CN112625207A - High-transparency anionic aqueous polyurethane dispersion and preparation method thereof - Google Patents
High-transparency anionic aqueous polyurethane dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-transparency anionic aqueous polyurethane dispersion and a preparation method thereof; the preparation method comprises the following steps: a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product; b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion. Compared with the prior art, the preparation method provided by the invention adopts a specific process, has good production controllability and high stability, has good product state and performance parameter parallelism of each production batch, and is suitable for industrial application; and the prepared product has high transparency, can meet the requirements of leather processing technology, and is suitable for coating and releasing PVC, PU, PET and other substrates.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to a high-transparency anionic waterborne polyurethane dispersion and a preparation method thereof.
Background
The waterborne polyurethane is a high molecular material formed by dispersing a polyurethane prepolymer in water under high-speed stirring. According to different polyurethane prepolymer compositions and structures, the performances of the waterborne polyurethane are different, so that different application ranges of the waterborne polyurethane, such as coating agents, coatings, adhesives and other functional applications, are directly determined.
Along with the improvement of the living standard of residents in China, the use requirement of people on leather is higher and higher in recent years. The characteristics of scratch resistance, friction resistance, smooth hand feeling, strong water resistance, strong tensile strength and the like are all excellent characteristics which are directly presented in the using process of the leather at present and in a period of time in the future, and thus higher requirements are provided for the processing technology of the leather. From the viewpoint of the leather finishing process, the selection of the leather finishing agent will affect the use performance of the leather. The waterborne polyurethane for coating the surface layer of the leather not only has excellent film-forming property, but also meets the requirement of a leather processing technology to achieve the requirement of improving the performance of the leather.
In contrast, the research on the waterborne polyurethane is relatively late in China, and a certain research and application gap exists. In recent years, technicians of a plurality of scientific research institutions make continuous efforts on research on the waterborne polyurethane, obtain various results, and market popularization and application of the research results are carried out. However, compared with some developed countries, the production and application of waterborne polyurethane in China still have many problems, and whether the appearance state and the application performance of the waterborne polyurethane product are unified and whether the products in different batches are stable in the supply process are the key to the normal popularization of the technology.
Disclosure of Invention
In view of the above, the invention aims to provide a high-transparency anionic aqueous polyurethane dispersion and a preparation method thereof, the preparation method provided by the invention has the advantages of good controllability and high stability in production, is suitable for industrial application, can obtain a product with high transparency, can meet the requirements of leather processing technology, and is suitable for coating and releasing PVC, PU, PET and other substrates.
The invention provides a preparation method of a high-transparency anionic aqueous polyurethane dispersion, which comprises the following steps:
a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product;
b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion.
Preferably, the polymer polyol in step a) is selected from polyester polyols and/or polyether polyols;
the isocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
Preferably, the dehydration temperature in the step a) is 100-130 ℃, the pressure is-0.09 MPa-0.1 MPa, and the time is 45-120 min.
Preferably, the prepolymerization process in the step a) is specifically as follows:
and (3) cooling the dehydrated polymer polyol to below 90 ℃, adding isocyanate, and reacting for 1-3 h at 60-90 ℃.
Preferably, the pre-chain extension process in step a) specifically comprises:
after the prepolymerization is judged to be finished according to the NCO detection result, adding a micromolecule polyol chain extender and a catalyst, and reacting for 2-6 h at 50-90 ℃ until the NCO is qualified;
the small-molecular polyol chain extender comprises 2, 2-dimethylolpropionic acid.
Preferably, the post-chain extension process in step a) specifically comprises:
cooling a product obtained by chain extension to below 60 ℃, adding a solvent for dilution, and slowly dropwise adding a micromolecule polyamine chain extender at the temperature of between 20 and 50 ℃;
the small molecular polyamine chain extender is selected from one or more of ethylenediamine, diethylenetriamine and hexamethylenediamine.
Preferably, the neutralizing agent used in the neutralization in step a) is triethylamine; the temperature of neutralization is 10-50 ℃, and the time is 5-10 min.
Preferably, the organosilicon modifier in step b) is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane.
