CN116622031A - Synthesis and application of aromatic aqueous polyurethane/acrylic ester composition - Google Patents

Synthesis and application of aromatic aqueous polyurethane/acrylic ester composition Download PDF

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CN116622031A
CN116622031A CN202210126909.6A CN202210126909A CN116622031A CN 116622031 A CN116622031 A CN 116622031A CN 202210126909 A CN202210126909 A CN 202210126909A CN 116622031 A CN116622031 A CN 116622031A
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isocyanate
terminated prepolymer
modified
aromatic
mass
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周操
胡海东
晋云全
沈如宝
孙常青
王传博
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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

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  • 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)

Abstract

The invention provides a preparation method and application of a water-based aromatic polyurethane composition, comprising the following steps: the method comprises the steps of (1) synthesizing isocyanate-terminated prepolymer, adding organic solvent diluent and isocyanate-terminated prepolymer, fully mixing and dissolving, (2) adding organic solvent solution of aromatic secondary amine, then adding acrylate monomer and neutralizer, then adding deionized water for shearing and dispersing, then adding polyamine chain extender after dispersing is finished to obtain pre-modified emulsion, (3) emulsifying another part of modified monomer in the pre-modified emulsion, performing free radical polymerization, and finally removing low-boiling-point organic solvent. The preparation process of the modified aromatic waterborne polyurethane composition prepared by the preparation method provided by the invention can well control side reactions of isocyanate and water, and has the advantages of small particle size and excellent performance.

Description

Synthesis and application of aromatic aqueous polyurethane/acrylic ester composition
Technical Field
The invention relates to a preparation method and application of an aromatic water-based polyurethane/acrylic ester composition, in particular to application of an aromatic water-based polyurethane/acrylic ester wood lacquer coating.
Background
In recent years, with the continuous improvement of environmental protection regulations, the proportion of water-based paint on the market is increasing. The aqueous polyurethane emulsion is used as one of the aqueous paint, and is widely used in the fields of wood paint, textile, synthetic leather, adhesive, glass fiber impregnating compound, personal care and the like due to its excellent low VOC, fullness, chemical resistance, mechanical property and mechanical property. However, recently, the price of isocyanate, especially 4,4' -dicyclohexylmethane diisocyanate, which is one of important raw materials of the aqueous polyurethane emulsion is increased from 50 yuan/kg to 90 yuan/kg, which greatly limits the development and application of the aqueous polyurethane emulsion.
Thus, the use of relatively inexpensive aromatic isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate to produce aqueous polyurethanes is urgent. The aromatic isocyanate has high reactivity, and is easy to react with water in a dispersing process to cause the particle size to be large and generate a large amount of carbon dioxide. In order to reduce the side reaction of isocyanate and water during the dispersion, the final isocyanate content is generally reduced by adding a small molecular diol chain extender, but this causes the problems of long time in the prepolymerization stage and excessive viscosity of the prepolymer. And brings a plurality of difficulties to the production of the aqueous polyurethane.
The aromatic secondary amine can be added after the pre-coalescence bundles, so that the problem of side reaction of the aromatic isocyanate and water is solved.
Disclosure of Invention
The invention provides a preparation method of an aromatic aqueous polyurethane/acrylic ester composition and application of the composition prepared by the preparation method in aqueous paint, and aims to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a modified aromatic waterborne polyurethane composition, which comprises the following steps:
the method comprises the steps of (1) synthesizing isocyanate-terminated prepolymer, adding organic solvent diluent and isocyanate-terminated prepolymer, fully mixing and dissolving, (2) adding organic solvent solution of aromatic secondary amine, then adding acrylate monomer and neutralizer, then adding deionized water for shearing and dispersing, then adding polyamine chain extender after dispersing is finished to obtain pre-modified emulsion, (3) emulsifying another part of modified monomer in the pre-modified emulsion, performing free radical polymerization, and finally removing low-boiling-point organic solvent.
In the invention, the isocyanate-terminated prepolymer in the step (1) is prepared by mixing and reacting raw materials comprising the following components: aromatic polyisocyanates, macromolecular polyols, small-molecule polyols, monohydric and/or dihydric alcohols with polyoxyethylene segments in their main and/or side chains, hydrophilic chain extenders, polyamine chain extenders, neutralizing agents, low boiling solvents, aromatic secondary diamines.
