CN109575226B - Preparation method of environment-friendly extinction type waterborne polyurethane resin - Google Patents
Preparation method of environment-friendly extinction type waterborne polyurethane resin Download PDFInfo
- Publication number
- CN109575226B CN109575226B CN201811396144.8A CN201811396144A CN109575226B CN 109575226 B CN109575226 B CN 109575226B CN 201811396144 A CN201811396144 A CN 201811396144A CN 109575226 B CN109575226 B CN 109575226B
- Authority
- CN
- China
- Prior art keywords
- chain extender
- reaction
- diisocyanate
- extinction
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of environment-friendly delustering waterborne polyurethane resin. Firstly, a polyurethane prepolymer is prepared. Polyethylene glycol reacts with aliphatic diisocyanate such as isophorone diisocyanate or hexamethylene diisocyanate, and then carboxylic acid type hydrophilic chain extender and polyether polyol are sequentially added to prepare the waterborne polyurethane prepolymer. The second step is a water dispersion and post-chain extension process. Adding deionized water into the waterborne polyurethane prepolymer for dispersion, and sequentially dripping a rear chain extender 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and a hydrazine hydrate aqueous solution to obtain the environment-friendly extinction waterborne polyurethane resin. The invention has the advantages that the extinction type waterborne polyurethane resin is prepared by adopting a chemical extinction method, the preparation process is simple, and no organic solvent or extinction agent is added. The resin emulsion has good stability, high solid content, good mechanical property of an adhesive film, good water resistance, glossiness (60 degrees) of less than 2.0, light transmittance (%) <11 and solid content of 45-50%.
Description
Technical Field
The invention relates to a preparation method of an environment-friendly extinction type waterborne polyurethane resin.
Background
With the change of aesthetic concept, the extinction coating is more popular for decorating the surface of the material. The matte coating on the surface of materials such as leather, fiber fabric, paper, etc. can produce very natural optical appearance, comfortable tactile sensation, and can mask fine scratches, dirt and fingerprints. The matting effect depends primarily on the ability of the coating surface to reflect light. The high light material surface has strong ability to reflect light, while the extinction material surface mainly generates refraction of light or reduces the intensity of reflected light.
The conventional matting method for the surface of a material is a physical matting method, that is, a large amount of a matting agent such as silica powder is added to a resin to produce a matting effect. The disadvantages of this method are: first, the matting agent added to the coating material is liable to settle with time, and causes uneven dyeing during printing, resulting in uneven surface gloss of the final material. Second, the compatibility of the resin with the matting agent is generally poor and the coating easily peels off. The gloss level also increases with time. Thirdly, due to the condensation of the matting agent inside the coating, the surface of the printed material can generate an uneven effect, and the flexibility of the material is reduced.
Some conventional coatings contain large amounts of organic solvents, which adversely affect human health and the environment.