Preferably, the emulsification process after adding the organosilicon modifier into the reaction product obtained in the step a) in the step b) is specifically as follows:
and c) slowly dripping the aqueous solution of the organic silicon modifier into the reaction product obtained in the step a) under the stirring of 500 r/min-5000 r/min, and immediately adding water for emulsification for 5 min-20 min to finish the emulsification process.
The invention also provides a high-transparency anionic aqueous polyurethane dispersion prepared by the preparation method of the technical scheme.
The invention provides a high-transparency anionic aqueous polyurethane dispersion and a preparation method thereof; the preparation method comprises the following steps: a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product; b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion. Compared with the prior art, the preparation method provided by the invention adopts a specific process, has good production controllability and high stability, has good product state and performance parameter parallelism of each production batch, and is suitable for industrial application; and the prepared product has high transparency, can meet the requirements of leather processing technology, and is suitable for coating and releasing PVC, PU, PET and other substrates. Experimental results show that the product obtained by the preparation method provided by the invention has the advantages of light transmittance of more than 92%, good film forming mechanical property, tensile strength of more than 18MPa and tensile rate of more than 500, can meet the requirements of leather processing technology, and is suitable for coating and releasing of substrates such as PVC, PU, PET and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a high-transparency anionic aqueous polyurethane dispersion, which comprises the following steps:
a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product;
b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion.
The method comprises the steps of dehydrating polymer polyol, carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product. In the present invention, the polymer polyol is preferably selected from polyester polyols and/or polyether polyols; the polyester polyol preferably comprises adipic acid polyester polyol, succinic acid polyester polyol, glutaric acid polyester polyol, sebacic acid polyester polyol and corresponding mixed dibasic acid polyester polybasic acid, and can also be unsaturated dibasic acid polyester polyol; the polyether polyol preferably includes polyoxypropylene polyol, polytetrahydrofuran and its copolymerized polyether polyol, and polyoxyethylene polyol. In a preferred embodiment of the invention, the polymer polyol is selected from adipic acid based polyester diol, or polytetrahydrofuran ether, or a mixture of glutaric acid based polyester diol and polyethylene glycol (mass ratio of 19: 6), or a mixture of polypropylene glycol, polyethylene glycol and adipic acid-neopentyl glycol polymer (mass ratio of 10: 3: 17). The source of the polymer polyol in the present invention is not particularly limited, and commercially available products or self-products known to those skilled in the art may be used.
In the present invention, the isocyanate is preferably selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, more preferably one or two of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, and more preferably one or two of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and diphenylmethane diisocyanate. The source of the isocyanate is not particularly limited in the present invention, and commercially available ones well known to those skilled in the art may be used.
In the present invention, the mass ratio of the polymer polyol to the isocyanate is preferably 1: (0.4 to 1).
In the present invention, the dehydration process is preferably carried out in a reaction kettle; the dehydration temperature is preferably 100-130 ℃, and more preferably 105-130 ℃; the pressure of the dehydration is preferably-0.09 MPa to-0.1 MPa, and more preferably-0.092 MPa to-0.098 MPa; the time for dehydration is preferably 45min to 120 min.
In the present invention, the prepolymerization process is preferably embodied as follows:
cooling the dehydrated polymer polyol to below 90 ℃, adding isocyanate, and reacting for 1-3 h at 60-90 ℃;
more preferably:
the dehydrated polymer polyol is cooled to 75-90 ℃, and isocyanate is added to react for 1.5-3 h at 65-85 ℃.
In the present invention, the pre-chain extension process preferably includes:
after the prepolymerization is judged to be finished according to the NCO detection result, adding a micromolecule polyol chain extender and a catalyst, and reacting for 2-6 h at 50-90 ℃ until the NCO is qualified;
more preferably:
and (3) after the prepolymerization is judged to be finished according to the NCO detection result, adding a micromolecule polyol chain extender and a catalyst, and reacting for 3-5 h at the temperature of 50-80 ℃ until the NCO is qualified.
