Self-extinction waterborne polyurethane resin, preparation method and application
阅读说明：本技术 一种自消光水性聚氨酯树脂、制备方法及应用 (Self-extinction waterborne polyurethane resin, preparation method and application ) 是由 周操 孙常青 胡海东 晋云全 纪学顺 曹玉阳 王震 于 2021-03-01 设计创作，主要内容包括：本发明公开了一种自消光水性聚氨酯树脂、制备方法及应用,所述树脂由包含如下组分的原料在催化剂存在下混合反应制得：S1、异氰酸酯；S2、具有多个羟基的二元胺；S3、大分子多元醇；S4、主链和/或侧链含有聚氧化乙烯链段的一元醇和/或二元醇；S5、小分子多元醇扩链剂；S6、亲水性化合物或具有亲水潜质的化合物；S7、中和剂；S8、小分子二元胺扩链剂。本发明提供的树脂侧链具有多个羟基,与异氰酸酯固化剂可以充分交联形成网状高分子链,从而在提高乳胶粒粒径的同时得到大分子量的自消光聚氨酯树脂,并且抗化学品性和抗划伤性优异。(The invention discloses a self-extinction waterborne polyurethane resin, a preparation method and application thereof, wherein the resin is prepared by mixing and reacting the following raw materials in the presence of a catalyst: s1, isocyanate; s2, a diamine having a plurality of hydroxyl groups; s3, macromolecular polyol; s4, monohydric alcohol and/or dihydric alcohol with a main chain and/or a side chain containing polyoxyethylene chain segments; s5, a small molecular polyol chain extender; s6, a hydrophilic compound or a compound having a hydrophilic potential; s7, neutralizing agent; s8 and a small molecular diamine chain extender. The resin side chain provided by the invention has a plurality of hydroxyl groups, and can be fully crosslinked with an isocyanate curing agent to form a reticular polymer chain, so that the self-extinction polyurethane resin with large molecular weight is obtained while the particle size of emulsion particles is improved, and the resin side chain has excellent chemical resistance and scratch resistance.)
1. The self-extinction aqueous polyurethane resin is characterized by being prepared by mixing and reacting raw materials in the presence of a catalyst, wherein the raw materials comprise the following components:
s1, isocyanate;
s2, a diamine having a plurality of hydroxyl groups;
s3, macromolecular polyol;
s4, monohydric alcohol and/or dihydric alcohol with a main chain and/or a side chain containing polyoxyethylene chain segments;
s5, a small molecular polyol chain extender;
s6, a hydrophilic compound or a compound having a hydrophilic potential;
s7, neutralizing agent;
s8 and a small molecular diamine chain extender.
2. The self-extinction aqueous polyurethane resin according to claim 1, wherein the raw materials comprise, by mass:
s1, isocyanate 15-50%, preferably 25.2-43.1%;
s2, 1-6% of diamine with a plurality of hydroxyl groups, preferably 2.3-4.4%;
s3, 30-70% of macromolecular polyol, and preferably 38.5-61.5%;
s4, monohydric alcohol and/or dihydric alcohol with main chain and/or side chain containing polyoxyethylene chain segment 0.1-2.0%, preferably 0.21-1.34%;
s5, 4-11% of a small molecular polyol chain extender, preferably 4.7-9.2%;
s6, a hydrophilic compound or a compound having a hydrophilic potential 0.2-2.5%, preferably 0.87-1.97%;
s7, 0-2.5% of neutralizer, preferably 0-1.68%;
s8, 0.2-6.0% of micromolecular diamine chain extender, preferably 0.4-3.9%;
the addition amount of the catalyst is 0.01-0.06% of the total mass of the components S1-S8.
3. The self-matting aqueous polyurethane resin according to claim 1 or 2, wherein the isocyanate is one or more selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate trimer and hexamethylene diisocyanate trimer, and more preferably one or both of isophorone diisocyanate and dicyclohexylmethane diisocyanate;
preferably, the macropolyol is selected from one or more of polycaprolactone diol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycarbonate diol, polyethylene adipate-ethylene glycol diol, polyethylene adipate-neopentyl glycol ester diol, polyethylene adipate-1, 6-hexanediol diol, and polyethylene adipate-1, 6-hexanediol-neopentyl glycol ester diol, preferably polycaprolactone diol, more preferably polycaprolactone diol having an average molecular weight of 500-.
