Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof

A water-based polyurethane and acrylate technology, which is applied in the field of water-based polyurethane materials, can solve problems such as difficult control of crosslinking equivalent, unstable emulsion, and insignificant improvement in tolerance, and achieve stable production process without abnormalities, stable and controllable prepolymerization reaction, The effect of improving physical and mechanical properties

Active Publication Date: 2020-04-03
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, the patent document CN101481451B discloses a high solid content, latently cured polyurethane acrylate hybrid emulsion, which adopts a post-crosslinking method to improve various resistances; when the post-crosslinking equivalent is too high, the emulsion is unstable, and the post-crosslinking When the equivalent is insufficient, the improvement of the resistance is not obvious, and the cross-linking equivalent is not easy to control
Patent document CN101157749A discloses a polyurethane-modified acrylic emulsion, which is prepared by introducing carbonyl groups into the polyurethane part and the acrylate part respectively, and adding self-made hydrazide to the emulsion for cross-linking, which solves the problem of polyurethane-acrylate hybrid emulsion. There is no problem of chemical cross-linking with polyacrylate, which increases a certain resistance; but the cross-linking method does not increase the resistance significantly, and the added self-made hydrazide has certain toxicity, which limits the application of the product
Patent document CN101544739A discloses a polyurethane-acrylate hybrid copolymer emulsion with a special structure, which is inserted into the polyurethane segment through a self-made monomer with a double bond in the side chain, and then copolymerized with the acrylate monomer It is prepared so that the polyurethane part and the polyacrylate part in the chain segment can achieve phase separation, so that the respective performances are maximized; however, the self-made monomer contains 4 functional groups that can react with isoaminoester, and the prepolymerization process cannot be controlled, which is extremely difficult. Easy to gel, the production process is unsafe, and the cost is high, it is extremely difficult to promote
Patent document CN108219106A discloses the preparation of a water-based polyurethane-acrylate hybrid copolymer modified by self-made soybean oil alcoholyzate, and the performance is improved by adding homemade soybean oil alcoholyzate, but because the prepared large The fatty acid chain of soybean oil alcoholyzate contains unsaturated double bonds. At the same time, the long fatty chain and the acrylate monomer will wrap part of the monomer. The encapsulation prevents some of the internal monomers from being polymerized, resulting in a high amount of residual monomers in the emulsion after multiple polymerizations. During the post-removal process of acetone, the residual acrylate monomers will undergo polymerization reactions, which will cause blockage of the acetone removal device, and the emulsion will be stored poor stability

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  • Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0084] Add 80g WANNATE HMDI, 40g hydrogenated castor oil (iodine value 10-15), 40g PCL220N, and 0.05g organic bismuth catalyst, 24g acetone into a four-neck flask equipped with a thermometer, reflux condenser, and stirrer, heat up to 85°C and keep it warm for reaction , when the NCO value is constant at 10.36%, lower the temperature to 55°C, add 8g of dimethylolpropionic acid, 10g of 1,4-butanediol and 23g of acetone, and react at 75-80°C for 3-4 hours until the NCO value is constant to 2.72wt%, lower the temperature to 50°C, add 76g of acetone, 153.73g of methyl methacrylate, and 6.04g of triethylamine, and stir for 10 minutes until uniform. After cooling down to room temperature, add 450 g of water at a shear rate of 1300 rpm, emulsify and disperse for 10 min, add 14.17 g of tris(4-aminophenyl)amine to the dispersed emulsion, dilute it with 4 times water, and stir for 5 min. Add 1.92g of 4,4-diaminodicyclohexylmethane, dilute it with 4 times of water and add it, and stir for...

Embodiment 2

[0087] Add 80g WANNATEHMDI, 20g hydrogenated castor oil (iodine value 10-15), 60gPCL220N, and 0.18g organic bismuth catalyst, 24g acetone to a four-neck flask equipped with a thermometer, reflux condenser, and stirrer, heat up to 85°C and keep warm for reaction After the NCO value is constant at 11.23wt%, cool down to 55°C, add 10g of dimethylol propionic acid, 12g of 1,4-butanediol and 20g of acetone, and react at 75-80°C for 3-4 hours to reach the NCO value Constant at 2.16wt%, lower the temperature to 40°C, add 77g of acetone, 154.65g of methyl methacrylate, 7.55g of triethylamine, and stir for 10 minutes until uniform. After cooling down to room temperature, add 451g of water at a shear rate of 1300rpm, emulsify and disperse for 10min, add 11.31g of tris(4-aminophenyl)amine to the dispersed emulsion, dilute with 4 times of water, add, and stir for 5min. Add 3.87g of 4,4-diaminodicyclohexylmethane, dilute it with 4 times of water and add it, and stir for 8 minutes.

[0088] ...

Embodiment 3

[0090] Add 80g WANNATE HMDI, 60g hydrogenated castor oil (iodine value 10-15), 20g PNA2000, and 0.18g organic bismuth catalyst, 24g acetone to the four-neck flask equipped with thermometer, reflux condenser and stirrer, heat up to 85°C and keep warm for reaction , when the NCO value is constant at 9.49wt%, cool down to 55°C, add 8g of dimethylolpropionic acid, 7g of 1,4-butanediol and 26.3g of acetone, and react at 75-80°C for 3-4h to NCO The value is constant at 3.07wt%. Cool down to 50°C, add 79g of acetone, 152.77g of methyl methacrylate, and 6.04g of triethylamine, and stir for 10 minutes until uniform. After cooling down to room temperature, add 451g of water at a shear rate of 1300rpm, emulsify and disperse for 10min, add 15.96g of tris(4-aminophenyl)amine to the dispersed emulsion, dilute it with 4 times of water, add it, and stir for 5min. Add 7.64g of 4,4-diaminodicyclohexylmethane, dilute it with 4 times of water and add it, and stir for 8min.

[0091] Add the emuls...

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Abstract

The invention provides a waterborne polyurethane-acrylate hybrid copolymer and a preparation method thereof. The copolymer prepared by the invention is subjected to cross-linking modification throughhydrogenated castor oil and amine containing a rigid structure and the low-molecular organic amine containing a cyclic structure is used, so that in the polymerization process, the number of initiation times is small, the residual monomer amount after polymerization is low, the production process is stable and free of abnormality, the emulsion stability is good, and finally the waterborne polyurethane-acrylate hybrid copolymer with excellent comprehensive properties such as hardness and wear resistance is obtained.

Description

technical field [0001] The invention belongs to the technical field of waterborne polyurethane materials, and in particular relates to a waterborne polyurethane-acrylate hybrid copolymer and a preparation method thereof. Background technique [0002] With the improvement of people's awareness of environmental protection and the country's restrictions on volatile organic compounds (VOC) emissions, traditional solvent-based polyurethane coatings are gradually abandoned by the market during the application process, and the development of low-pollution and environmentally friendly water-based polyurethane materials has become everyone's consensus. . Water-based polyurethane coatings use water instead of organic solvents as the dispersion medium, which has good environmental protection value. In many fields, it has gradually replaced traditional solvent-based polyurethane coatings. [0003] In order to obtain low-cost, high-performance water-based polyurethane products, various...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/75C08G18/66C08G18/42C08G18/36C08G18/34C08G18/32C08F283/00C08F220/14
CPCC08G18/758C08G18/755C08G18/6662C08G18/6659C08G18/664C08G18/6651C08G18/4277C08G18/36C08G18/4238C08F283/008C08F220/14
Inventor 王震朱文辉周操胡海东邢庆达刘云玲晋云全尹逊迪纪学顺
Owner WANHUA CHEM GRP CO LTD
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