CN109503800B - Modified waterborne polyurethane and preparation method thereof - Google Patents
Modified waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN109503800B CN109503800B CN201811281992.4A CN201811281992A CN109503800B CN 109503800 B CN109503800 B CN 109503800B CN 201811281992 A CN201811281992 A CN 201811281992A CN 109503800 B CN109503800 B CN 109503800B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention discloses a preparation method of modified waterborne polyurethane, which comprises the following raw material components in percentage by weight: 25-70 parts of macromolecular polyol; 10-30 parts of isocyanate; 0.5-10 parts of a carboxylic acid type hydrophilic chain extender; 3-5 parts of a neutralizing agent; 1-10 parts of a polyol chain extender; 0.5-5 parts of ester catechin; 0.5-10 parts of a micromolecular amine rear chain extender; when the ester catechin modified waterborne polyurethane prepared by the invention is formed into a film, the film forming property is good, and the thermal stability is improved.
Description
Technical Field
The invention relates to the technical field of high polymer resin, and particularly relates to modified waterborne polyurethane and a preparation method thereof.
Background
The aqueous polyurethane uses water as a dispersion medium and can be divided into three types, namely a water emulsion type, a water dispersion type and a water soluble type according to particle sizes. It contains no or less organic solvent, is non-inflammable, non-toxic, environment friendly, easy to transport, store and use, and has the excellent features of high strength, wear resistance, etc. of polyurethane.
However, the waterborne polyurethane is easily damaged by bacteria in the surrounding environment, particularly mould, the antibacterial and mildewproof performance is poor, and the thermal stability of the waterborne polyurethane with a single linear structure is not ideal. Most of the existing waterborne polyurethane products have poor thermal stability and antibacterial and mildewproof performance, and the ester catechin EGCG can not only effectively improve the thermal stability of the waterborne polyurethane, but also greatly improve the antibacterial and mildewproof effects of the waterborne polyurethane.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a modified aqueous polyurethane dispersion having good storage stability, good water resistance, and excellent antibacterial and antifungal properties, and a preparation method thereof.
In order to achieve the above objects and other related objects, the present invention provides a modified waterborne polyurethane, which is characterized by comprising the following raw material components in parts by weight:
optionally, the macromolecular polyol is any one or more of polycaprolactone diol, polytetrahydrofuran diol, polycarbonate diol and polybutylene adipate diol.
Optionally, the isocyanate is any one or more of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Optionally, the neutralizing agent is any one or more of triethylamine, diethanolamine and triethanolamine.
Optionally, the carboxylic acid type hydrophilic chain extender is selected to be DMPA; the polyol chain extender is one or a combination of more of 1, 4-dihydroxybutane, neopentyl glycol, methyl propylene glycol or 1, 4-cyclohexyl dimethanol.
Optionally, the small molecule amine post-chain extender comprises any one or more of ethylenediamine, isophorone diamine, hydrazine hydrate, and diaminodicyclohexylmethane.
Optionally, the ester-type catechin has a chemical formula of
The invention also provides a preparation method of the modified waterborne polyurethane, which comprises the following steps:
1) adding the amount of the macromolecular polyol and the amount of the isocyanate into a reactor, and stirring to obtain a first reaction mixture;
2) adding the amount of the carboxylic acid type hydrophilic chain extender and the amount of the polyol chain extender to the first reaction mixture, and stirring to obtain a second reaction mixture;
3) adding a catalyst and acetone into the second reaction mixture, reacting at constant temperature, and adding the ester catechin in the amount for reacting to obtain a waterborne polyurethane prepolymer;
4) cooling the aqueous polyurethane prepolymer, and then adding the neutralizer in the amount to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed dispersion machine, stirring, and adding deionized water while stirring the third reaction mixture;
6) and then adding the small molecular amine rear chain extender in the amount, and uniformly mixing to obtain the ester type catechin modified waterborne polyurethane.
Optionally, in step 2), when the carboxylic acid type hydrophilic chain extender and the amount of the polyol chain extender are added to the first reaction mixture, the first reaction mixture is in a stirring state.
Optionally, the stirring speed of the high-speed disperser while stirring the third reaction mixture is 1400 r/min.
By adopting the technical scheme, the ester catechin modified waterborne polyurethane prepared by the invention contains a plurality of hydroxyl groups, and can obviously increase the internal crosslinking of the waterborne polyurethane, thereby improving the heat resistance and the water resistance of the product.
Detailed Description
The present invention will be further illustrated by the following description of examples in conjunction with the accompanying drawings.