In the present invention, the modified aqueous polyurethane composition is prepared based on the total mass of the isocyanate terminated prepolymer from which the modified aqueous polyurethane composition is prepared, comprising the following components in the following amounts:
1) The aromatic polyisocyanate is used in an amount of 20 to 50wt%, preferably 22.8 to 43.8wt% based on the mass of the isocyanate terminated prepolymer;
2) The macromolecular polyol is used in an amount of 20 to 65wt%, preferably 28.7 to 56.3wt%, based on the mass of the isocyanate-terminated prepolymer;
3) The small molecular polyol is used in an amount of 0.5 to 15wt%, preferably 1.06 to 10.6wt%, based on the mass of the isocyanate-terminated prepolymer;
4) The amount of the monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain contains a polyethylene oxide chain segment is 0.2 to 10wt%, preferably 0.6 to 3.3wt% of the mass of the isocyanate terminated prepolymer;
5) The hydrophilic chain extender is used in an amount of 3 to 15wt%, preferably 4.16 to 9.44wt% based on the mass of the isocyanate terminated prepolymer;
6) The polyamine chain extender is used in an amount of 0.2 to 5wt%, preferably 0.6 to 1.3wt%, based on the mass of the isocyanate terminated prepolymer;
7) The amount of the neutralizing agent is 1.0 to 10wt%, preferably 2.4 to 7.1wt% based on the mass of the isocyanate terminated prepolymer;
8) The aromatic secondary diamine accounts for 1 to 10 weight percent, preferably 3.3 to 7.6 weight percent of the weight of the isocyanate terminated prepolymer;
9) The dosage of the low boiling point solvent is 0.7-1.45 times of the mass of the isocyanate end-capped prepolymer;
10 The amount of the modifying monomer is 0.7 to 1.4 times, preferably 0.7 to 1.1 times, the mass of the isocyanate terminated prepolymer;
11 The initiator is used in an amount of 0.05 to 0.3%, preferably 0.1 to 0.2% of the total mass of the modified monomers.
In the production method of the present invention, the aromatic polyisocyanate is one or more selected from toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, dimethylbiphenyl diisocyanate, dimethyldiphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and the like, and toluene diisocyanate is preferable.
In the preparation method of the invention, the macromolecular polyol is one or more of polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, dimer acid polyester polyol, polyolefin polyol, polycaprolactone diol, hydrogenated castor oil, 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 polypropylene glycol with the further number average molecular weight of 2000 daltons.
In the preparation method of the invention, the small molecular polyol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methylpentane-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 2-ethyl-3-propylpentanediol, 2-dimethylpentanediol, diethylene glycol, propylene glycol and trimethylolpropane, preferably 1, 4-cyclohexanedimethanol.
In the preparation method of the invention, the monohydric alcohol and/or dihydric alcohol containing polyethylene oxide chain segment in the main chain and/or the side chain contains 90-100wt% of ethylene oxide, preferably Tego Chemie companyOne or more of D-3403, ymerTM N120 from Pertrop corporation and MPEG1200 from Korean music day corporation, more preferably YmerTM N120 from Pertrop corporation and/or MPEG1200 from Korean music day corporation, and preferably MPEG1200 is used.
In the preparation method of the invention, the hydrophilic chain extender comprises an isocyanate-reactive compound with ionic or potential ionic groups, and comprises one or two of ethylenediamine ethanesulfonic acid sodium, dimethylolpropionic acid, dimethylolbutyric acid, amino acid, sulfamate, tartaric acid, N-dimethylolmaleamic acid, diaminobenzoic acid, dihydroxypropane sodium sulfonate and the like, preferably dimethylolpropionic acid.
In the preparation method of the invention, the initiator initiation system is a redox system.
Preferably, the oxidizing agent comprises one or more of ammonia persulfate, sodium persulfate, potassium persulfate, di-t-butyl peroxide, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide and t-butyl hydroperoxide, and further preferably t-butyl hydroperoxide.
Preferably, the reducing agent comprises one or more of sodium hydrosulfite, FF6M, N, N-dimethylaniline, ferrous sulfate, silver nitrate, mercaptan, ferrous chloride, tetraethyl imine, sodium metabisulfite, sodium bisulphite and isoascorbic acid, and sodium metabisulfite is further preferred.
