CN113881016A - Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof - Google Patents

Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof Download PDF

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CN113881016A
CN113881016A CN202111295832.7A CN202111295832A CN113881016A CN 113881016 A CN113881016 A CN 113881016A CN 202111295832 A CN202111295832 A CN 202111295832A CN 113881016 A CN113881016 A CN 113881016A
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aqueous polyurethane
polyurethane dispersion
component
silicone oil
reaction
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于丽
王海梅
李卫飞
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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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
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing compounds
    • 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
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms

Abstract

The invention belongs to the technical field of aqueous polyurethane dispersions, and particularly relates to an aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth, and a preparation method and application thereof. The aqueous polyurethane dispersion is prepared from the following components in percentage by weight: a. polyisocyanate, 18-28 wt%; b. polymer polyol, 28-41 wt%; c. 20-30 wt% of silanol; d. 1-6 wt% of micromolecular polyol chain extender; e. 1-6 wt% of hydrophilic chain extender containing active hydrogen; f. 10-20 wt% of silica gel; g. 1-6 wt% of small molecular polyamine chain extender containing active hydrogen. The invention can improve the mutual combination of the aqueous polyurethane dispersion resin and the heavy silicone oil treatment cloth, and achieves high adhesion and high washing fastness of printing.

Description

Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof
Technical Field
The invention belongs to the technical field of aqueous polyurethane dispersions, and particularly relates to an aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth, and a preparation method and application thereof.
Background
In the field, the aqueous polyurethane dispersion is adopted for printing, and only drying is needed in the operation procedure without water washing treatment, so that the process is simple, the discharge of solvent and sewage can be reduced, and the requirement of environmental protection is met. In addition, the aqueous polyurethane dispersion can form a dense and transparent film on the surface of the fabric, and the film has good adhesiveness and elasticity.
With the improvement of living standard of people, people have higher and higher requirements on clothes and shoe materials, so that the color fastness of printing or washing fastness on the clothes and shoe materials becomes one of the concerns. The existing base materials for printing are generally cotton cloth and cotton elastic cloth, and more base materials treated by heavy silicone oil are on the market, and the fastness of the common water-based resin on the base materials is poor when the common water-based resin is used for printing.
Patent document CN 109679059a discloses a polyurethane polyurea aqueous dispersion, a preparation method and applications thereof, wherein the polyurethane polyurea aqueous dispersion is prepared by components comprising one or more tertiary amine compounds, one or more polyols with functionality of 2-4, one or more polyisocyanates, and the like. However, the prepared polyurethane polyurea water dispersion can not achieve 10-wheel washing fastness and good adhesion after the formula is added with powder in a printing direction.
Therefore, there is a need to develop a resin capable of improving washing fastness and adhesion on heavy silicone oil-treated cloth.
Disclosure of Invention
The invention aims to provide an aqueous polyurethane dispersion for improving the washing fastness of heavy silicone oil treated cloth, and a preparation method and application thereof, aiming at the problem that resin on the heavy silicone oil treated cloth has poor washing fastness. According to the aqueous polyurethane dispersion, the silanol is grafted to a molecular chain in a prepolymerization stage, and a synergistic effect is generated with a silicone rubber substance added into a system before a post-chain extension reaction, so that the mutual combination of aqueous polyurethane dispersion resin and heavy silicone oil treatment cloth can be improved, and the requirements of high adhesion and high washing fastness of printing can be met.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, there is provided an aqueous polyurethane dispersion for improving wash fastness on heavy silicone oil-treated cloth, prepared by including the following components in weight percent, based on the solid content weight (e.g., 100 wt%) of the components in the aqueous polyurethane dispersion:
a. isocyanate, 18-28 wt% (e.g., 19 wt%, 22 wt%, 24 wt%, 26 wt%), preferably 20-25 wt%;
b. polymer polyol, 28-41 wt% (e.g., 30 wt%, 34 wt%, 36 wt%, 40 wt%), preferably 32-38 wt%;
c. silanol, 20-30 wt% (e.g., 22 wt%, 24 wt%, 26 wt%, 28 wt%), preferably 20-25 wt%;
d. a small molecule polyol chain extender having a number average molecular weight of 20 to 100, 1 to 6 wt% (e.g., 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 5 wt%), preferably 1.5 to 4 wt%;
e. 1 to 6 wt% (e.g., 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 5 wt%), preferably 2 to 5 wt% of an active hydrogen-containing hydrophilic chain extender;
f. silicone rubber, 10-20 wt% (e.g., 12 wt%, 14 wt%, 16 wt%, 18 wt%), preferably 10-15 wt%;
g. active hydrogen-containing small molecule polyamine chain extenders have a number average molecular weight of less than 500 (e.g., 20, 50, 100, 300, 400, 480), 1-6 wt% (e.g., 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 5 wt%), preferably 2-5 wt%.
