CN113185643A - Synthesis and application of modified aqueous polyurethane resin dispersoid - Google Patents
Synthesis and application of modified aqueous polyurethane resin dispersoid Download PDFInfo
- Publication number
- CN113185643A CN113185643A CN202110438721.0A CN202110438721A CN113185643A CN 113185643 A CN113185643 A CN 113185643A CN 202110438721 A CN202110438721 A CN 202110438721A CN 113185643 A CN113185643 A CN 113185643A
- Authority
- CN
- China
- Prior art keywords
- modified
- glycol
- polyol
- acrylate
- diisocyanate
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
- C08G18/30—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/42—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
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a synthetic method of a modified waterborne polyurethane resin dispersoid, which comprises the following steps: synthesizing isocyanate-terminated prepolymer, adding part of modified monomer, low-boiling-point organic solvent and isocyanate-terminated prepolymer for full dissolution, obtaining pre-modified emulsion under high-speed shearing, adding the other part of modified monomer into the pre-modified emulsion, carrying out free radical polymerization, and finally adding amino-functional nonionic hydrophilic polyoxyethylene ether. The modified waterborne polyurethane resin dispersion paint film prepared by the preparation method provided by the invention has good chemical resistance, long two-component construction activation period and good odor-removing effect, and is particularly suitable for the application in the field of environment-friendly two-component high-resistance wood paint.
Description
Technical Field
The invention belongs to the field of waterborne wood lacquer coatings, and particularly relates to a modified waterborne polyurethane resin dispersoid for preparing environment-friendly two-component wood lacquer with good chemical resistance, long two-component construction activation period and good odor purification effect.
Background
In recent years, with the coming of national environmental protection policy, the water-based wood lacquer has been developed greatly. Although the water-based wood lacquer is more environment-friendly, downstream customers generally reflect that the water-based wood lacquer has a large smell in the drying process, even is more serious than part of oil-based paint, and particularly has obvious performance when being coated in closed spaces such as cabinets and the like, thereby influencing the use feeling. With the continuous improvement of the performance requirements of the downstream waterborne wood lacquer, the future dual-component coating will gradually become the mainstream, which puts higher requirements on the dual-component activation period stability of the emulsion, and the more stable viscosity change and longer open time are the key points of the performance. In high-grade solid wood coating, better single-component resistance, excellent activation period performance and good odor-free effect are the primary investigation items for screening emulsions by downstream customers.
Chinese patent application CN104220474A discloses a preparation method of ketone hydrazine crosslinking modified waterborne polyurethane for waterborne wood lacquer, acrylic ester (methyl methacrylate, butyl methacrylate and n-butyl acrylate) is used for modifying waterborne polyurethane, diacetone acrylamide is added, introduced onto the acrylate polymer segment during free radical addition polymerization of the acrylate monomer, followed by addition of an amine or hydrazide group reactive with the carbonyl group, the PA chain segment ketone hydrazine crosslinking is realized in the film forming, dehydrating and surface drying process, the resin prepared by the method has poor water resistance and chemical resistance of a paint film due to the introduction of a hydrophilic hydrazide group and low ketone hydrazine crosslinking efficiency, and although the neutralization by introducing hard alkali has a certain odor-removing effect, the alkali metal ions have extremely poor water resistance, so that the application of the high-end wood lacquer field has certain limitation.
Chinese patent application CN108164650A discloses a method for synthesizing an end-alkenyl non-ionic waterborne polyurethane modified acrylate emulsion, which comprises the steps of synthesizing a double-bond-containing non-ionic waterborne polyurethane monomer by using end-alkenyl polyethylene glycol, and polymerizing the acrylate monomer and the prepared end-alkenyl polyurethane by an emulsion polymerization method to obtain a waterborne polyurethane modified acrylate resin.
Therefore, how to develop the waterborne wood lacquer resin with excellent chemical resistance, long two-component activation time and good odor-removing effect becomes one of the technical difficulties to be solved urgently in the field.
Disclosure of Invention
The preparation method provided by the invention not only has simple and controllable preparation process, but also has low cost, excellent performance and good odor-removing effect of the synthesized resin, and meets the requirement of the dual-component wood lacquer coating on ultra-long activation period.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides a method for preparing a modified aqueous polyurethane resin dispersion, comprising the steps of:
1) synthesizing an isocyanate terminated prepolymer;
2) adding a part of modified monomer, a low-boiling-point organic solvent and the isocyanate-terminated prepolymer, fully mixing and dissolving, and dispersing under high-speed shearing after neutralization reaction to obtain a pre-modified emulsion;
3) adding another part of modified monomer into the pre-modified emulsion, fully and uniformly swelling, and adding an initiator to initiate polymerization;
4) and removing the low-boiling-point organic solvent, and then adding amino-functional nonionic hydrophilic polyoxyethylene ether to obtain the modified aqueous polyurethane resin dispersion.