The preparation method of the environment-friendly extinction type polyurethane resin adopts a novel chemical extinction method, does not need to add any extinction agent, and generates the extinction effect in the polyurethane resin drying process. The preparation method is different from the traditional preparation method of waterborne polyurethane, and a large amount of organic solvent is not needed to be added in the preparation process to reduce the viscosity of the reaction system. The technical characteristics are as follows: (1) in the process of synthesizing the waterborne polyurethane, sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate and hydrazine hydrate are used as a rear chain extender and also as an internal emulsifier. The use of the hydrophilic chain extender DMPA in an excessive amount can reduce the hardness and the water resistance of a coating film, but the method of the invention can increase the hydrolytic stability and the thermal stability of the polyurethane film by connecting the 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt to the polyurethane skeleton. More importantly, if the sodium 2- [ (2-aminoethyl) amino ] ethanesulfonate is used in a suitable amount, it can form a large amount of latex particles with stereoregular spherical shapes in the polyurethane emulsion, thereby producing a significant matting effect on the coating surface. In addition, the combined use of the two chain extenders can also effectively prevent the deformation of the latex particles, thereby generating a delustering effect on the surface of the coating. (2) The aqueous polyurethane prepared by singly using the DMPA ionic monomer as the hydrophilic chain extender is sensitive to both the pH value and the electrolyte. And the more DMPA is used, the larger the emulsion viscosity is, the smaller the particle size is, the higher the film gloss is, a large amount of organic solvent is needed to reduce the system viscosity in the preparation process, and the solid content of the emulsion is reduced. The preparation method of the invention uses the synergistic effect of the nonionic hydrophilic monomer polyethylene glycol and the ionic monomer to synthesize the delustering type aqueous polyurethane, and reasonably designs the formula composition and the process method, thereby not only greatly reducing the usage amount of DMPA (2.2-2.4%), but also increasing the dispersion stability of the aqueous polyurethane, leading the aqueous polyurethane prepolymer to be easily dispersed in a small amount of water, and increasing the solid content of the dispersion (45-50%). In the preparation process, only a small amount of organic solvent (5-10%) is used, and the finished product can be directly coated and used, even if the residual organic solvent is removed easily. (3) In the reaction sequence of the polyol and the hydrophilic chain extender DMPA with the isocyanate, the isocyanate is firstly reacted with the nonionic hydrophilic monomer polyethylene glycol and then sequentially reacted with the ionic hydrophilic chain extender DMPA and the polytetrahydrofuran ether, so that hydrophilic groups can be preferentially occupied on a polyurethane macromolecular main chain, and the optimal effect of improving the dispersion stability of the emulsion is achieved. (4) The extinction type waterborne polyurethane resin prepared by the invention has the advantages of obvious extinction effect, high resin solid content, good hydrolytic stability and good mechanical property of a glue film. Gloss (60 °) <2.0, light transmittance (%) <11, solid content 45-50%.
Disclosure of Invention
In order to overcome the defects of the prior traditional extinction waterborne polyurethane preparation technology, the invention is a preparation method of environment-friendly extinction waterborne polyurethane resin.
The preparation method of the environment-friendly extinction type waterborne polyurethane resin comprises the following steps and conditions:
the environment-friendly extinction type waterborne polyurethane resin disclosed by the invention comprises the following materials in percentage by mass:
formula 1:
1-3% of polyethylene glycol;
33.7 to 36.2 percent of diisocyanate;
polytetrahydrofuran ether glycol 55.6-60.1%
0.015% of catalyst;
2.2 to 2.4 percent of carboxylic acid type hydrophilic chain extender;
1.65 to 1.81 percent of neutralizer;
rear chain extender A0.4-0.9%
Rear chain extender B0.4-0.7%;
the molecular weight Mn of the polyethylene glycol is 400, 600, 1000 and 2000;
the molecular weight Mn of the polytetrahydrofuran ether glycol is 1000;
the diisocyanate is isophorone diisocyanate;
the catalyst is organic bismuth;
the carboxylic acid type hydrophilic chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid;
the rear chain extender A is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt; (ii) a
The rear chain extender B is hydrazine hydrate water;
and (2) formula:
1-3% of polyethylene glycol;
27.7 to 33.6 percent of diisocyanate;
polytetrahydrofuran ether glycol 60.2-67.3%
0.015% of catalyst;
2.2 to 2.4 percent of carboxylic acid type hydrophilic chain extender;
1.65 to 1.81 percent of neutralizer;
rear chain extender A0.4-0.9%
Rear chain extender B0.4-0.7%;
the molecular weight Mn of the polyethylene glycol is 400, 600, 1000 and 2000;
the molecular weight Mn of the polytetrahydrofuran ether glycol is 1000;
the diisocyanate is hexamethylene diisocyanate;
the catalyst is organic bismuth;
the carboxylic acid type hydrophilic chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid;
the neutralizing agent is triethylamine
The rear chain extender A is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt; (ii) a
The rear chain extender B is hydrazine hydrate;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200rd/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300rd/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour.