4. The self-extinction aqueous polyurethane resin according to claim 1 or 2, wherein the diamine having a plurality of hydroxyl groups has a general structural formula:
wherein R ═ CxHyX is 2-6, y is 4-12, preferably x is 3-5 and y is 6-10.
5. The self-matting aqueous polyurethane resin according to claim 1 or 2 wherein the monohydric and/or dihydric alcohols having a polyoxyethylene chain segment in the main chain and/or the side chain contain 90 to 100% by weight of ethylene oxide in the polymerized units, preferably Tego ChemieD-3403, Ymer N120 from Perstrop, Inc., and MPEG1200 from Korea Letian, more preferably Ymer N120 from Perstrop, and/or MPEG1200 from Korea Letian, and most preferably MPEG1200 from Korea Letian;
preferably, the chain extender of the small-molecular polyol is one or more of 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol and 2-methyl-1, 5-pentanediol.
6. The self-matting aqueous polyurethane resin according to claim 1 or 2, characterized in that the hydrophilic compound is a sulfonic acid type compound, preferably one or more of sodium 2- (2-aminoethyl) taurate, sodium 3- (2-aminoethyl) taurate, sodium 1, 4-butanediol-2-sulfonate and sodium 1, 2-dihydroxy-3-propanesulfonate, more preferably sodium 2- (2-aminoethyl) taurate;
preferably, the neutralizing agent is selected from one or more of triethanolamine, triethylamine, sodium hydroxide and dimethylethanolamine;
preferably, the diamine chain extender is selected from one or more of ethylenediamine, hydrazine hydrate, isophoronediamine, hydroxyethylethylenediamine and 2-methyl-1, 5-pentanediamine, preferably ethylenediamine.
7. The self-matting aqueous polyurethane resin according to claim 1 or 2, characterized in that the compound having a hydrophilic potential is a carboxylic acid type compound, preferably one or more of 3-hydroxypropionic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, trihydroxysulfonic acid and dihydroxysuccinic acid, more preferably dimethylolpropionic acid.
8. The self-matting aqueous polyurethane resin according to claim 1 or 2 wherein the catalyst is selected from dibutyl tin dilaurate, organobismuth or organozinc.
9. A method for producing the self-matting aqueous polyurethane resin according to any one of claims 1 to 8, comprising the steps of:
A. mixing S1 isocyanate, S3 macromolecular polyol, monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain of S4 contains polyoxyethylene chain segments, S5 micromolecular polyol chain extender, S6 compound with hydrophilic potential and catalyst in a solvent, and reacting at 70-85 ℃ until NCO reaches a theoretical value to generate diisocyanate-terminated prepolymer;
B. cooling the diisocyanate-terminated prepolymer obtained in the step A to 40-60 ℃, adding a solvent for dissolving and diluting, adding an S7 neutralizing agent, reacting for 5-10min at 30-45 ℃, adding S2 diamine with a plurality of hydroxyl groups or a mixture of the diamine and an S8 micromolecule diamine chain extender, reacting for 15-30min at 45-50 ℃, and adding deionized water for shearing and dispersing to obtain an emulsion;
C. adding the rest S8 micromolecule diamine chain extender into the emulsion in the step B, carrying out chain extension reaction for 5-15min at the temperature of 20-45 ℃, and removing the solvent to obtain the aqueous polyurethane dispersion;
or the like, or, alternatively,
I. mixing S1 isocyanate, S3 macromolecular polyol, monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain of S4 contains polyoxyethylene chain segments, S5 micromolecular polyol chain extender and catalyst in a solvent, and reacting at 70-85 ℃ until NCO reaches a theoretical value to generate a diisocyanate-terminated prepolymer;
II. Cooling the diisocyanate-terminated prepolymer obtained in the step I to 40-60 ℃, adding a solvent for dissolving and diluting, adding an S6 hydrophilic compound, S2 diamine with a plurality of hydroxyl groups or a mixture of the diamine with S8 micromolecule diamine chain extender, reacting for 20-30min at 45-50 ℃, adding deionized water, and shearing and dispersing to obtain an emulsion;
III, adding an S8 micromolecule diamine chain extender into the emulsion obtained in the step II, carrying out chain extension reaction for 5-25min at the temperature of 30-45 ℃, and removing the solvent to obtain the aqueous polyurethane dispersion;
preferably, the solvent is selected from ketone solvents, preferably one of butanone, acetone and cyclohexanone, more preferably butanone, acetone, most preferably acetone.