In the preparation method, in step 1), the isocyanate-terminated prepolymer is prepared by mixing and reacting raw materials comprising the following components: polyisocyanate, macromolecular polyol and chain extender;
wherein the polyisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hexahydrotoluene diisocyanate, trimethylhexane diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate and dicyclohexylmethane diisocyanate, and dicyclohexylmethane diisocyanate is preferred;
wherein the number average molecular weight of the macromolecular polyol is 800-4000, preferably 1000-3000, and the macromolecular polyol comprises at least one of polyether polyol, polyester polyol, polycarbonate polyol, phthalic anhydride polyester polyol, dimer acid polyester polyol and hydroxyl-terminated polyolefin glycol, such as one or more of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetrahydrofuran ether glycol, dimer acid polyester polyol, polyolefin polyol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol and 1, 6-hexanediol adipate diol; preferably a dimer acid polyester polyol having a number average molecular weight of 1000-3000, more preferably a dimer acid polyester polyol having a number average molecular weight of 2000; the dimer acid is a natural oil product, has the characteristics of low toxicity, wide source and reproducibility, has noncrystallization, high flexibility and excellent chemical and water resistance due to the fact that the dimer acid contains two carboxyl groups and larger nonpolar hydrocarbon groups, and a long carbon chain consisting of a high-degree branch structure and 36 carbon atoms, and the performance of the synthesized polyurethane resin is superior to that of the traditional polyether polyester polyurethane;
the chain extender comprises a micromolecular polyol chain extender and a carboxylic acid type hydrophilic chain extender; the molecular weight of the chain extender of the small molecular polyol is preferably 30-200g/mol, and the chain extender of the small molecular polyol preferably comprises one or more of trimethylolpropane, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the carboxylic acid type hydrophilic chain extender preferably comprises a small molecule diol compound with a carboxylate group, and further preferably comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid and N, N-dimethylolmaleamic acid;
in the production method of the present invention, it is preferable that the raw materials for producing the isocyanate terminated prepolymer include the following components in the following amounts, based on the total mass of the raw materials for producing the isocyanate terminated prepolymer: 30-40 wt% of polyisocyanate, 6-15 wt% of chain extender and macromolecular polyol with the molar ratio of the macromolecular polyol to the polyisocyanate being 1:4.5-1: 5.5; in the chain extender, the use amounts of the micromolecule polyalcohol chain extender and the carboxylic acid type hydrophilic chain extender are respectively 3-6 wt% and 3-9 wt%. The isocyanate-terminated prepolymer may be prepared by a method conventional in the art, and preferably, the reaction temperature is 70 to 80 ℃.
In the preparation method of the present invention, step 2), the modifying monomer includes at least one of ethylenically unsaturated monomers, preferably, one or more of methyl (meth) acrylate, ethyl (meth) acrylate, hydroxypropyl acrylate, propyl acrylate, butyl (meth) acrylate, hydroxyethyl methacrylate, tetrahydrofuran acrylate, (meth) styrene, isobornyl acrylate and isooctyl acrylate, preferably styrene and/or methyl methacrylate; preferably, the amount of the modifying monomer is 0.1 to 1 times, preferably 0.3 to 0.6 times, the amount of the isocyanate-terminated prepolymer, wherein 40 to 60% is added in step 2). The low monomer consumption is not beneficial to the generation of free radical polymerization reaction; the emulsion is unstable due to the explosive polymerization of free radicals and slag discharge caused by high dosage, and the lowest film forming temperature is increased, so that the environment-friendly concept of low VOC is not met.
In step 2), the low-boiling organic solvent is an organic solvent with a boiling point lower than 100 ℃, preferably acetone, and the amount of the low-boiling solvent is preferably 0.5 to 1.2 times of the amount of the isocyanate-terminated prepolymer in step 1).
The mixing and dissolving of the modifying monomer with the isocyanate terminated prepolymer is preferably carried out at 46 to 56 ℃.
In the preparation method of the invention, in the step 2), the neutralizing agent used in the neutralization reaction comprises one or more of sodium hydroxide, potassium hydroxide, triethylamine, N, N-dimethylethanolamine, dimethylcyclohexylamine, triethanolamine, methyldiethanolamine, diisopropanolamine, ethyldiisopropylamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol and ammonia water. Preferred neutralizing agents are triethylamine and/or N, N-dimethylethanolamine, particularly preferably N, N-dimethylethanolamine. The degree of neutralization is 70 to 120% of the molar amount of carboxyl groups in the isocyanate terminated prepolymer, preferably 80 to 90%.