In the preparation method of the invention, the reaction temperature adopted in the preparation of the isocyanate-terminated prepolymer is 65-80 ℃;
preferably, the reaction temperature of the aromatic secondary diamine and the isocyanate-terminated prepolymer is 40-65 ℃;
preferably, the mixing and dissolving of the modified monomer and the isocyanate terminated prepolymer is carried out at 60-70 ℃;
preferably, the initiation temperature of the pre-modified emulsion initiated polymerization is 30-45 ℃.
In the present invention, the organic solvent in the step (1) is an organic solvent with a boiling point lower than 100 ℃, and is selected from one or more of acetone, methyl ethyl ketone, cyclohexane, dichloromethane, dichloroethane, trichloroethane, ethyl acetate, pentane, heptane and hexane, preferably acetone.
In the invention, the time of mixing and dissolving in the step (1) is 5-30 min;
in the invention, the aromatic secondary amine in the step (2) has the following structural general formula:
wherein R is 1 ＝C x H y ,R 2 ＝C x H y 1≤x≤6,3≤y≤20。
Specifically, the aromatic secondary amine can be selected from one or more of 4,4' -dimethylamino diphenyl methane, 4' -di-sec-butylamino diphenyl methane, 4' -di-butylamino diphenyl methane, 4' -diethylamino diphenyl methane and 4,4' -dihexylamino diphenyl methane;
referring to CN107501524a, the synthesis process of the aromatic secondary diamine is as follows: heating, stirring and dissolving 4, 4-diamino diphenyl methane, halogenated alkane and morpholine, adding macroporous strong base anion exchange resin, replacing nitrogen, heating to 40-180 ℃, controlling the pressure to 1-5Mpa, stirring and reacting for 1-5h, and fractionating to obtain the aromatic secondary diamine.
In the invention, the organic solvent in the step (2) is selected from one or more of acetone, butanone and cyclohexanone;
in the invention, the neutralizing agent in the step (2) is selected from 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. Preferred neutralizing agents are sodium hydroxide, triethylamine and/or N, N-dimethylethanolamine, more preferably N, N-dimethylethanolamine.
In the present invention, the polyamine chain extender in the step (2) is an organic or inorganic primary amine or secondary amine functional compound containing at least two active hydrogens, and specifically is one or more selected from ethylenediamine, 2-methyl-1, 5-pentanediamine, isophorone diamine, hydrazine, hydroxyethyl ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexane diamine, phenylenediamine, toluenediamine, dicyclohexylmethane diamine, and preferably isophorone diamine.
In the present invention, the time for shearing and dispersing in the step (2) is not particularly limited, and is 6min to 1h.
In the present invention, the modifying monomer in the step (3) includes at least one of ethylenically unsaturated monomers capable of undergoing free radical polymerization, and specifically one or more ethylenically unsaturated monomers selected from methyl acrylate, phosphoric acid acrylate, silicone acrylate, allyl methacrylate, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, hydroxyethyl methacrylate, butyl methacrylate, tetrahydrofuranyl acrylate, styrene, allylmethylstyrene, isobornyl acrylate, and isooctyl acrylate, and preferably methyl methacrylate and styrene.
In the invention, the reactor for free radical polymerization in the step (3) is a reaction kettle; the temperature of the free radical polymerization is 25-45 ℃, preferably 30-38 ℃, for 10min-2h, preferably 20min-1h, and the pressure is 0-100kpa, preferably 0-50kpa. In the invention, the mode of removing the low-boiling point organic solvent is reduced pressure distillation.
The second aspect of the invention also provides a wood lacquer coating, which comprises the modified aqueous polyurethane composition prepared by the preparation method.
The third aspect of the present invention provides the use of the modified aqueous polyurethane composition prepared by the preparation method described above, preferably for one-component wood lacquer coating applications.
The technical scheme provided by the invention has the following benefits:
the aromatic secondary diamine is used to reduce the isocyanate content of the prepolymer before dispersion, so that the probability of side reaction between isocyanate and water during dispersion is greatly reduced. The reaction of water and isocyanate can generate carbon dioxide, and the generation of carbon dioxide can be reduced by adding aromatic secondary diamine, so that the production process is safer and more controllable. The polyurethane urea generated by the reaction of water and isocyanate can further react with isocyanate, so that the viscosity and molecular weight of the emulsion are increased, the probability of generating polyurethane urea can be reduced by adding aromatic secondary amine, and the prepared emulsion is transparent, smaller in particle size and controllable in viscosity.
