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CN107857859B - Bio-based high-gloss aqueous polyurethane resin for textile coating and preparation method thereof - Google Patents

Bio-based high-gloss aqueous polyurethane resin for textile coating and preparation method thereof Download PDF

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Publication number
CN107857859B
CN107857859B CN201711137227.0A CN201711137227A CN107857859B CN 107857859 B CN107857859 B CN 107857859B CN 201711137227 A CN201711137227 A CN 201711137227A CN 107857859 B CN107857859 B CN 107857859B
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bio
polyol
aqueous polyurethane
chain extender
polyurethane dispersion
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CN107857859A (en
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戴家兵
魏星星
黄星
王启东
汪飞
李维虎
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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    • 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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    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/06—Polyurethanes from polyesters
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract

The invention provides a bio-based high-gloss aqueous polyurethane dispersion for textile coatings and a preparation method thereof, wherein the aqueous polyurethane dispersion comprises the following raw material components in parts by weight: 25-70 parts of polyol; 10-30 parts of polyisocyanate; 4-6 parts of a carboxylic acid type hydrophilic chain extender; 3-5 parts of a neutralizing agent; 5-15 parts of a bio-based chain extender; 2-10 parts of a micromolecular amine rear chain extender; the polyol is prepared from petroleum-based polyol and bio-based polyol according to the weight ratio (20-40): (5-30), wherein the bio-based polyol comprises any one or more of soybean oil polyol, palm oil polyol and rosin ester polyol. According to the invention, the bio-based polyol is used for replacing part of petroleum-based polyol, so that the natural degradability of the product is effectively improved, the price is low, and the production cost of the aqueous polyurethane is reduced.