In the preparation method, in the step 3), the using amount of the initiator is 0.05-0.5% of the total mass of the modified monomer, and preferably 0.1-0.3%;
preferably, the initiator comprises an oxidizing agent and a reducing agent;
the oxidant comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate and tert-butyl hydroperoxide;
the reducing agent comprises one or more of sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium hydrogen sulfite and isoascorbic acid.
The initiation temperature of the pre-modified emulsion initiated polymerization is 32-37 ℃.
In the preparation method of the present invention, in step 4), the amount of the amino-functional nonionic hydrophilic polyoxyethylene ether is preferably 0.5% to 1% based on the mass of the isocyanate terminated prepolymer;
the number average molecular weight of the amino-functional nonionic hydrophilic polyoxyethylene ether is 500-5000, and the amino-functional nonionic hydrophilic polyoxyethylene ether comprises one or more of amino-terminated polyether of polyethylene glycol, amino-terminated polyether of polypropylene glycol and amino-terminated polyether copolymerized in different proportions of ethylene glycol/propylene glycol, and preferably monoamino-functional polyoxyethylene ether with the number average molecular weight of 800-2000 and the molar ratio of ethylene glycol to propylene glycol of 5-8: 1. Different polyoxyalkylene structures are selected, and the application properties of the prepared resin are completely different by utilizing the difference of hydrophilicity and reactivity. The HLB value of the pure polyethylene glycol structure is too high, and the hydrophilicity is too strong, so that the chemical resistance of a final paint film is reduced; the polypropylene glycol accounts for too high, so that the emulsifying and dispersing effects of the polypropylene glycol are poor, particularly, the double-component curing agent cannot be fully emulsified, and the thickening response of the system is good due to the increase of the hydrophobic structure of the polypropylene glycol, so that the activation period is shortened finally.
The second aspect of the invention provides the application of the modified aqueous polyurethane resin dispersion prepared by the preparation method, and the modified aqueous polyurethane resin dispersion is preferably suitable for preparing wood paint, and particularly preferably used for preparing two-component wood paint with an ultra-long activation period.
The third aspect of the invention also provides a wood lacquer coating, which comprises the modified aqueous polyurethane resin dispersoid prepared by the preparation method.
The technical scheme provided by the invention has the following beneficial effects:
the resin prepared by the invention is surprisingly found that the chemical resistance and mechanical property of the resin are obviously improved compared with the traditional acrylate modified polyurethane by introducing dimer acid polyester polyol through a polyurethane segment, mainly because the dimer acid contains two carboxyl groups and larger nonpolar hydrocarbon groups, the high branch structure of the dimer acid and a long carbon chain formed by 36 carbon atoms ensure that the dimer acid has non-crystallinity, high flexibility and excellent chemical resistance, and has auxiliary improvement effect on the chemical resistance of the dimer acid due to the characteristic that partial ester groups of acrylate are easy to hydrolyze, and the performance of the synthesized acrylate modified polyurethane resin is superior to that of the traditional acrylate modified polyether polyester polyurethane resin product.
The resin prepared by the invention has the stability of the two-component activation period for a super-long time; the amino-functional nonionic hydrophilic polyoxyethylene ether is added in the back section of resin synthesis to be dissociated in the resin, and the hydrophilicity of the curing agent is improved by reaction with the curing agent in the using process of the two-component paint, so that the thickening response of the system is stabilized in a certain range, the viscosity of the system is continuously stable, the open time of the finished paint is long, the two-component paint is particularly beneficial to long-time construction operation, and the blockage of a spray gun is avoided.
The average particle size of the resin prepared by the invention is in the range of 30-80nm, and preferably in the range of 40-60 nm. The dry and wet film is good in transparency and the same color of the dry film is realized.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the examples and comparative examples, "%" means "% by weight" unless otherwise specified.
The test methods used in the examples or comparative examples are described below:
the solid content test method comprises the following steps: weighing appropriate amount of the emulsion in a container made of tinfoil paper, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
MFFT (minimum film formation temperature) test method: according to the national standard GB9267-88, a low-temperature film forming temperature instrument is adopted for testing.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
pH test method: a switzerland wantong pH meter was used.
Viscosity test method: the measurements were carried out using a BROOKFIELD viscometer, spindle 3/30 rpm.