The reactivity of the aromatic secondary diamine with the isocyanate is between the aliphatic diol and the aliphatic diamine, which may be added after the reaction of the aliphatic diol with the isocyanate is completed with the addition of the dilution solvent. Can be gently reacted with isocyanate at 40-60 ℃ without causing gel phenomenon caused by too fast reaction. When the isocyanate content is reduced by the aliphatic diol, the reaction temperature needs to reach 65-75 ℃, so that the use amount of the low-boiling point solvent needs to be reduced, and the prepolymer has excessive viscosity, and even cannot be diluted and dissolved by the low-boiling point solvent and cannot be dispersed. When the isocyanate content is reduced by the aliphatic diamine, the molecular weight is increased rapidly in a short time due to the excessive reactivity of the aliphatic diamine, and the gel phenomenon occurs.
The aromatic secondary amine can form a multi-benzene ring structure with the following special structure with isocyanate, so that the chemical resistance and water resistance of the resin can be effectively improved;
multi-benzene ring structure:
according to the scheme of adding the acrylic ester monomer step by step, the hydrophilic group content of the prepolymer can be reduced, so that the emulsion with transparent appearance can be obtained only by lower hydrophilic groups.
The preparation method of the invention is simple, safe, efficient and low in VOC content.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, 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 testing method comprises the following steps: and weighing the weight change of the emulsion before and after 20min at 150 ℃ in a container made of tinfoil paper, and calculating the solid content of the emulsion.
The particle size testing method comprises the following steps: the solution was diluted 1000 times with distilled water at room temperature using a Markov particle size analyzer.
The pH test method comprises the following steps: a swiss vanton pH meter was used.
The formulations used in preparing the coatings for the emulsions prepared in the following examples or comparative examples are shown in Table 1 below:
TABLE 1
Name of the name Material Mass/g
Emulsions prepared in examples or comparative examples Emulsion 80
BYK 024 Defoaming agent 0.4
Tego 245 Wetting agent 0.4
Tego 270 Wetting agent 0.4
DPM Film forming aid 3
DPnB Film forming aid 3
Vesmody@U605 Polyurethane thickener 0.2
Water and its preparation method Diluent agent 12.55
The method for detecting the application performance after the examples and the comparative examples is described as follows:
and (3) sample plate construction flow: the base material comprises a base material, a water-based under-color repairing, a water-based primer, a water-based Glaze, a water-based transparent primer, a water-based surface-color repairing and a water-based finishing paint.
Alcohol resistance test: and (5) respectively soaking the finished product sample plate in 50% ethanol solution for 1h and 24h, taking down and wiping the finished product sample plate and observing the state of a paint film.
And (3) water resistance test: and (5) soaking deionized water on the finished sample plate for 24 hours, taking off the water stain, and observing the state of a paint film.
Gloss test method: the 60℃angular gloss was tested according to paint film gloss assay GB 1743-79.
The method for testing the hardness of the swing rod comprises the following steps: hardness was tested according to paint film hardness assay pendulum damping test GB/T1730-1993.
The raw materials used in the examples or comparative examples are described below:
(toluene diisocyanate, wanhua chemical group Co., ltd.);
(4, 4' -diphenylmethane diisocyanate, wanhua chemical group Co., ltd.);
PPG2000 (polypropylene oxide ether glycol, number average molecular weight=2000, functionality 2, vancomic chemical group inc.);
PCL2000 (polycaprolactone diol, number average molecular weight=2000, functionality 2, macrocelluloid limited);
HB (hydrogenated castor oil, german BASF Co.)
MPEG1200 (methoxy polyethylene glycol ether, korean music day);
DMPA (dimethylolpropionic acid, buston);
BiCat8108 (organobismuth catalyst, leading in the united states);
DMEA (N, N-dimethylethanolamine, BASF company, germany);
TEA (triethylamine, a Ding Shiji Co., ltd.)