Description

Bio-based high-gloss aqueous polyurethane resin for textile coating and preparation method thereof
Technical Field
The invention relates to the technical field of high molecular polymers, and particularly discloses a bio-based high-gloss aqueous polyurethane resin for a textile coating 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 little organic solvent, is non-inflammable, non-toxic, no environmental pollution, easy to transport, store and use, and has the excellent features of high strength, wear resistance, etc. inherent in polyurethane.
Like solvent polyurethanes, waterborne polyurethanes are polymer structures containing urethane units in the backbone of the product of the reaction of a polyisocyanate with a polyol. However, the gloss of solvent-borne polyurethanes can generally reach more than 95%, while the gloss of waterborne polyurethanes can generally only be between 80% and 85%.
And the traditional polyurethane materials are all organic polymer products, are difficult to degrade in natural environment after being discarded, and can cause certain pollution to the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bio-based high-gloss aqueous polyurethane resin for a textile coating and a preparation method thereof.
In order to achieve the above purpose, the invention is realized by the following technical scheme: in a first aspect, the invention discloses a bio-based high-gloss aqueous polyurethane dispersion, which comprises the following raw material components in parts by weight:
Figure BDA0001470719190000011
preferably, the polyol is 45 to 55 parts.
Preferably, the isocyanate is 25 to 30 parts.
Preferably, the carboxylic acid type hydrophilic chain extender is 5 to 6 parts.
Preferably, the neutralizing agent is 4 to 5 parts.
Preferably, the bio-based polyol chain extender is 10-15 parts.
Preferably, the small molecule amine post-chain extender accounts for 1-2 parts.
Preferably, the polyol is prepared from petroleum-based polyol and bio-based polyol in a weight ratio (20-40): (5-30).
More preferably, the polyol is prepared from petroleum-based polyol and bio-based polyol in a weight ratio (40-45): (5-10).
Preferably, the bio-based polyol comprises any one or more of a soy oil polyol, a palm oil polyol, and a rosin ester polyol. According to the invention, the bio-based polyol is adopted to replace part of petroleum-based polyol, so that the obtained aqueous polyurethane dispersion has excellent chemical and physical properties, especially good hydrolysis resistance and thermal stability; because the polymer is easy to naturally degrade due to the existence of the bio-base, the polymer is beneficial to reducing the environmental pollution.
Preferably, the macropolyol comprises any one or more of polycaprolactone diol, polytetrahydrofuran diol, polycarbonate diol and polybutylene adipate diol.
Preferably, the polyisocyanate includes any one or more of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid.
Preferably, the neutralizing agent comprises any one or more of triethylamine, diethanolamine and triethanolamine.
Preferably, the bio-based polyol chain extender is castor oil or castor oil derivative polyol. According to the invention, the castor oil or castor oil derivative polyol is used as the bio-based polyol, so that the obtained aqueous polyurethane dispersion has good low-temperature performance, hydrolysis resistance, corrosion resistance and high glossiness. The castor oil or castor oil derivative polyol is subjected to chain extension reaction through OH groups, double bonds and ester bonds, so that the comprehensive performance of the aqueous polyurethane dispersion is improved.
In a second aspect, the present invention provides a method for preparing the bio-based highlight aqueous polyurethane dispersion as described above, comprising the steps of:
1) stirring the macromolecular polyol, the bio-based polyol and the polyisocyanate for 1-3 hours at 80-100 ℃, then adding the carboxylic acid type hydrophilic chain extender and stirring for 1-2 hours at 80-100 ℃, adding the bio-based polyol chain extender and stirring for 1-2 hours at 80-100 ℃ to obtain a waterborne polyurethane prepolymer;
2) cooling the aqueous polyurethane prepolymer to 1-20 ℃, adding the neutralizer, transferring to a high-speed dispersing machine, and adding deionized water under high-speed stirring; and then adding the micromolecular amine and then stirring the chain extender at a low speed for 1-10min to obtain the bio-based high-gloss aqueous polyurethane dispersion.
Preferably, the carboxylic acid type hydrophilic chain extender, the bio-based polyol chain extender and the micromolecular amine post-chain extender are added, and the solvent for adjusting the concentration of the solution is added simultaneously and respectively.
Preferably, the solvent is one or more of acetone, methyl ethyl ketone and methyl ethyl ketone.
In a third aspect, the invention discloses the use of a bio-based high-gloss aqueous polyurethane dispersion as described above for the preparation of textile coatings.
In summary, the invention provides a bio-based high-gloss aqueous polyurethane dispersion for textile coating and a preparation method thereof, and the invention has the following beneficial effects:
according to the invention, an isocyanate monomer is firstly adopted to react with bio-based polyol and macromolecular polyol to obtain a reactant with low viscosity, then a carboxylic acid type hydrophilic chain extender and a bio-based polyol chain extender are sequentially added to react, and after full reaction, emulsification and dispersion are carried out, so that the aqueous polyurethane dispersion with good storage stability, excellent heat resistance, cold resistance and water resistance and higher gloss is prepared. According to the invention, the bio-based polyol is used for replacing part of petroleum-based polyol, so that the natural degradability of the product is effectively improved, the price is low, and the production cost of the aqueous polyurethane is reduced.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
43g of polycaprolactone diol (PCL2000, relative molecular mass 2000) and 7.4g of bio-based polyol (HM10100, relative molecular mass 2500) were weighed into a reactor, 25g of isophorone diisocyanate was added with stirring, the temperature was maintained at 90 ℃ and the mixture was stirred for 2 hours. Cooling to 80 ℃, adding 5.7g of dimethylolpropionic acid (DMPA) and 11g of castor oil, keeping the temperature at 80 ℃, stirring for 2 hours, cooling to 65 ℃, adding a catalyst and 20g of acetone, and reacting at constant temperature for 3 hours to obtain the waterborne polyurethane prepolymer.
And (2) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 4.3g of triethylamine, stirring for 1 minute, transferring to a high-speed emulsifying machine, adding 184g of deionized water at the rotating speed of 1400r/min, slowly adding 1.5g of ethylenediamine after phase transition, and then carrying out chain extension on a reagent to obtain the bio-based high-gloss waterborne polyurethane dispersion.