The starting materials used in the examples or comparative examples are described below:
BY3022 (dimer acid polyester polyol, hydroxyl number 56mgKOH/g, number average molecular weight 2000, functionality 2, Beijing, Bai Yuan chemical Co., Ltd.);
PHA-2000 (polyhexamethylene adipate glycol, hydroxyl number 56mgKOH/g, number average molecular weight 2000, functionality 2, Vanhua chemical Co., Ltd.);
TMP (trimethylolpropane, BASF, germany);
DMPA (dimethylolpropionic acid, boston);
CHDM (1, 4-cyclohexanedimethanol, Korea SK)
BiCat8108 (organic bismuth catalyst, leading in the United states)
DMEA (N, N-dimethylethanolamine, BASF, germany);
MMA (methyl methacrylate, zilu petrochemical);
m1000 (polyetheramine, hensman);
sodium hydrosulfite (sodium hydrosulfite, available from Xiong chemical Co., Ltd.)
TBHP (tert-butyl hydroperoxide, Shigaku chemical Co., Ltd.)
U605 (thickener, Wanhua chemical group Co., Ltd.)
Tego 825 (antifoaming agent, Germany Digao Co.)
Tego 902W (antifoam, Germany Digao Co.)
Tego 245 (wetting agent, Germany Digao Co.)
Tego 270 (wetting agent, Germany Digao Co.)
DPM (film-forming aid, Dow chemical)
DPnB (coalescing agent, Dow chemical)
PMA (propylene glycol methyl ether acetate, chemical Co., Ltd., Jinan Guangyu Co., Ltd.).
The formulations used in the preparation of the coatings for the emulsions prepared in the examples or comparative examples are given in Table 1 below:
TABLE 1
The formulations used to test the pot life for the emulsions prepared in the examples or comparative examples are given in Table 2 below:
TABLE 2
The method for testing the application properties of the examples and comparative examples is described as follows:
template construction process: substrate-waterborne bottom color correction-waterborne top primer-waterborne Glaze-waterborne transparent primer-waterborne surface color correction-waterborne clear finish.
The odor-free testing method comprises the following steps: and (3) carrying out blade coating on the prepared component A paint sample on a PE film by using a 10-micrometer wire rod, standing at room temperature for 12h, airing, then placing in a 500ml closed-mouth wide-mouth bottle, sealing for 12h, and artificially smelling the smell, wherein the minimum smell is the best odor-removing effect.
Activation period test method: taking a prepared coating No. four cup for the bi-component paint to adjust the viscosity to about 60 seconds, putting the cup into a pre-adjusted constant-temperature oven at 35 ℃, taking out the viscosity of a test paint sample every 1 hour in a timing manner, recording the viscosity test data of each time, and observing the viscosity change trend, wherein the minimum viscosity change in the previous 4 hours is the optimal viscosity.
Chemical resistance test method: placing test item quantity of cotton white paper sheets on the fully dried sample plate after the preparation process is completed, wetting the paper sheets with pure water, boiling water, 50% ethanol, 10% acetic acid and 10% sodium carbonate solution respectively, and placing for 24 h. And (4) taking away the paper after the test is finished, and observing residual marks on the sample plate, wherein the mark-free condition is the optimal condition.
Comparative example 1:
87g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HMDI (dicyclohexylmethane diisocyanate), 37.28g
IPDI (isophorone diisocyanate), 140g PHA2000 (polyhexamethylene adipate glycol), 60g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ to react until the theoretical NCO value is reached, and cooling to the temperature ofAdding 3g of trimethylolpropane, 22g of dimethylolpropionic acid, 12.2g of CHDM and 108g of acetone at the temperature below 60 ℃, heating to 75 ℃ for reaction, sampling every 1h, measuring NCO until the NCO reaches a theoretical value, and stopping the reaction. Cooling to below 60 deg.C, adding 216g acetone and 87.5g MMA, stirring, cooling to below 40 deg.C, adding 13.15g DMEA, and neutralizing for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 787g of deionized water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate coarse emulsion. Transferring the emulsion into a four-neck flask provided with a reflux condenser tube, a thermometer and mechanical stirring, adding 87.5g of MMA, heating to 32 ℃, stirring for 1h, sequentially adding 0.35g of tert-butyl hydroperoxide and 0.35g of sodium hydrosulfite to initiate free radical polymerization, and removing acetone in the emulsion in a reduced pressure distillation mode after the polymerization is finished to obtain the semitransparent blue-emitting modified waterborne polyurethane emulsion with 40% solid content and 56nm particle size.