10. Use of the self-matting aqueous polyurethane resin according to any one of claims 1 to 8 in low-gloss coatings, in particular in the fields of leather finishing, wood plastic finishing, paper printing, printing inks, print coatings, packaging coatings, matting nail polish.
Technical Field
The invention relates to a self-extinction resin, in particular to a self-extinction aqueous polyurethane resin, a preparation method and application.
Background
Matte resins are becoming increasingly popular because of their ability to give them a unique visual perception. The matte resin can be divided into two modes of external addition of matting powder and self-matting, and the matting powder is easy to separate out by the external addition of the matting powder, so that the problems of poor scratch resistance and the like are solved. Self-extinction resin has been developed greatly in recent years, and the principle of the self-extinction resin is that latex particles with the particle size larger than 1100 nanometers are kept spherical after film forming, and diffuse reflection is formed after light incidence and cannot be emitted back, so that the glossiness is reduced. This tends to cause problems such as insufficient film formation density and insufficient chemical resistance of the resin. In order to solve such problems, a crosslinkable substance, for example, a substance of the class of azapyridines and carbodiimides which can be crosslinked with carboxyl groups, or an isocyanate curing agent which can be crosslinked with hydroxyl groups, is generally added at a later stage. Because the azopyridine and the carbodiimide have higher toxicity and stronger volatility, the mode of adding the isocyanate curing agent is more environment-friendly. Or components capable of post-crosslinking, such as alkyd resins, as disclosed in chinese patent CN1318471C, but this method requires additional addition of a drier and the drying speed is slow.
The isocyanate curing agent is matched with the condition that the resin must have hydroxyl, and the general method for synthesizing hydroxyl polyurethane is to react isocyanate and alcohol to generate prepolymer with isocyanate, and then to use polyol (such as trimethylolpropane) containing two or more hydroxyl groups or amine unit (such as diethanolamine) containing two or more hydroxyl groups to end-cap the resin to have hydroxyl groups. However, this has a problem that since the molecular chain of the resin is blocked, a molecular chain of a large molecular weight cannot be obtained, and thus even if the particle diameter of the emulsion is made large, self-extinction cannot be achieved because the molecular weight is too small.
There is therefore a need for a new self-immolative resin which can be used in combination with an isocyanate curing agent.
Disclosure of Invention
The invention aims to provide a self-extinction waterborne polyurethane resin, the side chain of which has a plurality of hydroxyl groups, and the self-extinction waterborne polyurethane resin can be fully crosslinked with an isocyanate curing agent to form a reticular polymer chain, so that the chemical resistance and the scratch resistance of the resin are greatly improved.
The invention also aims to provide a preparation method of the self-extinction aqueous polyurethane resin, which leads the resin and the isocyanate curing agent to have stronger reticular cross-linking property by introducing the polyhydroxy diamine to the side group of the molecular chain during chain extension, thereby obtaining the self-extinction polyurethane resin with large molecular weight while improving the particle size of the emulsion particles and ensuring the chemical resistance and scratch resistance of the resin.
Another object of the present invention is to provide a self-matting aqueous polyurethane resin for use in low-gloss coatings.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the self-extinction waterborne polyurethane resin is prepared by mixing and reacting the following raw materials in the presence of a catalyst:
s1, isocyanate;
s2, a diamine having a plurality of hydroxyl groups;
s3, macromolecular polyol;
s4, monohydric alcohol and/or dihydric alcohol with a main chain and/or a side chain containing polyoxyethylene chain segments;
s5, a small molecular polyol chain extender;
s6, a hydrophilic compound or a compound having a hydrophilic potential;
s7, neutralizing agent;
s8 and a small molecular diamine chain extender.