Acetone (refined by Wanhua chemical group Co., ltd., moisture content 200 ppm);
TMP (trimethylolpropane, wanhua chemical group Co., ltd.);
EDA (ethylenediamine, yangzi petrochemical);
MMA (methyl methacrylate, zilutarition);
MDBA: (4, 4' -Di-sec-butylaminodiphenyl methane, wanhua chemistry)
MDMA:4,4' -bis methylamino diphenylmethane:
99g (0.5 mol) of 4, 4-diaminodiphenylmethane, 142g (1 mol) of methyl iodide, 400g of morpholine, heating, stirring and dissolving, 6g of macroporous strong-base anion exchange resin (D201) and sealing the autoclave, replacing 3-5 times by N2, starting to heat to 50 ℃, controlling the pressure of a reaction system to be about 2MPa, stirring and reacting for 2 hours, and fractionating.
MDAA 4,4' -dihexyl aminodiphenyl methane;
99g (0.5 mol) of 4, 4-diaminodiphenylmethane and 198g (1.2 mol) of bromohexane are added into a 1L autoclave, 300g of morpholine is added, heating, stirring and dissolving are carried out, 14g of macroporous strong-base anion exchange resin (D201) is added, the autoclave is closed, N2 is used for replacement for 3 to 5 times, the temperature is raised to 140 ℃, the pressure of a reaction system is controlled to be about 5MPa, stirring and reacting are carried out for 4 hours, and fractionation is carried out.
st (styrene, qilu petrochemical)
Sodium metabisulfite (Xilan chemical industry Co., ltd.)
BDO (1, 4-butanediol, ala Ding Shiji Co., ltd.)
CHDM (1, 4-cyclohexanedimethanol, isman Co., ltd.)
TBHP (t-butyl hydroperoxide, 70%, west Long chemical Co., ltd.)
(thickener, wanhua chemical group Co., ltd.)
BYK 024 (defoamer, BYK Co.)
Tego 245 (wetting agent, german Digao)
Tego 270 (wetting agent, german Digao)
DPM (film forming aid, dow chemical)
DPnB (film forming aid, dow chemical)
NPG: (neopentyl glycol, wanhua chemical group Co., ltd.)
Example 1:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 98.0g(toluene diisocyanate), 115g of PPG2000 (polypropylene oxide ether glycol), 23gHB (hydrogenated castor oil), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30.7g of CHDM, 70g of acetone, and the temperature is raised to 80 ℃ to react until the theoretical NCO value, and the reaction is stopped. Cooling to below 60 ℃, adding 264g of acetone, uniformly stirring, cooling to 50 ℃, adding a mixed solution of 14g of MDBA and 56g of acetone, reacting until the theoretical NCO value is reached, and adding 275g of MMA. Cooling to 30 ℃, adding 9.6g of DMEA, stirring for 5min, adding 1000g of deionized water under high-speed shearing, and adding 2g of EDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. The emulsion is transferred into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 60g MMA is added, the temperature is raised to 35 ℃ and the mixture is stirred for 1h, 0.96g TBHP and 0.67g sodium metabisulfite are sequentially added to initiate free radical polymerization, and acetone in the emulsion is removed by a reduced pressure distillation mode after the polymerization is completed, so that a 40% solid content modified aqueous polyurethane composition with 75nm semitransparent blue light with the particle size is obtained.
Example 2:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 56g(toluene diisocyanate), 115g PCL2000 (polycaprolactone diol), 23gHB (hydrogenated castor oil), 2.6g TMP, 8g MPEG1200, 19g dimethylolpropionic acid, 0.05g BiCat8108, 70g acetone, and heating to 65 ℃ to reach a theoretical NCO value, and stopping the reaction. Cooling to below 60 ℃, adding 68g of acetone, uniformly stirring, cooling to 40 ℃, adding a mixed solution of 8g of MDBA and 32g of acetone, reacting until the theoretical NCO value is reached, and adding 275g of MMA. Cooling to 35deg.C, adding 11g DMEA, stirring 1900g of deionized water is added under high-speed shearing for 0min, and 2.5g of IPDA diluted by four times of water is added after the dispersion is finished, so that the modified waterborne polyurethane composition pre-emulsion is obtained. The emulsion is transferred into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 53g MMA is added, the temperature is raised to 45 ℃ and the mixture is stirred for 1h, 0.47g TBHP and 0.33g sodium metabisulfite are sequentially added to initiate free radical polymerization, and acetone in the emulsion is removed by a reduced pressure distillation mode after the polymerization is completed, so that a 40% solid content and semitransparent blue light modified aqueous polyurethane composition with the particle size of 70nm is obtained.