Comparative example 2:
87g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HMDI (dicyclohexylmethane diisocyanate), 37.28g
IPDI (isophorone diisocyanate), 140g PHA2000 (polyhexamethylene adipate glycol), 60g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ for reaction until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 22g dimethylolpropionic acid, 12.2g CHDM, 108g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until the theoretical NCO value is reached, and stopping the reaction. Cooling to below 60 deg.C, adding 216g acetone, stirring, cooling to below 40 deg.C, adding 13.15g DMEA, and neutralizing for 5 min. Pouring the prepared prepolymer into a dispersion cup, adding 542g of deionized water under the high-speed shearing condition of 1500r/min to obtain a waterborne polyurethane crude emulsion, removing acetone in the emulsion by a reduced pressure distillation mode, adding 2.8gM1000, adjusting the solid content to 40 percent, and obtaining the translucent blue-emitting waterborne polyurethane with the particle size of 32nmAn ester emulsion.
Example 1:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 78g
HMDI (dicyclohexylmethane diisocyanate), 33.42g
IPDI (isophorone diisocyanate), 140g PHA2000 (polyhexamethylene adipate glycol), 60g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ for reaction until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 21g dimethylolpropionic acid, 8g CHDM, 103g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until the NCO value reaches the theoretical value, and stopping the reaction.
Cooling to about 50 ℃, adding 206g of acetone and 84g of MMA, uniformly stirring, cooling to below 40 ℃, adding 12.55g of DMEA, and carrying out neutralization reaction for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 768g of deionized water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate coarse emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, 84g of MMA was added, the temperature was raised to 32 ℃ and stirring was carried out for 1 hour, and 0.34g of t-butyl hydroperoxide and 0.34g of sodium dithionite were sequentially added to initiate radical polymerization.
After the polymerization is finished, removing acetone from the emulsion in a reduced pressure distillation mode, adding 2.7gM1000, and adjusting the solid content to 40% to obtain the semitransparent blue light-emitting modified waterborne polyurethane emulsion with the particle size of 57 nm.
Example 2:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 96g
HMDI (dicyclohexylmethane diisocyanate), 41.14g
IPDI (isophorone diisocyanate), 140g PHA2000 (polyhexamethylene adipate glycol), 60g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ to react until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 23g dimethylolpropionic acid, 17.2g CHDM, 114g acetone, heating to 75 ℃ to react, sampling every 1h to measure NCO until the NCO reaches the theoretical value, and stopping the reaction.
Cooling to below 60 deg.C, adding 228g acetone and 91g MMA, stirring, cooling to below 40 deg.C, adding 13.75g DMEA, and neutralizing for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 820g of deionized water under the high-speed shearing condition of 1500r/min to obtain the waterborne polyurethane-acrylate coarse emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, 91g of MMA was added, the temperature was raised to 32 ℃ and the mixture was stirred for 1 hour, and then 0.36g of t-butyl hydroperoxide and 0.36g of sodium dithionite were added in this order to initiate radical polymerization.
After the polymerization is finished, removing acetone from the emulsion in a reduced pressure distillation mode, adding 3gM1000, and adjusting the solid content to 40% to obtain the semitransparent blue-emitting modified waterborne polyurethane emulsion with the particle size of 60 nm.
Example 3 (preferred)
87g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged into the flask
HMDI (dicyclohexylmethane diisocyanate), 37.28g
IPDI (isophorone diisocyanate), 140g PHA2000 (polyhexamethylene adipate glycol), 60g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ for reaction until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 22g dimethylolpropionic acid, 12.2g CHDM, 108g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until the NCO reaches the theoretical value, and stopping the reaction.
Cooling to below 60 deg.C, adding 216g acetone and 87.5g MMA, stirring, cooling to below 40 deg.C, adding 13.15g DMEA, and neutralizing for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 787g of deionized water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate coarse emulsion.
This emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, 87.5g of MMA was added, the temperature was raised to 32 ℃ and stirring was carried out for 1 hour, and 0.35g of t-butyl hydroperoxide and 0.35g of sodium dithionite were successively added to initiate radical polymerization.
After the polymerization is finished, removing acetone from the emulsion in a reduced pressure distillation mode, adding 2.8gM1000, and adjusting the solid content to 40% to obtain the semitransparent blue light-emitting modified waterborne polyurethane emulsion with the particle size of 56 nm.
Example 4
Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed 82g
HMDI (dicyclohexylmethane diisocyanate), 35g
IPDI (isophorone diisocyanate), 133g PCL2000 (polycaprolactone diol), 54g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ for reaction until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 21g dimethylolpropionic acid, 11.4g CHDM, 101g acetone, heating to 75 ℃ for reaction, sampling every 1h for NCO measurement until the NCO reaches the theoretical value, and stopping the reaction.