(2) Heating the oil bath to 83 ℃, keeping the stirring speed at 300rd/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding 5-10% (the mass of the prepolymer is 100%) of acetone for dilution, and then adding triethylamine to neutralize carboxylic acid for salt formation to obtain a prepolymer with an NCO end group;
(3) deionized water with the temperature of 30 ℃ is added into the prepolymer with the NCO end group for dispersion, and the stirring speed is 1000 rd/min. Sequentially dripping the 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and the hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction for 30 minutes;
(4) removing acetone in the system under certain conditions (the temperature is 40 ℃, and the vacuum degree is-0.09 MPa) to obtain the environment-friendly extinction type waterborne polyurethane resin.
Detailed Description
Example 1 a method for preparing an environment-friendly matting aqueous polyurethane resin, comprising the steps of:
the environment-friendly extinction type waterborne polyurethane resin comprises the following materials in percentage by mass:
1% of polyethylene glycol, 34.8% of diisocyanate, 59.5% of polytetrahydrofuran ether glycol, 0.015% of catalyst, 2.2% of carboxylic acid type hydrophilic chain extender, 1.65% of neutralizer and 0.41% of rear chain extender A; and the rear chain extender B is 0.43 percent.
The specific addition amounts are as follows: the molecular weight of the polyethylene glycol is 400, and the mass is 1 g; the diisocyanate was isophorone diisocyanate, with a mass of 38.4 g; the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the mass is 59.5 g; the catalyst is organic bismuth, the mass is 0.015 g; the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid, and the mass is 2.2 g; the neutralizing agent is triethylamine, and the mass is 1.65 g; the rear chain extender A is 2- [ (2-aminoethyl) amino ] sodium ethanesulfonate with the mass of 0.41g, and the rear chain extender B is hydrazine hydrate with the mass of 0.43 g;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200rd/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300rd/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour.
(2) Heating the oil bath to 83 ℃, keeping the stirring speed at 300rd/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding 5% (the mass of the prepolymer is 100%) of acetone for dilution, and then adding triethylamine to neutralize carboxylic acid for salifying to obtain a prepolymer with an NCO end group;
(3) deionized water with the temperature of 30 ℃ is added into the prepolymer with the NCO end group for dispersion, and the stirring speed is 1000 rd/min. Sequentially dripping the 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and the hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction for 30 minutes;
(4) removing acetone in the system under certain conditions (the temperature is 40 ℃, and the vacuum degree is-0.09 MPa) to obtain the environment-friendly extinction type waterborne polyurethane resin.
Embodiment 2 a method for preparing an environment-friendly extinction type aqueous polyurethane resin, comprising the steps of:
the environment-friendly extinction type waterborne polyurethane resin comprises the following materials in percentage by mass:
3% of polyethylene glycol, 34% of diisocyanate, 57.3% of polytetrahydrofuran ether glycol, 0.015% of catalyst, 2.4% of carboxylic acid type hydrophilic chain extender, 1.81% of neutralizing agent and 0.84% of rear chain extender A; and the rear chain extender B is 0.64 percent.
The specific addition amounts are as follows: the molecular weight of the polyethylene glycol is 2000, and the mass is 3 g; the diisocyanate is isophorone diisocyanate and has the mass of 34 g; the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the mass is 57.3 g; the catalyst is organic bismuth, the mass is 0.015 g; the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid, and the mass is 2.4 g; the neutralizing agent is triethylamine, and the mass of the neutralizing agent is 1.81 g; the rear chain extender A is 2- [ (2-aminoethyl) amino ] sodium ethanesulfonate with the mass of 0.84g, and the rear chain extender B is hydrazine hydrate with the mass of 0.64 g;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200rd/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300rd/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour.