Example 3:
130.0g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged with(toluene diisocyanate), 170g of PPG2000 (polypropylene oxide ether glycol), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30g of BDO and 70g of acetone, and heating to 75 ℃ to reach a theoretical NCO value, and stopping the reaction. Cooling to below 60 ℃, adding 230g of acetone, adding a mixed solution of 30g of MDAA and 120g of acetone, reacting until the theoretical NCO value, and adding 275g of MMA. Cooling to 30 ℃, adding 9.6g of DMEA, stirring for 5min, adding 1200g of deionized water under high-speed shearing, and adding 5g of IPDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. Transferring the emulsion into a four-neck flask with a reflux condenser, a thermometer and mechanical stirring, adding 60g of styrene, heating to 40 ℃, sequentially adding 0.72g of TBHP and 0.5g of sodium metabisulfite to initiate free radical polymerization, and removing acetone in the emulsion by a reduced pressure distillation mode after the polymerization is completed to obtain a 40% solid modified aqueous polyurethane composition with 100nm semitransparent blue light of particle size.
Example 4:
130.0g of a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged with(4, 4' -diphenylmethane diisocyanate), 85g PPG1000 (polypropylene oxide ether glycol)) 2.6g MPEG1200, 28g dimethylolpropionic acid, 0.05g BiCat8108,6gBDO and 50g acetone, and heating to 75 ℃ to reach a theoretical NCO value, and stopping the reaction. Cooling to below 60 ℃, adding 220g of acetone, adding a mixed solution of 20g of MDAA and 80g of acetone, reacting until the theoretical NCO value, and adding 160g of MMA. Cooling to 30 ℃, adding 18.5g of DMEA, stirring for 5min, adding 900g of deionized water under high-speed shearing, and adding 4g of EDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. The emulsion is transferred into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 33g MMA is added, the temperature is raised to 35 ℃, 0.55g TBHP and 0.39g sodium metabisulfite are sequentially added to initiate free radical polymerization, and acetone in the emulsion is removed by a reduced pressure distillation mode after the polymerization is completed, so that a 40% solid content modified aqueous polyurethane composition with 65nm semitransparent blue light with particle size is obtained.
Comparative example 1:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 98.0g(toluene diisocyanate), 115g of PPG2000 (polypropylene oxide ether glycol), 23gHB (hydrogenated castor oil), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30.7g of CHDM, 70g of acetone, and the temperature is raised to 80 ℃ to react until the theoretical NCO value, and the reaction is stopped. Cooling to below 60deg.C, adding 264g of acetone, stirring, cooling to 50deg.C, and adding 275g of MMA. Cooling to 30 ℃, adding 9.6g of DMEA, stirring for 5min, adding 1000g of deionized water under high-speed shearing, and adding 2g of EDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. The emulsion is transferred into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 60g MMA is added, the temperature is raised to 35 ℃ and the mixture is stirred for 1h, 0.96g TBHP and 0.67g sodium metabisulfite are sequentially added to initiate free radical polymerization, and acetone in the emulsion is removed by a reduced pressure distillation mode after the polymerization is completed, so that a 40% solid content modified aqueous polyurethane composition with the particle size of 200nm bluish light is obtained.
Comparative example 2:
to be provided with reflux cooling98.0g of the mixture was charged into a four-necked flask equipped with a condenser, a thermometer and mechanical stirring(toluene diisocyanate), 115g of PPG2000 (polypropylene oxide ether glycol), 23gHB (hydrogenated castor oil), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30.7g of CHDM, 70g of acetone, and the temperature is raised to 80 ℃ to react until the theoretical NCO value, and the reaction is stopped. Cooling to below 60deg.C, adding 264g of acetone, stirring, cooling to 50deg.C, and adding 275g of MMA. Cooling to 30 ℃, adding 9.6g of DMEA, stirring for 5min, adding 1000g of deionized water under high-speed shearing, and adding 14g of MDBA and 2g of EDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. The emulsion is transferred into a four-neck flask equipped with a reflux condenser, a thermometer and mechanical stirring, 60g MMA is added, the temperature is raised to 35 ℃ and the mixture is stirred for 1h, 0.96g TBHP and 0.67g sodium metabisulfite are sequentially added to initiate free radical polymerization, and acetone in the emulsion is removed by a reduced pressure distillation mode after the polymerization is completed, so that a 40% solid content modified aqueous polyurethane composition with 180nm bluish particle size is obtained.