Cooling to below 60 deg.C, adding 204g acetone and 98g MMA, stirring, cooling to below 40 deg.C, adding 12.55g DMEA, and neutralizing for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 783g of deionized water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate coarse emulsion.
The emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, 98g of MMA was added, the temperature was raised to 32 ℃ and stirred for 1 hour, and 0.37g of t-butyl hydroperoxide and 0.37g of sodium dithionite were sequentially added to initiate radical polymerization.
After the polymerization is finished, removing acetone from the emulsion in a reduced pressure distillation mode, adding 2.6gM1000, and adjusting the solid content to 40% to obtain the semitransparent blue light-emitting modified waterborne polyurethane emulsion with the particle size of 56 nm.
Example 5
Into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was placed 82g
HMDI (dicyclohexylmethane diisocyanate), 35g
IPDI (isophorone diisocyanate), 133g PHA2000 (polyhexamethylene adipate glycol), 54g BY3022 (dimer acid polyester polyol), 0.18g BiCat8108, heating to 80 ℃ for reaction until the theoretical NCO value, cooling to below 60 ℃, adding 3g trimethylolpropane, 21g dimethylolpropionic acid, 11.4g CHDM, 101g acetone, heating to 75 ℃ for reaction, sampling every 1h to measure NCO until the NCO reaches the theoretical value, and stopping the reaction.
Cooling to below 60 deg.C, adding 204g acetone, 49g MMA and 49g 49gSt, stirring, cooling to below 40 deg.C, adding 12.55g DMEA, and neutralizing for 5 min. And pouring the prepared prepolymer into a dispersion cup, and adding 783g of deionized water under the high-speed shearing condition of 1500r/min to obtain the aqueous polyurethane-acrylate coarse emulsion.
This emulsion was transferred to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring, 49g of MMA and 49g of 49gSt were added, the temperature was raised to 32 ℃ and stirring was carried out for 1 hour, and 0.37g of t-butyl hydroperoxide and 0.37g of sodium dithionite were sequentially added to initiate radical polymerization.
After the polymerization is finished, removing acetone from the emulsion in a reduced pressure distillation mode, adding 2.6gM1000, and adjusting the solid content to 40% to obtain the semitransparent blue light modified waterborne polyurethane emulsion with the particle size of 72 nm.
The emulsions prepared in the examples and comparative examples were used to prepare wood lacquer coatings according to the coating formulations provided above and were tested for performance. The performance test results of the obtained wood lacquer coating are shown in the following table:
it can be seen from the application data of the examples that the resin prepared by the invention can meet the performance requirements of the wood lacquer field in the aspects of the two-component activation period, the chemical resistance and the odor-free effect, the example 3 is the most optimal scheme, and compared with the comparative example 1, the viscosity of the polyether-free amine formula in the activation period is always in an increasing trend and is gelled; from comparative example 2, it is seen that the resistance of the non-monomer modified chemical is reduced significantly;
in the embodiment, the lowest film-forming temperature of the resin is higher due to the excessively high hard segment content of the polyurethane part, so that the addition amount of the film-forming additive is increased, the environment is not favorable, and the chemical resistance is reduced due to the low hard segment content; the scope of the claims used in the embodiments includes, but is not limited to, soft segment and monomer properties that meet the requirements of the application.
From production practice, the preparation method of the modified waterborne polyurethane resin is simple and controllable in process, can obtain excellent chemical resistance, a two-component activation period of a super-long time and a good odor-removing effect, and has a large practical use value.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A preparation method of a modified aqueous polyurethane resin dispersion is characterized by comprising the following steps:
1) synthesizing an isocyanate terminated prepolymer;
2) adding a part of modified monomer, a low-boiling-point organic solvent and the isocyanate-terminated prepolymer, fully mixing and dissolving, and dispersing after neutralization reaction to obtain a pre-modified emulsion;
3) adding another part of modified monomer into the pre-modified emulsion, fully and uniformly swelling, and adding an initiator to initiate polymerization;
4) and removing the low-boiling-point organic solvent, and then adding amino-functional nonionic hydrophilic polyoxyethylene ether to obtain the modified aqueous polyurethane resin dispersion.
2. The method according to claim 1, wherein the raw materials for preparing the isocyanate terminated prepolymer comprise: 30-40 wt% of polyisocyanate, 6-15 wt% of chain extender and macromolecular polyol with the molar ratio of the macromolecular polyol to the polyisocyanate being 1:4.5-1: 5.5.