Example 2
30g of polycaprolactone diol (PCL2000, relative molecular mass 2000) and 14.7g of bio-based polyol (HM10100, relative molecular mass 2500) were weighed into a reactor, 25g of isophorone diisocyanate was added with stirring, the temperature was maintained at 90 ℃ and the mixture was stirred for 2 hours. Cooling to 80 ℃, adding 5.7g of dimethylolpropionic acid (DMPA) and 11g of castor oil, keeping the temperature at 80 ℃, stirring for 2 hours, cooling to 65 ℃, adding a catalyst and 20g of acetone, and reacting at constant temperature for 3 hours to obtain the waterborne polyurethane prepolymer.
And (2) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 4.3g of triethylamine, stirring for 1 minute, transferring to a high-speed emulsifying machine, adding 180g of deionized water at the rotating speed of 1400r/min, slowly adding 1.5g of ethylenediamine after phase transition, and then carrying out chain extension on a reagent to obtain the bio-based high-gloss waterborne polyurethane dispersion.
Example 3
30g of polytetrahydrofuran diol (PTMG2000, relative molecular mass 2000) and 14.7g of bio-based polyol (HM10100, relative molecular mass 2500) were weighed into a reactor, 25g of isophorone diisocyanate was added with stirring, the temperature was maintained at 90 ℃ and the mixture was stirred for 2 hours. Cooling to 80 ℃, adding 5.7g of dimethylolpropionic acid (DMPA) and 11g of castor oil, keeping the temperature at 80 ℃, stirring for 2 hours, cooling to 65 ℃, adding a catalyst and 20g of acetone, and reacting at constant temperature for 3 hours to obtain the waterborne polyurethane prepolymer.
And (2) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 4.3g of triethylamine, stirring for 1 minute, transferring to a high-speed emulsifying machine, adding 180g of deionized water at the rotating speed of 1400r/min, slowly adding 1.5g of ethylenediamine after phase transition, and then carrying out chain extension on a reagent to obtain the bio-based high-gloss waterborne polyurethane dispersion.
Example 4
30g of polybutylene adipate diol (PAA2000, relative molecular mass 2000) and 14.7g of bio-based polyol (HM10100, relative molecular mass 2500) were weighed into a reactor, 25g of isophorone diisocyanate was added with stirring, the temperature was maintained at 90 ℃, and the mixture was stirred for 2 hours. Cooling to 80 ℃, adding 5.7g of dimethylolpropionic acid (DMPA) and 11g of castor oil, keeping the temperature at 80 ℃, stirring for 2 hours, cooling to 65 ℃, adding a catalyst and 20g of acetone, and reacting at constant temperature for 3 hours to obtain the waterborne polyurethane prepolymer.
And (2) cooling the waterborne polyurethane prepolymer to 15 ℃, adding 4.3g of triethylamine, stirring for 1 minute, transferring to a high-speed emulsifying machine, adding 180g of deionized water at the rotating speed of 1400r/min, slowly adding 1.5g of ethylenediamine after phase transition, and then carrying out chain extension on a reagent to obtain the bio-based high-gloss waterborne polyurethane dispersion.
Comparative example 1
50.4g of polycaprolactone diol (PCL2000, relative molecular mass 2000) was weighed into a reactor, 25g of isophorone diisocyanate was added with stirring, the temperature was maintained at 90 ℃ and stirring was carried out for 2 hours. Cooling to 80 ℃, adding 16.7g of dimethylolpropionic acid (DMPA), keeping the temperature of 80 ℃, stirring for 2 hours, cooling to 65 ℃, adding a catalyst and 20g of acetone, and reacting at constant temperature for 3 hours to obtain the waterborne polyurethane prepolymer.
And (2) cooling the aqueous polyurethane prepolymer to 15 ℃, adding 4.3g of triethylamine, stirring for 1 minute, transferring to a high-speed emulsifying machine, adding 184g of deionized water at the rotating speed of 1400r/min, slowly adding 1.5g of ethylenediamine after phase transition, and then carrying out chain extension to obtain the aqueous polyurethane dispersion.
And (3) detection results:
1. the performance tests were performed on the bio-based high-gloss aqueous polyurethane dispersions prepared in examples 1 to 4 and the aqueous polyurethane dispersion prepared in comparative example 1:
(1) viscosity: the test was performed with paint number 4 cup. The viscosity test results are shown in table 1.
(2) Storage stability: the emulsion was placed in an environment of 50 ℃ for three weeks, and then observed for abnormalities in viscosity and appearance, such as increase in viscosity, whitening and opacity of the appearance, and presence of dregs. The results of the storage stability test are shown in table 1.
2. The bio-based high-gloss aqueous polyurethane dispersion prepared in the embodiments 1 to 4 and the aqueous polyurethane dispersion prepared in the comparative example 1 are thickened, leveled and defoamed, then the obtained mixture is coated on the surface layer of a textile fabric, the textile fabric is placed in a drying box at 120 ℃ for drying for 1 to 2 minutes to obtain a textile coating, the performance of the aqueous polyurethane dispersions prepared in the embodiments 1 to 4 and the comparative example 1 is evaluated according to the national standard GB/T28463-2012 textile decorative coating fabric, and the test results are shown in the table 1.
3. Gloss: the textile finish was tested for gloss and the results are shown in table 2.
TABLE 1 Performance results for aqueous polyurethane dispersions prepared in examples 1-4 and comparative example 1
Example 1 Example 2 Example 3 Example 4 Comparative example 1
Appearance of the product Is transparent Is transparent Semi-transparent Is transparent Semi-transparent
Viscosity/s 43 35 45 52 47
modulus/MPa 3.6 4.0 3.5 3.2 3.2
Mechanical strength/MPa 27.53 30.16 29.25 28.73 25.23
Elongation/percent 426 456 527 420 447
Storage stability (50 ℃, 3 weeks) No abnormality No abnormality No abnormality No abnormality No abnormality
Low temperature resistance (-20 ℃ C.) Not brittle Not brittle Not brittle Not brittle Brittle fracture
TABLE 2 gloss results for aqueous polyurethane dispersions prepared in examples 1-4 and comparative example 1
Item Example 1 Example 2 Example 3 Example 4 Comparative example 1
Degree of gloss (°) 90.21 91.35 91.35 92.13 82.17
As can be seen from tables 1 and 2, compared with comparative example 1, the appearance, viscosity, storage stability and elongation of the bio-based high-gloss aqueous polyurethane dispersions prepared in examples 1 to 4 are equivalent, but the bio-based high-gloss aqueous polyurethane dispersions prepared in examples 1 to 4 have better mechanical strength and low temperature resistance and higher glossiness, and are beneficial to the wide application of the bio-based high-gloss aqueous polyurethane dispersions in the preparation of textile coatings.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.