In the present invention, the small molecule polyol chain extender preferably includes 2, 2-dimethylolpropionic acid; on the basis, one or more of 1, 3-propylene glycol, ethylene glycol, diethylene glycol, trimethylolpropane or 1, 6-hexanediol can be added. In the present invention, the addition amount of the small molecule polyol chain extender is preferably 5 to 15% of the mass of the polymer polyol.
In the present invention, the catalyst is one or more selected from the group consisting of a fatty amine catalyst, an organotin catalyst and an organobismuth catalyst, and more preferably a fatty amine catalyst, an organotin catalyst or an organobismuth catalyst. The source of the catalyst in the present invention is not particularly limited, and commercially available products of the above aliphatic amine-based catalyst, organotin-based catalyst and organobismuth-based catalyst known to those skilled in the art may be used. In the present invention, the amount of the catalyst added is preferably 1 to 3 drops, more preferably 2 drops; the present invention is not particularly limited in this regard.
In the present invention, the post-chain extension process preferably specifically comprises:
cooling a product obtained by chain extension to below 60 ℃, adding a solvent for dilution, and slowly dropwise adding a micromolecule polyamine chain extender at the temperature of between 20 and 50 ℃;
more preferably:
and cooling the product obtained by chain extension to 55 ℃, adding a solvent for dilution, and slowly dripping the micromolecule polyamine chain extender at the temperature of 30-45 ℃. In the present invention, the solvent is preferably acetone; the amount of the solvent to be added is preferably 2 to 4 times the mass of the polymer polyol.
In the invention, the small molecule polyamine chain extender is preferably selected from one or more of ethylenediamine, diethylenetriamine and hexamethylenediamine, and more preferably from one or two of ethylenediamine, diethylenetriamine and hexamethylenediamine. In the invention, the small molecule polyamine chain extender is firstly mixed with water in the dropping process, so that the dropping process is convenient to carry out, and the invention has no special limitation. In the present invention, the amount of the small-molecule polyamine chain extender added is preferably 1 to 10% by mass of the polymer polyol.
In the present invention, the neutralizing agent used for the neutralization is preferably triethylamine; the temperature of the neutralization is preferably 10-50 ℃, and more preferably 15-40 ℃; the neutralization time is preferably 5 to 10min, more preferably 5 to 8 min.
After the reaction product is obtained, adding an organic silicon modifier into the obtained reaction product, emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersoid. In the present invention, the silicone modifier is preferably selected from one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane and 3-diethylenetriaminopropyltrimethoxysilane, more preferably N- (N-butyl) -3-aminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, 3-diethylenetriaminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-methyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-methyldimeth, One or two of gamma-aminopropyltriethoxysilane and N-cyclohexyl-3-aminopropylmethyldimethoxysilane. The source of the silicone modifier is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the silicone modifier is preferably added to the reaction product in the form of an aqueous solvent; the mass concentration of the silicone modifier in the aqueous solvent is preferably 1% to 10%, more preferably 5%.
The invention realizes modification through an organic silicon mosaic mode after the aqueous polyurethane macromolecular polymer is formed. In the present invention, the emulsification process after adding the silicone modifier to the obtained reaction product is preferably specifically:
under the stirring of 500 r/min-5000 r/min, controlling the temperature to be 0-50 ℃, slowly dripping the aqueous solution of the organic silicon modifier into the reaction product obtained in the step a), and immediately adding water to emulsify for 5-20 min to finish the emulsification process;
more preferably:
and c), under the stirring of 600 r/min-1000 r/min, controlling the temperature to be 15-25 ℃, slowly dripping the aqueous solution of the organic silicon modifier into the reaction product obtained in the step a), and immediately adding water to emulsify for 8-15 min to finish the emulsification process.
In the present invention, the amount of the aqueous solution of the silicone modifier added is preferably 40% to 85% by mass of the polymer polyol.
In the present invention, the amount of water added is preferably 2 to 5 times the mass of the polymer polyol.
The present invention is not particularly limited in the kind, source and amount of the defoaming agent used in the defoaming process, and commercially available defoaming agents known to those skilled in the art to achieve defoaming effect may be used.