According to the aqueous polyurethane dispersion provided by the invention, the component a is selected from aliphatic isocyanate or aromatic isocyanate. In some embodiments, component a is selected from aliphatic and/or cycloaliphatic isocyanates, preferably from one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and 1, 6-hexyl diisocyanate, more preferably dicyclohexylmethane diisocyanate, isophorone diisocyanate, and mixtures thereof. In some embodiments, component a is a mixture of dicyclohexylmethane diisocyanate and isophorone diisocyanate, where the two isocyanates in the mixture can act synergistically to provide better overall performance of the resulting dispersion.
In some embodiments, component b is a 5000-number average molecular weight (e.g., 300, 500, 1000, 2000, 4000) polymer polyol, preferably selected from one or more of polytetrahydrofuran ether glycol, polyethylene glycol diol, polypropylene glycol diol, polyethylene glycol-propylene glycol diol, polyethylene oxide polyol, polypropylene oxide polyol, and polysiloxane polyol. In some preferred embodiments, component b is selected from one or more of polypropylene glycol diol and polytetrahydrofuran ether glycol having a number average molecular weight of 300 to 3000.
In some embodiments, component c is selected from one or more of trimethylsilanol, triethylsilanol, and triphenylsilanol.
In some embodiments, component d is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, 2, 3-butanediol, neopentyl glycol, diethylene glycol and 1, 4-cyclohexanedimethanol, preferably from 1, 4-butanediol and/or 1, 6-hexanediol.
In some embodiments, component e is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid and dimethyloloctanoic acid, preferably dimethylolbutyric acid.
In some embodiments, component f is selected from one or more of methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, and diethyl silicone rubber.
In some embodiments, component g is selected from one or more of ethylenediamine, propylenediamine, hexamethylenediamine, 4-diphenylmethanediamine, hydroxyethylethylenediamine, di-n-butylamine, isophoronediamine and 1, 3-bis [ (trimethylol) methylamino ] propane, preferably from one or more of 1, 3-bis [ (trimethylol) methylamino ] propane, hydroxyethylethylenediamine and isophoronediamine.
In accordance with the aqueous polyurethane dispersions provided herein, in some embodiments, the aqueous polyurethane dispersion has a solids content of 45 to 55 wt.% (e.g., 48 wt.%, 52 wt.%, 54 wt.%), preferably 50 to 55 wt.%; the particle size is 50-200nm (e.g., 80nm, 120nm, 160nm), preferably 100-150 nm.
In another aspect, there is provided a method of preparing an aqueous polyurethane dispersion as described above, comprising the steps of:
(1) mixing the component a, the component b and the component c, reacting, and measuring the NCO content in the system to generate a prepolymer; for example, the reaction temperature is 80-95 ℃ and the reaction time is 1-3 h;
(2) adding the component d, the component e and a catalyst into the prepolymer, optionally adding a solvent (such as acetone) for dilution, and carrying out chain extension reaction; for example, the temperature of the reaction is 75 to 85 ℃; stopping the reaction after the theoretical NCO% is reached, optionally adding a solvent (such as acetone) for dilution, and cooling the system;
in this step, for example, the temperature of the system may be first reduced to 55 to 60 ℃, then the raw material components and the catalyst may be added, and the mixture may be diluted and stirred uniformly by adding a solvent, and then heated to 75 to 85 ℃ to perform the reaction;
in the step, for example, the temperature of the system can be reduced to 55-60 ℃ after the reaction is stopped, a solvent is added for dilution and stirring for 5-10min, so that the prepolymer and the solvent are fully mixed, and then the temperature of the system is continuously reduced to 30-35 ℃;
(3) adding deionized water into the cooled system for dispersion treatment; for example, the dispersion treatment is carried out under high-speed shearing conditions;
(4) after dispersion treatment, adding the component f into the system, uniformly mixing, adding the component g, and carrying out chain extension reaction, wherein the reaction temperature is 30-50 ℃, and the reaction time is 3-10 min; alternatively, the aqueous polyurethane dispersion is obtained after removing the solvent (e.g., acetone) from the resulting emulsion by distillation under reduced pressure.