Claims (6)

1. A method for preparing a bio-based high-gloss aqueous polyurethane dispersion for textile coating, characterized in that: the bio-based high-gloss aqueous polyurethane dispersion for the textile coating comprises the following raw material components in parts by weight:
Figure FDA0002699725240000011
wherein the polyol is prepared from petroleum-based polyol and bio-based polyol according to the weight ratio of (40-45): (5-10), wherein the bio-based polyol is HM10100 type, the relative molecular mass of the bio-based polyol is 2500, the polyisocyanate is isophorone diisocyanate, and the bio-based chain extender is castor oil or castor oil derivative polyol;
the method comprises the following steps:
1) stirring the petroleum-based polyol, the bio-based polyol and the polyisocyanate for 1-3 hours at the temperature of 80-100 ℃, then adding the carboxylic acid type hydrophilic chain extender, stirring for 1-2 hours at the temperature of 80-100 ℃, adding the bio-based chain extender, and stirring for 1-2 hours at the temperature of 80-100 ℃ to obtain a waterborne polyurethane prepolymer;
2) cooling the aqueous polyurethane prepolymer to 1-20 ℃, adding the neutralizer, transferring to a high-speed dispersing machine, and adding deionized water while stirring; and then adding the micromolecular amine and then stirring the chain extender for 1 to 10min to obtain the bio-based high-gloss aqueous polyurethane dispersion.
2. A process for the preparation of bio-based high gloss aqueous polyurethane dispersions for textile coatings according to claim 1 wherein: the petroleum-based polyol comprises any one or more of polycaprolactone diol, polytetrahydrofuran diol, polycarbonate diol and polybutylene adipate diol.
3. The method of preparing a bio-based highlight aqueous polyurethane dispersion for textile coating according to claim 1 characterized by: the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid.
4. The method of preparing a bio-based highlight aqueous polyurethane dispersion for textile coating according to claim 1 characterized by: the neutralizing agent comprises one or more of triethylamine, diethanolamine and triethanolamine.
5. The method of preparing a bio-based highlight aqueous polyurethane dispersion for textile coating according to claim 1 characterized by: and adding the carboxylic acid type hydrophilic chain extender, the bio-based polyol chain extender and the micromolecular amine rear chain extender, and simultaneously and respectively adding a solvent for adjusting the concentration of the solution.
6. The method of preparing a bio-based highlight aqueous polyurethane dispersion for textile coating according to claim 5 characterized by: the solvent is one or more of acetone, butanone and methyl ethyl ketone.
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