Comparative example 3:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 98.0g(toluene diisocyanate), 115g of PPG2000 (polypropylene oxide ether glycol), 23gHB (hydrogenated castor oil), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30.7g of CHDM, 70g of acetone, and the temperature is raised to 80 ℃ to react until the theoretical NCO value, and the reaction is stopped. Cooling to below 60 ℃, adding 264g of acetone, uniformly stirring, cooling to 50 ℃, adding a mixed solution of 14g of NPG and 56g of acetone, heating to 60 ℃ for reaction until the theoretical NOC value, stopping the reaction, uniformly stirring, cooling to 50 ℃, and adding 275g of MMA. Cooling to 30 ℃, adding 9.6g of DMEA, stirring for 5min, adding 1000g of deionized water under high-speed shearing, and adding 2g of EDA diluted by four times of water after dispersing to obtain the modified waterborne polyurethane composition pre-emulsion. Transferring the emulsion to a reflux condenser and thermometerAnd adding 60g of MMA into a mechanically stirred four-neck flask, heating to 35 ℃ and stirring for 1h, sequentially adding 0.96g of TBHP and 0.67g of sodium metabisulfite to initiate free radical polymerization, and removing acetone in the emulsion by a reduced pressure distillation mode after polymerization to obtain the 40% solid content and the semitransparent blue-light modified waterborne polyurethane composition with the particle size of 150 nm.
Comparative example 4:
into a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was charged 98.2g(toluene diisocyanate), 115g of PPG2000 (polypropylene oxide ether glycol), 23gHB (hydrogenated castor oil), 2.6g of TMP, 2.6g of MPEG1200, 16.5g of dimethylolpropionic acid, 0.05g of BiCat8108, 30.7g of CHDM, 56g of acetone, and the temperature was raised to 75 ℃ to react until the theoretical NCO value, and the reaction was stopped. Cooling to below 60 ℃, adding 264g of acetone, uniformly stirring, cooling to 30 ℃, adding 9g of IPDA and 36g of acetone mixed solution, and causing excessive viscosity and climbing. The prepolymer cannot be normally dispersed.
The compositions prepared in each example and comparative example were prepared into wood coatings according to the coating formulations listed in the specific embodiments and tested for performance. The performance test results of the obtained wood coating are shown in the following table:
those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.

Claims (10)

1. A preparation method of a modified aromatic waterborne polyurethane composition comprises the following steps:
the method comprises the steps of (1) synthesizing isocyanate-terminated prepolymer, adding organic solvent diluent and isocyanate-terminated prepolymer, fully mixing and dissolving, (2) adding organic solvent solution of aromatic secondary amine, then adding acrylate monomer and neutralizer, then adding deionized water for shearing and dispersing, then adding polyamine chain extender after dispersing is finished to obtain pre-modified emulsion, (3) emulsifying another part of modified monomer in the pre-modified emulsion, performing free radical polymerization, and finally removing low-boiling-point organic solvent.
2. The process of claim 1, wherein the isocyanate-terminated prepolymer in step (1) is prepared by mixing and reacting raw materials comprising: aromatic polyisocyanates, macromolecular polyols, small-molecule polyols, monohydric and/or dihydric alcohols with polyoxyethylene segments in their main and/or side chains, hydrophilic chain extenders, polyamine chain extenders, neutralizing agents, low boiling solvents, aromatic secondary diamines.