According to the preparation process of the present invention, in some embodiments, the catalyst is selected from an organobismuth catalyst, for example, a bismuth isooctanoate catalyst, a bismuth laurate acid catalyst, a bismuth neodecanoate catalyst, preferably selected from one or more of organobismuth Coscat83, organobismuth 1610, organobismuth 2010, organobismuth 2810, and organobismuth 2808.
In yet another aspect, there is also provided a use of the aqueous polyurethane dispersion as described above, the field of the use including clothing, footwear, ink. For example, in such applications, the resulting aqueous polyurethane dispersion is used in combination with an adjuvant and combined with a heavy silicone oil treated cloth in a printing process.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
according to the aqueous polyurethane dispersion, the silanol is grafted to a molecular chain in the prepolymerization stage, and a synergistic effect is generated with a silicone rubber substance added before the post-chain extension reaction, so that the combination effect of the aqueous polyurethane dispersion and the heavy silicone oil treatment cloth is improved, and the high adhesion and high washing fastness of printing is finally realized.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
1. Test methods related to the present invention
The construction process for preparing textile prints using the aqueous polyurethane dispersions prepared in the examples and comparative examples is as follows:
according to the formula shown in table 1, the prepared formula system consisting of the aqueous polyurethane dispersion resin and the auxiliary agent is coated on the heavy silicone oil treatment cloth by adopting manual screen printing, screen printing or rotary screen printing, and the two times and four times of operation are carried out. The prepared sample is put in a 50 ℃ oven for curing for 24 hours, and then is continuously balanced and dried for 48 hours in a constant temperature and humidity room (temperature: 25 ℃, humidity: 65% rh) to be used as a sample to be tested for testing.
TABLE 1 formulation for textile printing construction (based on 100 wt% of the total weight of the components)
Figure BDA0003336553500000051
Figure BDA0003336553500000061
The particle size test method comprises the following steps: the product was tested using a malvern particle sizer.
Viscosity test method: a Brookfield viscometer, No. 3 rotor, was used at 30 rpm.
And (3) testing the water washing resistance: the printing sample after balanced drying is intensively washed by a Siemens washing machine under the cotton standard, and is washed by water according to 60 ℃/1200rpm/10 times; after washing, the surface of the printed sample is required to be not washed off, delaminated, abraded or exposed, and the washing resistance is rated according to the number of damage (for example, 1 to 5 points): washing with water for 10 times to obtain 5 min; washing with water for 8 times without breaking, and washing with water for 10 times without breaking to obtain 4 min; the mixture is not broken after 6 times of washing and is broken after 8 times of washing, and 3 minutes is obtained; washing with water for 4 times without breaking, and washing with water for 6 times without breaking to obtain 2 min; the product is not broken after 2 times of washing and broken after 4 times of washing, and the score is 1. The water wash score for each sample was repeated 5 times and averaged.
And (3) testing the adhesion performance: the stamp sample after the balanced drying is with 1 yuan of coin normal power way from the edge scraping, and the scraping number of times when the record is scraped brokenly scores the adhesion: no damage is caused for 10 times, and 5 points are obtained; no damage for 8 times and no damage for 10 times, and 4 min is obtained; no damage for 6 times and 8 times, and 3 points are obtained; 4 times of no damage and 6 times of damage, and 2 points are obtained; the number of breakage was 4 times, and the number of breakage was 2 times, and the score was 1. The adhesion score for each sample was repeated 5 times and averaged.
And (3) testing the smoothness: randomly select 10 individuals, and sequentially score the touch smoothness of the print samples after balanced drying (e.g., 1 to 5 points): 1 minute-the worst hand feeling, extremely unsmooth; 5 min-best hand feeling and extremely smooth. Then, the average value is taken according to the rating data of 10 persons.