(2) Heating the oil bath to 83 ℃, keeping the stirring speed at 300rd/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding 7% (the mass of the prepolymer is 100%) of acetone for dilution, and then adding triethylamine to neutralize carboxylic acid for salifying to obtain a prepolymer with an NCO end group;
(3) deionized water with the temperature of 30 ℃ is added into the prepolymer with the NCO end group for dispersion, and the stirring speed is 1000 rd/min. Sequentially dripping the 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and the hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction for 30 minutes;
(4) removing acetone in the system under certain conditions (the temperature is 40 ℃, and the vacuum degree is-0.09 MPa) to obtain the environment-friendly extinction type waterborne polyurethane resin.
Embodiment 3 a method for preparing an environment-friendly extinction type aqueous polyurethane resin, comprising the steps of:
the environment-friendly extinction type waterborne polyurethane resin comprises the following materials in percentage by mass:
2% of polyethylene glycol, 34.3% of diisocyanate, 58.9% of polytetrahydrofuran ether glycol, 0.015% of catalyst, 2.2% of carboxylic acid type hydrophilic chain extender, 1.65% of neutralizer and 0.52% of rear chain extender A; and the rear chain extender B is 0.42 percent.
The specific addition amounts are as follows: the molecular weight of the polyethylene glycol is 1000, and the mass is 2 g; the diisocyanate was isophorone diisocyanate, with a mass of 34.3 g; the molecular weight of the polytetrahydrofuran ether glycol is 1000, and the mass is 58.9 g; the catalyst is organic bismuth, the mass is 0.015 g; the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid, and the mass is 2.2 g; the neutralizing agent is triethylamine, and the mass is 1.65 g; the rear chain extender A is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt with the mass of 0.52g, and the rear chain extender B is hydrazine hydrate with the mass of 0.42 g;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200rd/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300rd/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour.
(2) Heating the oil bath to 83 ℃, keeping the stirring speed at 300rd/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding 7% (the mass of the prepolymer is 100%) of acetone for dilution, and then adding triethylamine to neutralize carboxylic acid for salifying to obtain a prepolymer with an NCO end group;
(3) deionized water with the temperature of 30 ℃ is added into the prepolymer with the NCO end group for dispersion, and the stirring speed is 1000 rd/min. Sequentially dripping the 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and the hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction for 30 minutes;
(4) removing acetone in the system under certain conditions (the temperature is 40 ℃, and the vacuum degree is-0.09 MPa) to obtain the environment-friendly extinction type waterborne polyurethane resin.
The physical properties and adhesive film properties of the environmentally friendly matting type aqueous urethane resins of examples 1 to 3 were measured.
The detection method comprises the following steps:
solid content determination: weighing quantitative polyurethane emulsion M1Spreading on a watch glass with a diameter of 40mm, drying in an oven at 110 deg.C until the weight is constant, and weighing the mass M of the solid material in the watch glass2. The solids content was calculated as follows:
C(%)=M2/ M1×100%
in the formula: c-polyurethane resin solid content (%); m1-polyurethane emulsion mass (g); m2Mass of solid (g)
Testing the particle size of the emulsion: the particle size was measured by a particle size analyzer using dynamic light scattering. The emulsion particle size test was performed at 25 ℃. The polyurethane emulsion was first diluted with distilled water to a concentration of 0.5% prior to testing.
And (3) centrifugal stability determination: a certain amount of polyurethane emulsion is filled in a centrifuge tube, the centrifuge tube is placed in a centrifuge, the polyurethane emulsion is centrifuged for 15 min at the temperature of 25 ℃ and the rotating speed of 3000 r/min, the stability of the emulsion is evaluated by observing the state of the emulsion, and if no layering or precipitation exists, the polyurethane emulsion can be considered to be stable after being placed at normal temperature for 6 months.
And (3) testing the glossiness: and measuring the glossiness of the polyurethane adhesive film by using a single-angle gloss meter. All tests used 60 degree incidence angles.