3. The method of preparing according to claim 2, wherein the preparation of the modified aqueous polyurethane composition comprises the following components in the following amounts based on the total mass of the isocyanate-terminated prepolymer from which the modified aqueous polyurethane composition is prepared:
1) The aromatic polyisocyanate is used in an amount of 20 to 50wt%, preferably 22.8 to 43.8wt% based on the mass of the isocyanate terminated prepolymer;
2) The macromolecular polyol is used in an amount of 20 to 65wt%, preferably 28.7 to 56.3wt%, based on the mass of the isocyanate-terminated prepolymer;
3) The small molecular polyol is used in an amount of 0.5 to 15wt%, preferably 1.06 to 10.6wt%, based on the mass of the isocyanate-terminated prepolymer;
4) The amount of the monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain contains a polyethylene oxide chain segment is 0.2 to 10wt%, preferably 0.6 to 3.3wt% of the mass of the isocyanate terminated prepolymer;
5) The hydrophilic chain extender is used in an amount of 3 to 15wt%, preferably 4.16 to 9.44wt% based on the mass of the isocyanate terminated prepolymer;
6) The polyamine chain extender is used in an amount of 0.2 to 5wt%, preferably 0.6 to 1.3wt%, based on the mass of the isocyanate terminated prepolymer;
7) The amount of the neutralizing agent is 1.0 to 10wt%, preferably 2.4 to 7.1wt% based on the mass of the isocyanate terminated prepolymer;
8) The aromatic secondary diamine accounts for 1 to 10 weight percent, preferably 3.3 to 7.6 weight percent of the weight of the isocyanate terminated prepolymer;
9) The dosage of the low boiling point solvent is 0.7-1.45 times of the mass of the isocyanate end-capped prepolymer;
10 The amount of the modifying monomer is 0.7 to 1.4 times, preferably 0.7 to 1.1 times, the mass of the isocyanate terminated prepolymer;
11 The initiator is used in an amount of 0.05 to 0.3%, preferably 0.1 to 0.2% of the total mass of the modified monomers.
4. A process according to any one of claims 1 to 3, wherein the organic solvent in step (1) is an organic solvent having a boiling point below 100 ℃, and is selected from one or more of acetone, methyl ethyl ketone, cyclohexane, dichloromethane, dichloroethane, trichloroethane, ethyl acetate, pentane, heptane, hexane, preferably acetone.
5. The process according to any one of claims 1 to 4, wherein the aromatic secondary amine in the step (2) has the following structural formula:
wherein R is 1 ＝C x H y ,R 2 ＝C x H y 1≤x≤6,3≤y≤20。
6. The process according to claim 5, wherein the aromatic secondary amine is specifically one or more selected from the group consisting of 4,4' -dimethylaminodiphenylmethane, 4' -di-sec-butylaminodiphenylmethane, 4' -di-butylaminodiphenylmethane, 4' -diethylaminodiphenylmethane and 4,4' -dihexylaminodiphenylmethane.
7. The process according to any one of claims 1 to 6, wherein the neutralizing agent in step (2) is selected from 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, aqueous ammonia; preferred neutralizing agents are sodium hydroxide, triethylamine and/or N, N-dimethylethanolamine, further preferably N, N-dimethylethanolamine; and/or the polyamine chain extender in the step (2) is an organic or inorganic primary amine or secondary amine functional compound containing at least two active hydrogens, and is specifically selected from one or more of ethylenediamine, 2-methyl-1, 5-pentanediamine, isophorone diamine, hydrazine, hydroxyethyl ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexane diamine, phenylenediamine, toluenediamine and dicyclohexylmethane diamine, and preferably isophorone diamine.
8. The method according to any one of claims 1 to 7, wherein the modified monomer in the step (3) comprises at least one of ethylenically unsaturated monomers capable of undergoing free radical polymerization, and is specifically selected from one or more of methyl acrylate, phosphoric acid acrylate, silicone acrylate, allyl methacrylate, ethyl acrylate, hydroxypropyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, hydroxyethyl methacrylate, butyl methacrylate, tetrahydrofuranacrylate, styrene, allylmethylstyrene, isobornyl acrylate, isooctyl acrylate, and the like, preferably methyl methacrylate and styrene.
9. A modified aromatic aqueous polyurethane composition obtained by the production process according to any one of claims 1 to 8.
10. A one-component wood lacquer coating, characterized in that the one-component wood lacquer coating comprises the modified aromatic aqueous polyurethane composition obtained by the preparation method according to any one of claims 1 to 8 or according to claim 9.
CN202210126909.6A 2022-02-11 2022-02-11 Synthesis and application of aromatic aqueous polyurethane/acrylic ester composition Pending CN116622031A (en)

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