The solvent removal process is not particularly limited in the present invention, and a technical scheme of reduced pressure distillation well known to those skilled in the art can be adopted. In the preferred embodiment of the invention, the acetone solvent is recovered by vacuum distillation, and the recovered acetone can be used for the next batch of product production.
The preparation method provided by the invention adopts a specific process, has good production controllability and high stability, has good product state and performance parameter parallelism of each production batch, and is suitable for industrial application.
The invention also provides a high-transparency anionic aqueous polyurethane dispersion prepared by the preparation method of the technical scheme. In the invention, the high-transparency anionic aqueous polyurethane dispersion, namely the aqueous polyurethane coating agent is in a transparent state, can meet the requirements of leather processing technology, and is suitable for coating and releasing base materials such as PVC, PU, PET and the like (the aqueous polyurethane can show the best performance when being used for the coating agent such as leather and the like).
The invention provides a high-transparency anionic aqueous polyurethane dispersion and a preparation method thereof; the preparation method comprises the following steps: a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product; b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion. Compared with the prior art, the preparation method provided by the invention adopts a specific process, has good production controllability and high stability, has good product state and performance parameter parallelism of each production batch, and is suitable for industrial application; and the prepared product has high transparency, can meet the requirements of leather processing technology, and is suitable for coating and releasing PVC, PU, PET and other substrates. Experimental results show that the product obtained by the preparation method provided by the invention has the advantages of light transmittance of more than 92%, good film forming mechanical property, tensile strength of more than 18MPa and tensile rate of more than 500, can meet the requirements of leather processing technology, and is suitable for coating and releasing of substrates such as PVC, PU, PET and the like.
To further illustrate the present invention, the following examples are provided for illustration. The starting materials used in the following examples of the present invention are all commercially available.
Example 1
(1) 60g of adipic acid polyester glycol 2000(PDA2000) is put into a 500ml reaction bottle, and dehydration is carried out for 90min at the temperature of 130 ℃ and the pressure of-0.098 MPa; after the system is dehydrated, the temperature is reduced to 90 ℃, 32g of isophorone diisocyanate is added, and the reaction is carried out for 2.5h at 85 ℃; after the NCO is qualified, adding 4.5g of micromolecular chain extender 2, 2-dimethylolpropionic acid, dropwise adding 2 drops of dibutyltin dilaurate catalyst, and reacting for 5 hours at 80 ℃ until the NCO is qualified; cooling to 55 ℃, slowly adding 130g of acetone, slowly dropwise adding 1.5g of water-miscible aqueous solution of ethylenediamine and 5g of water while stirring after dispersion, controlling the temperature to be not more than 45 ℃, dropwise adding 3.4g of triethylamine for neutralization at 40 ℃ after dropwise addition is completed, and stirring for 8min to obtain a reaction product.
(2) And (2) controlling the temperature to be about 25 ℃ under the stirring of a dispersion machine at 600r/min, slowly dropwise adding 30g of 5% N- (N-butyl) -3-aminopropyltrimethoxysilane aqueous solution into the reaction product obtained in the step (1), immediately adding 190g of water for emulsification after the organosilicon modifier is added, completing the emulsification for about 10min, adding a defoaming agent for defoaming, and distilling acetone under reduced pressure to obtain the organosilicon-modified high-transparency waterborne polyurethane finishing agent, namely the high-transparency anionic waterborne polyurethane dispersion.
Example 2
(1) 60g of polytetrahydrofuran ether 2000(PTMG2000) is put into a 500ml reaction bottle, and dehydration is carried out for 60min at 105 ℃ and under-0.092 MPa; after the system is dehydrated, cooling to 80 ℃, adding 26g of hexamethylene diisocyanate, and reacting for 3h at 70 ℃; after the NCO is qualified, adding 5g of micromolecule chain extender 2, 2-dimethylolpropionic acid and 0.6g of diethylene glycol, dropwise adding 2 drops of diethylenetriamine catalyst, and reacting for 3.5 hours at 65 ℃ until the NCO is qualified; cooling to 55 ℃, slowly adding 120g of acetone, slowly adding dropwise 3.2g of aqueous solution of diethylene triamine and 12g of water which are miscible under stirring after dispersion, controlling the temperature to be not more than 35 ℃, dropwise adding 3.8g of triethylamine for neutralization at 20 ℃ after dropwise addition is finished, and stirring for 5min to obtain a reaction product.