And (3) testing light transmittance: the light transmittance of the polyurethane adhesive film was measured by a haze meter. The thickness of the adhesive film is 0.5mm.
And (3) testing mechanical properties: the polyurethane adhesive film is cut into a standard sample (dumbbell shape), the test is carried out on an electronic tensile testing machine, the test temperature is 25 ℃, the tensile speed is 100mm/min, and the measurement result is the average value of the three test results.
Water absorption test: cutting the dried polyurethane adhesive film into sample blocks of 1cm multiplied by 1cm, measuring the mass of the sample block film at 25 ℃, then soaking the sample block film in deionized water at 25 ℃ for 24 hours at room temperature, sucking water on the surface of the sample block film by using filter paper, weighing the mass of the sample block film, and calculating the water absorption rate according to the following formula:
W =［(M2 －M1) / M1］× 100%
wherein W is the water absorption (%) of the sample film, M1Mass (g) before immersion of sample film, M2The mass (g) of the sample film after immersion.
TABLE 1 Environment-friendly extinction type aqueous polyurethane emulsion performance table
TABLE 2 Environment-friendly extinction type waterborne polyurethane film performance table
TABLE 1 Environment-friendly extinction type aqueous polyurethane emulsion performance table
TABLE 2 Environment-friendly extinction type waterborne polyurethane film performance table
Claims (2)
1. The preparation method of the environment-friendly extinction type waterborne polyurethane resin is characterized by comprising the following materials in percentage by mass:
1-3% of polyethylene glycol;
33.7 to 36.2 percent of diisocyanate;
polytetrahydrofuran ether glycol 55.6-60.1%
0.015% of catalyst;
2.2 to 2.4 percent of carboxylic acid type hydrophilic chain extender;
1.65 to 1.81 percent of neutralizer;
rear chain extender A0.4-0.9%
Rear chain extender B0.4-0.7%;
the molecular weight Mn of the polyethylene glycol is 400, 600, 1000 and 2000;
the molecular weight Mn of the polytetrahydrofuran ether glycol is 1000;
the diisocyanate is isophorone diisocyanate;
the catalyst is organic bismuth;
the carboxylic acid type hydrophilic chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid;
the neutralizing agent is triethylamine
The rear chain extender A is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the rear chain extender B is hydrazine hydrate;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200 r/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300 r/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour;
(2) heating the oil bath to 83 ℃, keeping the stirring speed at 300 r/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding acetone accounting for 5-10% of the total mass of the prepolymer into the system for dilution, and then adding triethylamine to neutralize carboxylic acid for salt formation to obtain a prepolymer with an NCO end group;
(3) adding deionized water with the temperature of 30 ℃ into a prepolymer of an NCO end group for dispersion, wherein the stirring speed is 1000 r/min, and sequentially dripping 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction, wherein the reaction time is 30 minutes;
(4) removing acetone in the system at the temperature of 40 ℃ and the vacuum degree of-0.09 MPa to obtain the organic solvent-free extinction aqueous polyurethane resin.