3. The preparation method according to claim 2, wherein the chain extender comprises a small molecular polyol chain extender and a carboxylic acid type hydrophilic chain extender, and the use amounts are 3-6 wt% and 3-9 wt%, respectively; preferably, the molecular weight of the small-molecular polyol chain extender is 30-200g/mol, and preferably comprises one or more of trimethylolpropane, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the carboxylic acid type hydrophilic chain extender comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid and N, N-dimethylolmaleamic acid.
4. The method of claim 2, wherein the polyisocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hexahydrotoluene diisocyanate, trimethylhexane diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate; and/or
The number average molecular weight of the macromolecular polyol is 800-4000, and the macromolecular polyol comprises at least one of polyether polyol, polyester polyol, polycarbonate polyol, phthalic anhydride polyester polyol, dimer acid polyester polyol and hydroxyl-terminated polyolefin glycol, preferably one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, dimer acid polyester polyol, polyolefin polyol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol and 1, 6-hexanediol adipate diol, and more preferably dimer acid polyester polyol with the number average molecular weight of 1000-3000.
5. The method of claim 1, wherein the modifying monomer comprises at least one of ethylenically unsaturated monomers, preferably one or more of methyl (meth) acrylate, ethyl (meth) acrylate, hydroxypropyl acrylate, propyl acrylate, butyl (meth) acrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl acrylate, (meth) styrene, isobornyl acrylate, and isooctyl acrylate; the amount of the modified monomer is 0.1-1 time of the mass of the isocyanate-terminated prepolymer, wherein 40-60% is added in the step 2).
6. The process according to claim 1, wherein in step 2), the low-boiling organic solvent is an organic solvent having a boiling point of less than 100 ℃, preferably acetone, and the amount of the solvent is preferably 0.5 to 1.2 times the amount of the isocyanate-terminated prepolymer; and/or
The neutralizing agent used in the neutralization reaction comprises one or more of sodium hydroxide, potassium hydroxide, triethylamine, N-dimethylethanolamine, dimethylcyclohexylamine, triethanolamine, methyldiethanolamine, diisopropanolamine, ethyldiisopropylamine, diisopropylcyclohexylamine, N-methylmorpholine, 2-amino-2-methyl-1-propanol and ammonia water.
7. The preparation method according to claim 1, wherein in the step 3), the amount of the initiator is 0.05 to 0.3 percent of the total mass of the modified monomer;
preferably, the initiator comprises an oxidizing agent and a reducing agent, the oxidizing agent comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate and tert-butyl hydroperoxide, and the reducing agent comprises one or more of sodium hydrosulfite, sodium erythorbate.
8. The method according to claim 1, wherein in step 4), the amino-functional nonionic hydrophilic polyoxyethylene ether is used in an amount of 0.5% to 1% based on the mass of the isocyanate terminated prepolymer;
the number average molecular weight of the amino-functional nonionic hydrophilic polyoxyethylene ether is 500-5000, and the amino-functional nonionic hydrophilic polyoxyethylene ether is selected from one or more of amino-terminated polyether of polyethylene glycol, amino-terminated polyether of polypropylene glycol and amino-terminated polyether copolymerized in different proportions of ethylene glycol/propylene glycol, preferably monoamino-functional polyoxyethylene ether with the number average molecular weight of 800-2000 and the molar ratio of ethylene glycol to propylene glycol of 5-8: 1.
9. The modified aqueous polyurethane resin dispersion produced by the production method according to any one of claims 1 to 8.