(2) And (2) controlling the temperature to be about 20 ℃ under the stirring of a dispersion machine at 800r/min, slowly dropwise adding 25g of 5% gamma-aminopropyltrimethoxysilane aqueous solution into the reaction product obtained in the step (1), immediately adding 185g of water for emulsification after the organosilicon modifier is added, completing about 8min, adding a defoaming agent for defoaming, and distilling acetone under reduced pressure to obtain the organosilicon-modified high-transparency waterborne polyurethane finishing agent, namely the high-transparency anionic waterborne polyurethane dispersion.
Example 3
(1) 38g of glutaric acid polyester diol 2000(PAA2000) and 12g of polyethylene glycol 2000(PEG2000) are put into a 500ml reaction bottle, and dehydration is carried out for 120min at 120 ℃ and-0.098 MPa; after the system is dehydrated, cooling to 75 ℃, adding 36g of dicyclohexylmethane diisocyanate, and reacting for 3 hours at 75 ℃; after the NCO is detected to be qualified, 4g of micromolecule chain extender 2, 2-dimethylolpropionic acid and 2.1g of 1, 6-hexanediol are added, 2 drops of stannous octoate catalyst are added dropwise, and the reaction is carried out for 4.5 hours at the temperature of 75 ℃ until the NCO is detected to be qualified; cooling to 55 ℃, slowly adding 160g of acetone, slowly dropwise adding 0.8g of water-miscible aqueous solution of ethylenediamine and 4g of water while stirring after dispersion, controlling the temperature to be not more than 45 ℃, dropwise adding 3.0g of triethylamine at 25 ℃ after dropwise addition is completed for neutralization, and stirring for 5min to obtain a reaction product.
(2) And (2) controlling the temperature to be about 20 ℃ under the stirring of a dispersion machine at 800r/min, slowly dropwise adding 40g of 5% 3-diethylenetriaminopropyltrimethoxysilane aqueous solution into the reaction product obtained in the step (1), immediately adding 200g of water for emulsification after the organosilicon modifier is added, completing the emulsification for about 12min, adding a defoaming agent for defoaming, and distilling acetone under reduced pressure to obtain the organosilicon-modified high-transparency waterborne polyurethane finishing agent, namely the high-transparency anionic waterborne polyurethane dispersion.
Example 4
(1) 20g of polypropylene glycol 2000(PPG2000), 6g of polyethylene glycol 2000(PEG2000) and 34g of a laboratory-synthesized adipic acid and neopentyl glycol polymer (molecular weight 2000) are put into a 500ml reaction flask, and dehydration is carried out for 45min at 110 ℃ and-0.098 MPa; after the system is dehydrated, cooling to 90 ℃, adding 15g of dicyclohexylmethane diisocyanate and 21g of diphenylmethane diisocyanate, and reacting for 1.5h at 65 ℃; after the NCO is qualified, adding 6g of micromolecular chain extender 2, 2-dimethylolpropionic acid and 0.8g of neopentyl glycol, dropwise adding 2 drops of bismuth neodecanoate catalyst, and reacting for 3 hours at 50 ℃ until the NCO is qualified; cooling to 55 ℃, slowly adding 140g of acetone, slowly dropwise adding an aqueous solution of 0.3g of ethylenediamine, 1.8g of hexamethylenediamine and 10g of water which are mixed and dissolved under stirring after dispersion, controlling the temperature to be not more than 30 ℃, dropwise adding 4.5g of triethylamine for neutralization at 15 ℃ after dropwise addition is finished, and stirring for 5min to obtain a reaction product.