The invention discloses modified waterborne polyurethane, which is prepared from the following raw materials in parts by weight: 25-70 parts of macromolecular polyol; 10-30 parts of isocyanate; 3-5 parts of a neutralizing agent; 0.5-10 parts of a carboxylic acid type hydrophilic chain extender; 1-10 parts of a polyol chain extender; 0.5-5 parts of ester catechin; 0.5-10 parts of a micromolecule amine post-chain extender.
Wherein the macromolecular polyol is any one or a combination of more of polycaprolactone diol, polytetrahydrofuran diol, polycarbonate diol and polybutylene adipate diol; the isocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methane diisocyanate; the neutralizer is any one or a plurality of combinations of triethylamine, diethanolamine and triethanolamine; the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid (DMPA); the polyol chain extender is one or more of 1, 4-dihydroxy butane, neopentyl glycol, methyl propylene glycol or 1, 4-cyclohexyl dimethanol; the micromolecule amine post-chain extender comprises any one or more of ethylenediamine, isophorone diamine, hydrazine hydrate and diaminodicyclohexyl methane; the ester catechin EGCG has a chemical formula of
Example 1
The preparation method of the ester catechin modified waterborne polyurethane comprises the following steps:
1) weighing 96g of polytetrahydrofuran diol (PTMG2000, the relative molecular mass is 2000) and putting the polytetrahydrofuran diol into a reactor, adding 26.8g of isophorone diisocyanate under stirring, keeping the temperature at 90 ℃, and stirring for 2 hours to obtain a first reaction mixture;
2) cooling the first reaction mixture to 80 ℃, adding 2.6g dimethylolpropionic acid (DMPA) and 1.58g methyl propylene glycol, and keeping the temperature at 80 ℃ to stir for 2 hours to obtain a second reaction mixture;
3) cooling the second reaction mixture to 65 ℃, adding a catalyst and 20g of acetone, reacting for 3 hours at constant temperature, and then adding 1.24g of EGCE to prepare a waterborne polyurethane prepolymer;
4) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 1.96g of triethylamine, and stirring for 1 minute to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed emulsifying machine, and adding 307g of deionized water at the rotating speed of 1400 r/min;
6) and after the phase of the third reaction mixture is changed, slowly adding 1.69g of ethylenediamine into the high-speed emulsifying machine, and then carrying out chain extension on the ethylene diamine to obtain the ester type catechin modified waterborne polyurethane.
Example 2
The preparation method of the ester catechin modified waterborne polyurethane comprises the following steps:
1) weighing 96g of polytetrahydrofuran diol (PTMG2000, the relative molecular mass is 2000) and putting the polytetrahydrofuran diol into a reactor, adding 26.8g of isophorone diisocyanate under stirring, keeping the temperature at 90 ℃, and stirring for 2 hours to obtain a first reaction mixture;
2) cooling the first reaction mixture to 80 ℃, adding 2.6g dimethylolpropionic acid (DMPA) and 1.58g methyl propylene glycol, and keeping the temperature at 80 ℃ to stir for 2 hours to obtain a second reaction mixture;
3) cooling the second reaction mixture to 65 ℃, adding a catalyst and 13g of acetone, reacting for 3 hours at constant temperature, and then adding 1.6g of EGCE to prepare a waterborne polyurethane prepolymer;
4) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 1.96g of triethylamine, and stirring for 1 minute to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed emulsifying machine, and adding 307g of deionized water at the rotating speed of 1400 r/min;
6) and after the phase of the third reaction mixture is changed, slowly adding 1.69g of ethylenediamine into the high-speed emulsifying machine, and then carrying out chain extension on the ethylene diamine to obtain the ester type catechin modified waterborne polyurethane.
Example 3
The preparation method of the ester catechin modified waterborne polyurethane comprises the following steps:
1) weighing 96g of polytetrahydrofuran diol (PTMG2000, the relative molecular mass is 2000) and putting the polytetrahydrofuran diol into a reactor, adding 26.8g of isophorone diisocyanate under stirring, keeping the temperature at 90 ℃, and stirring for 2 hours to obtain a first reaction mixture;
2) cooling the first reaction mixture to 80 ℃, adding 2.6g dimethylolpropionic acid (DMPA) and 1.58g methyl propylene glycol, and keeping the temperature at 80 ℃ to stir for 2 hours to obtain a second reaction mixture;
3) cooling the second reaction mixture to 65 ℃, adding a catalyst and 20g of acetone, reacting for 3 hours at constant temperature, and then adding 4.8g of EGCE to prepare a waterborne polyurethane prepolymer;
4) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 1.96g of triethylamine, and stirring for 1 minute to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed emulsifying machine, and adding 307g of deionized water at the rotating speed of 1400 r/min;
6) and after the phase of the third reaction mixture is changed, slowly adding 1.69g of ethylenediamine into the high-speed emulsifying machine, and then carrying out chain extension on the ethylene diamine to obtain the ester type catechin modified waterborne polyurethane.