2. Sources of Experimental raw materials
Component a
Figure BDA0003336553500000063
HMDI (dicyclohexylmethane diisocyanate, having an NCO% content of about 32.0%, Vanhua Chemicals Ltd.);
Figure BDA0003336553500000062
IPDI (isophorone diisocyanate, NCO% content about 37.8%, Vanhua chemical group Co., Ltd.);
component b
PPG2000 (Polypropylene glycol diol, hydroxyl number 56mgKOH/g, number average molecular weight ≈ 2000, functionality 2, great east Chemicals);
PTMG2000 (polytetrahydrofuran ether glycol, hydroxyl value 56mgKOH/g, number average molecular weight 2000, functionality of 2, Tahitawa Daochien);
PTMG1000 (polytetrahydrofuran ether glycol, hydroxyl value 112mgKOH/g, number average molecular weight 1000, functionality of 2, dawsonia macrochemical);
component c
Trimethylsilanol (shanghai kaiser chemical limited);
triethylsilanol (alatin reagent);
triphenylsilanol (Hubei Koufole materials science and technology, Inc.);
component f
Methyl vinyl silicone rubber (Shenzhen Hongye science and technology Limited);
methyl phenyl vinyl silicone rubber (Anhui Eyota Silicone oil Co., Ltd.);
diethyl silicone rubber (Shenzhen Hongyeljie science and technology Co., Ltd.);
component d
HDO (1, 6-hexanediol, BASF, germany);
BDO (1, 4-butanediol, BASF, Germany);
component e
Dimethylolbutanoic acid (carbofuran technologies ltd., analytical purity);
component g
IPDA (isophoronediamine, BASF, Germany);
EDA (ethylenediamine, BASF, germany);
1, 3-bis [ (trihydroxymethyl) methylamino ] propane (Dalian Meiren Biotechnology Co., Ltd.);
organic bismuth Coscat 83: the leading chemical company in the United states, analytically pure.
Example 1
Adding 20g of IPDI, 24.2g of HMDI, 20g of PPG2000, 60.5g of PTMG1000 and 42.8g of triethylsilanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 4g of BDO, 4.2g of HDO, 9.4g of dimethylolbutyric acid, 0.8 g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
173g of deionized water is added into the cooled system, and dispersion treatment is carried out under the condition of high-speed shearing;
adding 22g of methyl phenyl vinyl silicone rubber into the system, uniformly stirring, diluting 2.1g of isophorone diamine and 3g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 40g of deionized water, slowly adding the diluted materials into the system, reacting for 5min at a constant temperature of 35 ℃, and then distilling the prepared emulsion under reduced pressure to remove acetone, thereby obtaining the blue-light-evident aqueous polyurethane dispersion with the particle size of 120nm and the solid content of 50%.
Example 2
Adding 28.5g of IPDI, 20g of HMDI, 35g of PPG2000, 20g of PTMG2000, 15g of PTMG1000 and 43g of trimethylsilanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 2g of BDO, 2g of HDO, 4.7g of dimethylolbutyric acid, 0.3g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
173g of deionized water is added into the cooled system, and dispersion treatment is carried out under the condition of high-speed shearing;
adding 31.9g of methyl vinyl silicone rubber into the system, uniformly stirring, diluting 5g of isophorone diamine and 5.6g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 40g of deionized water, slowly adding the diluted materials into the system, reacting for 5min at a constant temperature of 35 ℃, and then distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane dispersion with the particle size of 110nm and the solid content of 50%.
Example 3
Adding 15g of IPDI, 36g of HMDI, 35g of PPG2000, 32.5g of PTMG2000, 15g of PTMG1000 and 57.5g of triphenyl silanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 1g of BDO, 2.5g of HDO, 4.5g of dimethylolbutyric acid, 0.4g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
adding 148g of deionized water into the cooled system, and performing dispersion treatment under a high-speed shearing condition;
adding 24.6g of diethyl silicone rubber into the system, stirring uniformly, diluting 3g of isophorone diamine and 3g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 40g of deionized water, slowly adding the diluted materials into the system, reacting for 5min at a constant temperature of 35 ℃, and then distilling the prepared emulsion under reduced pressure to remove acetone, thereby obtaining the blue-light-evident aqueous polyurethane dispersion with the particle size of 100nm and the solid content of 55%.
Example 4
Adding 50g of IPDI, 70PPG2000, 20g of trimethylsilanol and 29.2g of triethylsilanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 6g of BDO, 5g of dimethylolbutyric acid, 0.8 g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, stirring uniformly, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
173g of deionized water is added into the cooled system, and dispersion treatment is carried out under the condition of high-speed shearing;
adding 27g of methyl vinyl silicone rubber into the system, stirring uniformly, diluting 5g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 40g of deionized water, slowly adding into the system, reacting at a constant temperature of 35 ℃ for 5min, and then distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane dispersion with the particle size of 100nm and the solid content of 50%.
Example 5
Adding 42.6g of IPDI, 68.7 g of PPG2000, 24g of trimethylsilanol and 29g of triethylsilanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 6g of BDO, 5g of dimethylolbutyric acid, 0.8 g of organic bismuth Coscat83 and 40g of acetone for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
adding 149g of deionized water into the cooled system, and performing dispersion treatment under a high-speed shearing condition;
adding 31.9g of methyl vinyl silicone rubber into the system, uniformly stirring, diluting 5g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane with 40g of deionized water, slowly adding the diluted solution into the system, reacting at a constant temperature of 35 ℃ for 5min, and then distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident aqueous polyurethane dispersion with the particle size of 100nm and the solid content of 53%.