(2) And (2) slowly dripping 50g of 5% of gamma-aminopropyltriethoxysilane and N-cyclohexyl-3-aminopropylmethyldimethoxysilane aqueous solution into the reaction product obtained in the step (1) under the stirring of a dispersion machine at 1000r/min, immediately adding 180g of water for emulsification after the organosilicon modifier is added, finishing after about 15min, adding a defoaming agent for defoaming, and distilling acetone under reduced pressure to obtain the organosilicon-modified high-transparency waterborne polyurethane finishing agent, namely the high-transparency anionic waterborne polyurethane dispersion.
The high-transparency anionic aqueous polyurethane dispersions obtained by the preparation methods provided in examples 1 to 4 were tested for various properties, and the results are shown in table 1.
Table 1 Performance data of high-transparency anionic aqueous polyurethane dispersions obtained by the preparation methods provided in examples 1 to 4
In Table 1, the emulsion is the high-transparency anionic waterborne polyurethane dispersion, and the adhesive film is formed by placing the emulsion in a polytetrafluoroethylene mold, naturally drying and molding the emulsion, and drying the emulsion for 6 hours at 60 ℃ under the vacuum condition of-0.095 MPa, wherein the thickness of the adhesive film is about 1 mm.
As can be seen from Table 1, the product prepared by the preparation method provided by the invention has high transparency, light transmittance of more than 92%, good film forming mechanical property, tensile strength of more than 18MPa and tensile rate of more than 500, can meet the requirements of leather processing technology, and is suitable for coating and releasing base materials such as PVC, PU, PET and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a high-transparency anionic aqueous polyurethane dispersion comprises the following steps:
a) dehydrating polymer polyol, then carrying out prepolymerization on the dehydrated polymer polyol and isocyanate, and then sequentially carrying out chain pre-extension, chain post-extension and neutralization to obtain a reaction product;
b) adding an organic silicon modifier into the reaction product obtained in the step a), emulsifying, defoaming, and removing the solvent to obtain the high-transparency anionic aqueous polyurethane dispersion.
2. The method of claim 1, wherein the polymer polyol in step a) is selected from polyester polyols and/or polyether polyols;
the isocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
3. The method according to claim 1, wherein the dehydration in step a) is carried out at a temperature of 100 ℃ to 130 ℃, a pressure of-0.09 MPa to-0.1 MPa, and a time of 45min to 120 min.
4. The process according to claim 1, wherein the prepolymerization in step a) is carried out by:
and (3) cooling the dehydrated polymer polyol to below 90 ℃, adding isocyanate, and reacting for 1-3 h at 60-90 ℃.
5. The preparation method according to claim 1, wherein the pre-chain extension in step a) is specifically performed by:
after the prepolymerization is judged to be finished according to the NCO detection result, adding a micromolecule polyol chain extender and a catalyst, and reacting for 2-6 h at 50-90 ℃ until the NCO is qualified;
the small-molecular polyol chain extender comprises 2, 2-dimethylolpropionic acid.
6. The preparation method according to claim 1, wherein the post-chain extension process in step a) is specifically:
cooling a product obtained by chain extension to below 60 ℃, adding a solvent for dilution, and slowly dropwise adding a micromolecule polyamine chain extender at the temperature of between 20 and 50 ℃;
the small molecular polyamine chain extender is selected from one or more of ethylenediamine, diethylenetriamine and hexamethylenediamine.
7. The method according to claim 1, wherein the neutralizing agent used in the neutralization in step a) is triethylamine; the temperature of neutralization is 10-50 ℃, and the time is 5-10 min.
8. The method of claim 1, wherein the organosilicon modifier in step b) is selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane and 3-divinyltriaminopropyltrimethoxysilane.
9. The preparation method according to claim 1, wherein the emulsification process after adding the organosilicon modifier into the reaction product obtained in step a) in step b) is specifically:
and c) slowly dripping the aqueous solution of the organic silicon modifier into the reaction product obtained in the step a) under the stirring of 500 r/min-5000 r/min, and immediately adding water for emulsification for 5 min-20 min to finish the emulsification process.
10. A high-transparency anionic aqueous polyurethane dispersion, which is prepared by the preparation method of any one of claims 1 to 9.
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