2. A preparation method of environment-friendly extinction type water-based polyurethane resin is characterized in that,
1-3% of polyethylene glycol;
27.7 to 33.6 percent of diisocyanate;
polytetrahydrofuran ether glycol 60.2-67.3%
0.015% of catalyst;
2.2 to 2.4 percent of carboxylic acid type hydrophilic chain extender;
1.65 to 1.81 percent of neutralizer;
rear chain extender A0.4-0.9%
Rear chain extender B0.4-0.7%;
the molecular weight Mn of the polyethylene glycol is 400, 600, 1000 and 2000;
the molecular weight Mn of the polytetrahydrofuran ether glycol is 1000;
the diisocyanate is hexamethylene diisocyanate;
the catalyst is organic bismuth;
the carboxylic acid type hydrophilic chain extender is one or two of dimethylolpropionic acid and dimethylolbutyric acid;
the neutralizing agent is triethylamine
The rear chain extender A is 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the rear chain extender B is hydrazine hydrate;
the preparation steps and conditions were as follows:
(1) adding polyethylene glycol into a reaction vessel, heating in an oil bath at 50 ℃ and mechanically stirring at 200 r/min, adding diisocyanate and a catalyst into a reaction system, increasing the stirring speed to 300 r/min, increasing the reaction temperature to 83 ℃, and carrying out heat preservation reaction for 1 hour; then reducing the reaction temperature to 70 ℃, adding a carboxylic acid type hydrophilic chain extender into the reaction system, and carrying out heat preservation reaction for 1 hour;
(2) heating the oil bath to 83 ℃, keeping the stirring speed at 300 r/min, adding polytetrahydrofuran ether glycol into the reaction system, and reacting for 1.5 hours under the condition of heat preservation; when the mass fraction of NCO in the reaction system reaches 50%, reducing the temperature of the system to 50 ℃, adding acetone accounting for 5-10% of the total mass of the prepolymer into the system for dilution, and then adding triethylamine to neutralize carboxylic acid for salt formation to obtain a prepolymer with an NCO end group;
(3) adding deionized water with the temperature of 30 ℃ into a prepolymer of an NCO end group for dispersion, wherein the stirring speed is 1000 r/min, and sequentially dripping 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt aqueous solution and hydrazine hydrate aqueous solution into the aqueous polyurethane dispersion at the dripping speed of 3-4g/min for post-chain extension reaction, wherein the reaction time is 30 minutes;
(4) removing acetone in the system at the temperature of 40 ℃ and the vacuum degree of-0.09 MPa to obtain the organic solvent-free extinction aqueous polyurethane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811396144.8A CN109575226B (en) | 2018-11-22 | 2018-11-22 | Preparation method of environment-friendly extinction type waterborne polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811396144.8A CN109575226B (en) | 2018-11-22 | 2018-11-22 | Preparation method of environment-friendly extinction type waterborne polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109575226A CN109575226A (en) | 2019-04-05 |
| CN109575226B true CN109575226B (en) | 2021-06-08 |
Family
ID=65923357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811396144.8A Expired - Fee Related CN109575226B (en) | 2018-11-22 | 2018-11-22 | Preparation method of environment-friendly extinction type waterborne polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575226B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280003A (en) * | 2020-11-04 | 2021-01-29 | 湖南中泰特种装备有限责任公司 | Copolymerization type extinction aqueous polyurethane emulsion and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912093A (en) * | 1997-05-15 | 1999-06-15 | National Science Council | Polyurethane-based polymeric electrolyte and process for producing same |
| US6077897A (en) * | 1997-12-01 | 2000-06-20 | Wen; Ten-Chin | Polymeric composite electrolyte and process for producing same |
| CN102485763A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院福建物质结构研究所 | Preparation of water dispersible polyurethane |
| CN102492110A (en) * | 2011-12-07 | 2012-06-13 | 富思特新材料科技有限公司 | Preparation method for waterborne polyurethane applied to elastic coating |
| CN105801810A (en) * | 2016-05-18 | 2016-07-27 | 长春工业大学 | Preparation method of high-glossiness high-water-permeability polyurethane resin |
| CN106380569A (en) * | 2016-09-27 | 2017-02-08 | 华南理工大学 | Water-based polyurethane anti-glare coating material and preparation method thereof |