10. A wood lacquer coating comprising the modified aqueous polyurethane resin dispersion of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110438721.0A CN113185643B (en) | 2021-04-23 | 2021-04-23 | Synthesis and application of modified aqueous polyurethane resin dispersoid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110438721.0A CN113185643B (en) | 2021-04-23 | 2021-04-23 | Synthesis and application of modified aqueous polyurethane resin dispersoid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113185643A true CN113185643A (en) | 2021-07-30 |
| CN113185643B CN113185643B (en) | 2023-01-13 |
Family
ID=76978170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110438721.0A Active CN113185643B (en) | 2021-04-23 | 2021-04-23 | Synthesis and application of modified aqueous polyurethane resin dispersoid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113185643B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181353A (en) * | 2021-12-02 | 2022-03-15 | 万华化学集团股份有限公司 | Synthesis and application of modified waterborne polyurethane composition |
| WO2024078045A1 (en) * | 2022-10-13 | 2024-04-18 | 立邦涂料（中国）有限公司 | Waterborne polyurethane dispersion for automobile coating, and preparation method therefor and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532463A (en) * | 2011-12-26 | 2012-07-04 | 四川达威科技股份有限公司 | Aqueous polyurethane and preparation method thereof |
| CN108219076A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating |
| CN112175162A (en) * | 2019-07-05 | 2021-01-05 | 万华化学（宁波）有限公司 | Modified waterborne polyurethane resin, preparation method and application thereof |
| CN112322162A (en) * | 2020-11-11 | 2021-02-05 | 惠州市惠阳区嘉泰涂料有限公司 | Polyurea coating and preparation method thereof |
| CN112680087A (en) * | 2020-12-24 | 2021-04-20 | 华南理工大学 | Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof |
-
2021
- 2021-04-23 CN CN202110438721.0A patent/CN113185643B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532463A (en) * | 2011-12-26 | 2012-07-04 | 四川达威科技股份有限公司 | Aqueous polyurethane and preparation method thereof |
| CN108219076A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating |
| CN112175162A (en) * | 2019-07-05 | 2021-01-05 | 万华化学（宁波）有限公司 | Modified waterborne polyurethane resin, preparation method and application thereof |
| CN112322162A (en) * | 2020-11-11 | 2021-02-05 | 惠州市惠阳区嘉泰涂料有限公司 | Polyurea coating and preparation method thereof |
| CN112680087A (en) * | 2020-12-24 | 2021-04-20 | 华南理工大学 | Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张芳: "二聚酸聚酯多元醇在聚氨酯弹性体中的应用研究", 《中国聚氨酯工业协会弹性体专业委员会2011年年会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181353A (en) * | 2021-12-02 | 2022-03-15 | 万华化学集团股份有限公司 | Synthesis and application of modified waterborne polyurethane composition |
| CN114181353B (en) * | 2021-12-02 | 2023-12-19 | 万华化学集团股份有限公司 | Synthesis and application of modified waterborne polyurethane composition |
| WO2024078045A1 (en) * | 2022-10-13 | 2024-04-18 | 立邦涂料（中国）有限公司 | Waterborne polyurethane dispersion for automobile coating, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113185643B (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106519133B (en) | A kind of sulfonic acid type water-based polyurethane-acrylate is from matting resin and its preparation method and application | |
| CN104628982B (en) | A kind of preparation method of alkali lignin base water polyurethane | |
| CN113185643B (en) | Synthesis and application of modified aqueous polyurethane resin dispersoid | |
| CN103319680B (en) | Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate | |
| CN101481451A (en) | High solid content latent curing polyurethane acroleic acid hybrid emulsion | |
| US11274229B2 (en) | Aqueous coating composition | |
| CN110746571B (en) | APAO modified polyurethane waterborne resin and preparation method thereof | |
| CN109293871B (en) | Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating | |
| CN112028801B (en) | Chain extender and preparation method and application thereof | |
| CN112175162B (en) | Modified waterborne polyurethane resin, preparation method and application thereof | |
| CN112646114A (en) | Triplecene derivative modified polyurethane aqueous resin and preparation method thereof | |
| CN108977157A (en) | A kind of Aqueous Polyurethane Adhesives and preparation method thereof | |
| CN111217964B (en) | Waterborne polyurethane-acrylate hybrid resin, preparation method thereof and application thereof in leather finishing agent | |
| CN108164650B (en) | Alkenyl-terminated nonionic waterborne polyurethane modified acrylate emulsion and preparation method thereof | |
| CN112225878B (en) | High-alkali-resistance aqueous bi-component isocyanate curing agent and preparation method thereof | |
| CN114181353B (en) | Synthesis and application of modified waterborne polyurethane composition | |
| CN112159509B (en) | Waterborne polyurethane and preparation method and application thereof | |
| CN115197395A (en) | Aqueous polyurethane for impregnation of microfiber leather and preparation method and application thereof | |
| CN113683741A (en) | Water-based UV resin for UV-Monocoat and preparation method thereof | |
| JP4159422B2 (en) | Process for producing aqueous polyurethane dispersions derived from polycarbonate diols | |
| US3948847A (en) | Process for the manufacture of polymer solutions | |
| CN115926106A (en) | Reactive polyurethane anionic emulsifier and preparation method and application thereof | |
| CN115572379B (en) | Preparation method of azido-containing polyester polyol and application of azido-containing polyester polyol in post-crosslinking single-component waterborne polyurethane | |
| CN114479742B (en) | Bio-based high-crystallinity aqueous polyurethane adhesive for shoes and preparation process thereof | |
| WO2024078045A1 (en) | Waterborne polyurethane dispersion for automobile coating, and preparation method therefor and use thereof |
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 |