Example 4
The preparation method of the ester catechin modified waterborne polyurethane comprises the following steps:
1) weighing 96g of polytetrahydrofuran diol (PTMG2000, the relative molecular mass is 2000) and putting the polytetrahydrofuran diol into a reactor, adding 26.8g of isophorone diisocyanate under stirring, keeping the temperature at 90 ℃, and stirring for 2 hours to obtain a first reaction mixture;
2) cooling the first reaction mixture to 80 ℃, adding 2.6g dimethylolpropionic acid (DMPA) and 1.58g methyl propylene glycol, and keeping the temperature at 80 ℃ to stir for 2 hours to obtain a second reaction mixture;
3) cooling the second reaction mixture to 65 ℃, adding a catalyst and 20g of acetone, reacting for 3 hours at constant temperature, and then adding 0.9g of EGCE to prepare a waterborne polyurethane prepolymer;
4) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 1.96g of triethylamine, and stirring for 1 minute to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed emulsifying machine, and adding 307g of deionized water at the rotating speed of 1400 r/min;
6) and after the phase of the third reaction mixture is changed, slowly adding 1.69g of ethylenediamine into the high-speed emulsifying machine, and then carrying out chain extension on the ethylene diamine to obtain the ester type catechin modified waterborne polyurethane.
The experimental results of examples 1 to 4 are shown in Table 1 below.
TABLE 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (8)
1. The modified waterborne polyurethane is characterized by comprising the following raw material components in parts by weight:
25-70 parts of macromolecular polyol;
10-30 parts of isocyanate;
3-5 parts of a neutralizing agent;
0.5-10 parts of a carboxylic acid type hydrophilic chain extender;
1-10 parts of a polyol chain extender;
0.5-5 parts of ester catechin;
0.5-10 parts of a micromolecular amine rear chain extender;
the ester type catechin has a chemical formula of
The preparation method of the modified waterborne polyurethane comprises the following steps:
1) adding the amount of the macromolecular polyol and the amount of the isocyanate into a reactor, and stirring to obtain a first reaction mixture;
2) adding the amount of the carboxylic acid type hydrophilic chain extender and the amount of the polyol chain extender to the first reaction mixture, and stirring to obtain a second reaction mixture;
3) adding a catalyst and acetone into the second reaction mixture, reacting at constant temperature, and adding the ester catechin in the amount for reacting to obtain a waterborne polyurethane prepolymer;
4) cooling the aqueous polyurethane prepolymer, and then adding the neutralizer in the amount to obtain a third reaction mixture;
5) transferring the third reaction mixture into a high-speed dispersion machine, stirring, and adding deionized water while stirring the third reaction mixture;
6) and then adding the small molecular amine rear chain extender in the amount, and uniformly mixing to obtain the ester type catechin modified waterborne polyurethane.
2. The modified aqueous polyurethane as claimed in claim 1, wherein: the macromolecular polyol is any one or a combination of more of polycaprolactone diol, polytetrahydrofuran diol, polycarbonate diol and polybutylene adipate diol.
3. The modified aqueous polyurethane as claimed in claim 1, wherein: the isocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
4. The modified aqueous polyurethane as claimed in claim 1, wherein: the neutralizing agent is any one or a combination of triethylamine, diethanolamine and triethanolamine.
5. The modified aqueous polyurethane as claimed in claim 1, wherein: the carboxylic acid type hydrophilic chain extender is DMPA; the polyol chain extender is one or a combination of more of 1, 4-dihydroxybutane, neopentyl glycol, methyl propylene glycol or 1, 4-cyclohexyl dimethanol.
6. The modified aqueous polyurethane as claimed in claim 1, wherein: the micromolecular amine post-chain extender comprises any one or more of ethylenediamine, isophorone diamine, hydrazine hydrate and diaminodicyclohexyl methane.
7. The modified aqueous polyurethane as claimed in claim 1, wherein: in the preparation method, in the step 2), when the carboxylic acid type hydrophilic chain extender and the polyol chain extender are added to the first reaction mixture, the first reaction mixture is in a stirred state.
8. The modified aqueous polyurethane as claimed in claim 1, wherein: in the preparation method, the stirring speed of the high-speed disperser during stirring the third reaction mixture is 1400 r/min.
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| CN110643013A (en) * | 2019-10-08 | 2020-01-03 | 浙江合力革业有限公司 | Novel synthetic leather material and preparation method thereof |
| CN114634701B (en) * | 2022-03-25 | 2024-02-13 | 苏州瑞高新材料股份有限公司 | Modified polyurethane, efficient antibacterial synthetic leather material, yoga mat and preparation method of yoga mat |
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