Comparative example 1
Adding 28.5g of IPDI, 20g of HMDI, 35g of PPG2000, 20g of PTMG2000 and 15g of PTMG1000 into a four-neck flask provided with a reflux condenser, a thermometer and mechanical stirring, reacting at 80 ℃ for 1h, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 2g of BDO, 2g of HDO, 4.7g of dimethylolbutyric acid, 0.3g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
173g of deionized water is added into the cooled system, and dispersion treatment is carried out under the condition of high-speed shearing;
adding 31.9g of methyl vinyl silicone rubber into the system, uniformly stirring, diluting 5g of isophorone diamine and 5.6g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane by using 40g of deionized water, slowly adding the diluted materials into the system, reacting for 5min at a constant temperature of 35 ℃, adding 43g of trimethyl silanol, uniformly stirring, and then distilling the prepared emulsion under reduced pressure to remove acetone to obtain the blue-light-evident waterborne polyurethane dispersion with the particle size of 100nm and the solid content of 50%.
Comparative example 2
Adding 40g of IPDI, 17g of HMDI, 30g of PPG2000, 17g of PTMG2000, 40g of PTMG1000 and 57.5g of trimethylsilanol into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, uniformly mixing, reacting at 80 ℃ for 1 hour, and determining that the NCO content of a system is close to a theoretical value to obtain a prepolymer;
cooling the reaction system to 60 ℃, adding 5g of BDO, 4.2g of HDO, 11.5g of dimethylolbutyric acid, 0.4g of organic bismuth Coscat83 and 40g of acetone into the system for dilution, uniformly stirring, heating the system to 80 ℃ for reaction, and stopping the reaction when the reaction reaches theoretical NCO%; cooling the system to 60 ℃, adding 50g of acetone for dilution, stirring and mixing for 5min to fully mix the prepolymer and the acetone, and continuously cooling to 30-35 ℃;
adding 148g of deionized water into the cooled system, and performing dispersion treatment under a high-speed shearing condition;
2.4g of isophorone diamine and 5g of 1, 3-bis [ (trihydroxymethyl) methylamino ] propane are diluted by 40g of deionized water, slowly added into the system, reacted for 5min at a constant temperature of 35 ℃, and then the prepared emulsion is subjected to reduced pressure distillation to remove acetone, so that the blue-light-evident aqueous polyurethane dispersion with the particle size of 110nm and the solid content of 55% is obtained.
According to the textile printing construction formula shown in the table 1 and the operation steps of the construction process, the aqueous polyurethane dispersions prepared in the examples and the comparative examples are used for preparing textile printing samples, and the test results are shown in the table 2:
TABLE 2 Properties of the textile print samples obtained
Water wash performance/rating Adhesion/scoring Smoothness/score
Example 1 5 5 4
Example 2 5 5 4
Example 3 5 5 4
Example 4 5 5 4
Example 5 5 5 4
Comparative example 1 2 2 2
Comparative example 2 2 2 2
The above experimental results show that: in the synthesis formula of the aqueous polyurethane dispersion, as the silanol added in the prepolymerization stage is grafted on the molecular chain segment of the polymer and generates a synergistic effect with the silicone rubber substances added before the post-chain extension reaction, the effective combination of the aqueous polyurethane dispersion resin and the heavy silicone oil treatment cloth can be improved, and finally the high adhesion, the high washing fastness and the high smoothness of the printing are realized. In the preparation process of the aqueous polyurethane dispersion, if the silanol substances used in the formula are not added in the prepolymerization stage, the synergistic effect of silanol and silicone rubber cannot be realized, and the good combination of the aqueous polyurethane dispersion resin and the heavy silicone oil treatment cloth cannot be further realized; or if the silicone rubber substances are not added in the formula, the good combination of the aqueous polyurethane dispersion resin and the heavy silicone oil treatment cloth can not be achieved, and finally the improvement of the adhesion and the washing fastness of the printing can not be realized.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (9)

1. The aqueous polyurethane dispersion for improving the washing fastness of heavy silicone oil treated cloth is characterized by being prepared from the following components in percentage by weight based on the solid content of the components in the aqueous polyurethane dispersion:
a. isocyanate, 18 to 28% by weight, preferably 20 to 25% by weight;
b. polymer polyol, 28-41 wt%, preferably 32-38 wt%;
c. silanol, 20-30 wt%, preferably 20-25 wt%;
d. a small molecular polyol chain extender having a number average molecular weight of 20 to 100, 1 to 6 wt%, preferably 1.5 to 4 wt%;
e. 1-6 wt%, preferably 2-5 wt% of hydrophilic chain extender containing active hydrogen;
f. silicone rubber, 10-20 wt.%, preferably 10-15 wt.%;
g. the number average molecular weight of the small molecular polyamine chain extender containing active hydrogen is less than 500, 1-6 wt%, and preferably 2-5 wt%.
2. The aqueous polyurethane dispersion according to claim 1, wherein component a is selected from aliphatic and/or cycloaliphatic isocyanates, preferably from one or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and 1, 6-hexyl diisocyanate, and/or
Component b is a polymer polyol having a number average molecular weight of 100-.
3. The aqueous polyurethane dispersion according to claim 1, wherein component c is selected from one or more of trimethylsilanol, triethylsilanol and triphenylsilanol.
4. The aqueous polyurethane dispersion according to claim 1, characterised in that component d is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, 2, 3-butanediol, neopentyl glycol, diethylene glycol and 1, 4-cyclohexanedimethanol, preferably from 1, 4-butanediol and/or 1, 6-hexanediol; and/or
Component e is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid and dimethyloloctanoic acid.
5. The aqueous polyurethane dispersion according to claim 1, wherein component f is selected from one or more of methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, and diethyl silicone rubber.
6. The aqueous polyurethane dispersion according to claim 1, wherein component g is selected from one or more of ethylenediamine, propylenediamine, hexamethylenediamine, 4-diphenylmethanediamine, hydroxyethylethylenediamine, di-n-butylamine, isophoronediamine and 1, 3-bis [ (trimethylol) methylamino ] propane, preferably from one or more of 1, 3-bis [ (trimethylol) methylamino ] propane, hydroxyethylethylenediamine and isophoronediamine.
7. The aqueous polyurethane dispersion according to claim 1, wherein the aqueous polyurethane dispersion has a solid content of 45 to 55 wt.% and a particle diameter of 50 to 200 nm.
8. The process for preparing an aqueous polyurethane dispersion according to any one of claims 1 to 7, comprising the steps of:
(1) mixing the component a, the component b and the component c, reacting, and measuring the NCO content in the system to generate a prepolymer;
(2) adding the component d, the component e and a catalyst into the prepolymer for chain extension reaction, stopping the reaction after theoretical NCO% is reached, and cooling the system;
(3) adding deionized water into the cooled system for dispersion treatment;
(4) and after the dispersion treatment, adding the component f into the system, uniformly mixing, and adding the component g for chain extension reaction to obtain the aqueous polyurethane dispersion.
9. Use of the aqueous polyurethane dispersion according to any one of claims 1 to 7 or of the aqueous polyurethane dispersion obtained by the process according to claim 8 in the fields of clothing, footwear, inks.
CN202111295832.7A 2021-11-03 2021-11-03 Aqueous polyurethane dispersion for improving washing fastness of heavy silicone oil treated cloth and preparation method and application thereof Pending CN113881016A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974287A (en) * 2010-10-27 2011-02-16 大连三达奥克化学股份有限公司 Modified polyurethane coating for flow string renovation and manufacturing method thereof
CN107903358A (en) * 2017-11-21 2018-04-13 鹤山市河本聚脂化工有限公司 Solvent-free self-crosslinking modified aqueous polyurethane resin for printing in textiles
CN108017991A (en) * 2016-08-30 2018-05-11 段宝荣 Fire-retardant, waterproof and the polyurethane coating of low VOC
CN109970948A (en) * 2019-04-10 2019-07-05 武汉纺织大学 A kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974287A (en) * 2010-10-27 2011-02-16 大连三达奥克化学股份有限公司 Modified polyurethane coating for flow string renovation and manufacturing method thereof
CN108017991A (en) * 2016-08-30 2018-05-11 段宝荣 Fire-retardant, waterproof and the polyurethane coating of low VOC
CN107903358A (en) * 2017-11-21 2018-04-13 鹤山市河本聚脂化工有限公司 Solvent-free self-crosslinking modified aqueous polyurethane resin for printing in textiles
CN109970948A (en) * 2019-04-10 2019-07-05 武汉纺织大学 A kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof

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