-
2018
- 2018-11-22 CN CN201811396144.8A patent/CN109575226B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912093A (en) * | 1997-05-15 | 1999-06-15 | National Science Council | Polyurethane-based polymeric electrolyte and process for producing same |
| US6077897A (en) * | 1997-12-01 | 2000-06-20 | Wen; Ten-Chin | Polymeric composite electrolyte and process for producing same |
| CN102485763A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院福建物质结构研究所 | Preparation of water dispersible polyurethane |
| CN102492110A (en) * | 2011-12-07 | 2012-06-13 | 富思特新材料科技有限公司 | Preparation method for waterborne polyurethane applied to elastic coating |
| CN105801810A (en) * | 2016-05-18 | 2016-07-27 | 长春工业大学 | Preparation method of high-glossiness high-water-permeability polyurethane resin |
| CN106380569A (en) * | 2016-09-27 | 2017-02-08 | 华南理工大学 | Water-based polyurethane anti-glare coating material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《Effects of the reagent molar ratio on the phase separation and properties of waterborne polyurethane for application in a water‐based ink binder》;Yang Zhihui .etc;《JOURNAL OF APPLIED POLYMER SCIENCE》;wiley;20170716;第134卷(第42期);第45406（1-11）页 * |
| 《水性聚氨酯防水涂膜材料的制备与性能》;杨智慧，吴广峰;《材料保护》;机械院武汉材料保护研究所;20171031;第50卷(第10期);第61-64页 * |
| 水性UV固化聚氨酯丙烯酸酯涂料的制备及其合成工艺的研究;李红强等;《涂料工业》;20070701(第07期);第1-4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109575226A (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867388B (en) | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof | |
| CN101225150B (en) | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer and its uses | |
| JP3493796B2 (en) | Waterborne polyurethane resin paint | |
| Yong et al. | Synthesis and characterization of solvent-free waterborne polyurethane dispersion with both sulfonic and carboxylic hydrophilic chain-extending agents for matt coating applications | |
| ES2927734T3 (en) | Radiation-curable aqueous compositions with controlled polymer flow | |
| CN104212330B (en) | A kind of preparation method of baking vanish type water-polyurethane/amido resin compounded emulsion | |
| CN106380569B (en) | A kind of aqueous polyurethane Anti Glare Coatings material and preparation method thereof | |
| CN106752851B (en) | A kind of preparation method of the composite modified aqueous polyurethane matting resin of organic/inorganic silicon | |
| CN108840987A (en) | The polyalcohol modified aqueous polyurethane emulsion of organosilicon and preparation method | |
| CN105801810B (en) | A kind of preparation method of bloom high water-permeability polyurethane resin | |
| CN111944111B (en) | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof | |
| CN107141442A (en) | A kind of method of terminal hydroxy liquid modified rubber aqueous polyurethane matting resin | |
| CN108822675A (en) | A kind of leather aqueous coating agent, preparation method and roll coating process | |
| CN109535372B (en) | Waterborne polyurethane and preparation method thereof | |
| CN108329342B (en) | Organic silicon coupling agent and preparation method and application thereof | |
| CN105175670B (en) | A kind of amino resins modified aqueous polyurethane and preparation method and application | |
| CN109575226B (en) | Preparation method of environment-friendly extinction type waterborne polyurethane resin | |
| CN110982017A (en) | Self-extinction aqueous acrylic acid-polyurethane core-shell emulsion and preparation method thereof | |
| CN106009903B (en) | A kind of preparation method of low crystallization aqueous polyurethane oil ink connecting material | |
| CN105622886A (en) | Alcohol/water-soluble polyurethane resin used for intaglio ink and preparation method thereof | |
| CN108997554B (en) | Organosilicon modified polyurethane emulsion, paint, and preparation method and application thereof | |
| CN109251300B (en) | Cross-linked sulfonic acid and carboxylic acid salt aqueous polyurethane emulsion and preparation method thereof | |
| Ou et al. | Preparation, properties, and applications of acrylic–polyurethane hybrid emulsions in extinction electrophoresis | |
| CN103275298B (en) | A kind of organosilicon modified aqueous polyurethane resin and preparation method thereof | |
| CN112961315B (en) | Preparation method of fluorine-containing polyurethane leather waterproof coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210608 Termination date: 20211122 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |