooled to 35 ℃, adds the neutralizing agent methyldiethanolamine, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 1500rpm, dispersed with stirring 1h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
Embodiment 5
(1) gets the raw materials ready according to following component and weight part content: 10kg polycaprolactone glycol (molecular weight 1000), 20kg polytetramethylene ether diol, 25kg hexamethylene diisocyanate, 8kg hydrophilic chain extender second diamino ethyl sulfonic acid sodium, 3kg collagen protein bombyx mori silk fibroin, 5kg neutralizing agent tri-n-butylamine, 55kg acetone, 180kg deionized water;
(2) polycaprolactone glycol and polytetramethylene ether diol are mixed, at 130 ℃ of lower decompression dehydration 2h, then be cooled to 65 ℃, add hexamethylene diisocyanate and be warming up to again 80 ℃, react to the NCO amount of solution and reach 7% (wt%);
(3) product that obtains to step (2) adds hydrophilic chain extender second diamino ethyl sulfonic acid sodium, reacts to the NCO amount of solution and reaches 5% (wt%);
(4) product that obtains to step (3) adds collagen protein bombyx mori silk fibroin and acetone, under 54 ℃ of acetone reflux temperatures, react to solution the NCO amount reach 3% (wt%);
(5) product that step (4) is obtained is cooled to 40 ℃, adds the neutralizing agent tri-n-butylamine, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 3000rpm, dispersed with stirring 0.5h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
Claims (6)
1. a degradable aqueous polyurethane dispersion is characterized in that, this dispersion comprises following component and weight part content:
Polymer polyatomic alcohol 10-30;
Vulcabond 15-25;
Hydrophilic chain extender 3-8;
Collagen protein 1-3;
Neutralizing agent 3-5;
Acetone 45-55;
Deionized water 140-180;
Described collagen protein comprises animal raw hide or bombyx mori silk fibroin; Described polymer polyatomic alcohol comprises one or more in polycarbonate diol, polytetramethylene ether diol or the polycaprolactone.
2. a kind of degradable aqueous polyurethane dispersion according to claim 1, it is characterized in that, described vulcabond comprises one or more in '-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate or the hexamethylene diisocyanate.
3. a kind of degradable aqueous polyurethane dispersion according to claim 1 is characterized in that, described hydrophilic chain extender comprises one or more of dimethylol propionic acid, dimethylolpropionic acid or quadrol base ethyl sulfonic acid sodium.
4. a kind of degradable aqueous polyurethane dispersion according to claim 1 is characterized in that, described neutralizing agent comprises triethylamine, tri-n-butylamine, potassium hydroxide or N methyldiethanol amine.
5. the preparation method of a degradable aqueous polyurethane dispersion is characterized in that, the method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Polymer polyatomic alcohol 10-30,
Vulcabond 15-25,
Hydrophilic chain extender 3-8,
Collagen protein 1-3,
Neutralizing agent 3-5,
Acetone 45-55,
Deionized water 140-180,
Described collagen protein comprises animal raw hide or bombyx mori silk fibroin; Described polymer polyatomic alcohol comprises one or more in polycarbonate diol, polytetramethylene ether diol or the polycaprolactone;
(2) with polymer polyatomic alcohol at 110-130 ℃ of lower decompression dehydration 1-2h, then be cooled to 60-70 ℃, add vulcabond and be warming up to again 80-100 ℃, react to the isocyano amount of solution and reach theoretical value 1-7wt%;
(3) product that obtains to step (2) adds hydrophilic chain extender, reacts to solution isocyano amount and reaches theoretical value 1-7wt%;
(4) product that obtains to step (3) adds collagen protein and acetone, reacts under the acetone reflux temperature to the isocyano amount of solution and reaches theoretical value 1-7wt%;
(5) product that step (4) is obtained is cooled to 25-40 ℃, adds neutralizing agent, continues reaction 0.5h;
(6) add deionized water in the product that obtains to step (5), the control stirring velocity is 1500-3000rpm, dispersed with stirring 0.5-1h;
(7) product that step (6) is obtained distills, and reclaims acetone wherein, namely obtains the degradable polyurethane water dispersion.
6. the preparation method of a kind of degradable aqueous polyurethane dispersion according to claim 5 is characterized in that, the reflux temperature of described acetone is 50-56 ℃.
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| CN 200910199893 CN101717486B (en) | 2009-12-03 | 2009-12-03 | Degradable aqueous polyurethane dispersion and preparation method thereof |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329555A (en) * | 2011-07-27 | 2012-01-25 | 吴江市瑞丰织造有限公司 | Micro-bubble elastic polyurethane waterproof coating |
| CN102633975A (en) * | 2012-04-10 | 2012-08-15 | 嘉兴市罗星化工有限公司 | Epoxidized soybean oil based modified waterborne polyurethane gloss oil and preparation method thereof |
| CN103254390B (en) * | 2013-05-06 | 2015-04-22 | 陕西科技大学 | Preparation method of collagen fiber based polyurethane composite material |
| CN105732926A (en) * | 2016-03-09 | 2016-07-06 | 陕西科技大学 | Cationic-type skin collagen/waterborne polyurethane composite leather tanning agent and preparation method thereof |
| CN106188457A (en) * | 2016-07-14 | 2016-12-07 | 武汉理工大学 | Cross-linking type castor oil-base aqueous polyurethane emulsion and preparation method thereof in a kind of |
| CN106753159B (en) * | 2016-11-16 | 2020-02-07 | 四川大学 | Degradable collagen-polyurethane water-based wood adhesive and preparation method thereof |
| CN108531067B (en) * | 2018-05-17 | 2020-06-30 | 安徽朗凯奇防水科技股份有限公司 | Polylactic acid embedded polyurethane environment-friendly waterproof coating and preparation process thereof |
| CN113121785A (en) * | 2019-12-31 | 2021-07-16 | 广州麦吉高分子新材料科技有限公司 | Preparation method of degradable aqueous high-molecular polymer |
| CN115558073A (en) * | 2022-01-19 | 2023-01-03 | 广东新辉化学有限公司 | Hyperbranched degradable polyurethane material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327195A (en) * | 1980-09-29 | 1982-04-27 | Seton Company | Polyurethane containing polypeptides |
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2009
- 2009-12-03 CN CN 200910199893 patent/CN101717486B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327195A (en) * | 1980-09-29 | 1982-04-27 | Seton Company | Polyurethane containing polypeptides |
Non-Patent Citations (3)
| Title |
|---|
| 刘堃."胶原蛋白改性聚氨酯皮革涂饰剂的研制".《中国优秀博硕士论文全文数据库（硕士） 工程科技I辑》.2006,(第11期),16-53. |
| 刘堃."胶原蛋白改性聚氨酯皮革涂饰剂的研制".《中国优秀博硕士论文全文数据库(硕士) 工程科技I辑》.2006,(第11期),16-53. * |
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