Further, the raw materials comprise the following components in percentage by mass:
s1, isocyanate 15-50%, preferably 25.2-43.1%;
s2, 1-6% of diamine with a plurality of hydroxyl groups, preferably 2.3-4.4%;
s3, 30-70% of macromolecular polyol, and preferably 38.5-61.5%;
s4, monohydric alcohol and/or dihydric alcohol with main chain and/or side chain containing polyoxyethylene chain segment 0.1-2.0%, preferably 0.21-1.34%;
s5, 4-11% of a small molecular polyol chain extender, preferably 4.7-9.2%;
s6, a hydrophilic compound or a compound having a hydrophilic potential 0.2-2.5%, preferably 0.87-1.97%;
s7, 0-2.5% of neutralizer, preferably 0-1.68%;
s8, 0.2-6.0% of micromolecular diamine chain extender, preferably 0.4-3.9%;
the addition amount of the catalyst is 0.01-0.06% of the total mass of the components S1-S8.
Further, the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate trimer and hexamethylene diisocyanate trimer, and is further preferably one or two of isophorone diisocyanate and dicyclohexylmethane diisocyanate;
preferably, the macropolyol is selected from one or more of polycaprolactone diol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycarbonate diol, polyethylene adipate-ethylene glycol diol, polyethylene adipate-neopentyl glycol ester diol, polyethylene adipate-1, 6-hexanediol diol, and polyethylene adipate-1, 6-hexanediol-neopentyl glycol ester diol, preferably polycaprolactone diol, more preferably polycaprolactone diol having an average molecular weight of 500-.
Further, the diamine with a plurality of hydroxyl groups has a structural general formula as follows:
wherein R ═ CxHyX is 2-6, y is 4-12, preferably x is 3-5 and y is 6-10.
The preparation process of the diamine with a plurality of hydroxyl groups comprises the following steps:
mixing Br-R-Br and trihydroxymethyl aminomethane in a solvent according to a molar ratio of 1:1-8, reacting for 7-12h under a reflux condition, carrying out deep cold crystallization (-5 ℃ to-10 ℃) or normal temperature crystallization after the reaction is finished, filtering, adding HBr into filtrate to acidify until the pH value is 1-3, carrying out deep cold crystallization, carrying out suction filtration, dissolving a filter cake in absolute ethyl alcohol, adjusting the pH value to 9-11 by using a sodium hydroxide solution, carrying out deep cold crystallization, suction filtration and drying to obtain a crude product. Dissolving the crude product in hot absolute ethyl alcohol, naturally cooling for 20-40 minutes, carrying out vacuum filtration to remove insoluble substances, then recrystallizing at room temperature, and filtering to obtain a pure product.
Among them, Br-R-Br is preferably one or more of 1, 2-dibromobutane, 1, 3-dibromopropane, 1, 4-dibromobutane and 1, 5-dibromopentane.
Further, the monohydric alcohol and/or dihydric alcohol having a polyoxyethylene chain segment in the main chain and/or the side chain contains 90-100 wt% of ethylene oxide in the polymerization unit, preferably Tego ChemieD-3403, Ymer N120 from Perstrop, Inc., and MPEG1200 from Korea Letian, more preferably Ymer N120 from Perstrop, and/or MPEG1200 from Korea Letian, and most preferably MPEG1200 from Korea Letian;
preferably, the chain extender of the small molecular weight polyol is one or more of 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol and 2-methyl-1, 5-pentanediol, and preferably one or more of neopentyl glycol, 1, 2-propanediol and 1, 4-cyclohexanedimethanol.
Further, the hydrophilic compound is a sulfonic acid type compound, preferably one or more of sodium 2- (2-aminoethyl) aminoethane sulfonate, sodium 3- (2-aminoethyl) aminopropane sulfonate, sodium 1, 4-butanediol-2-sulfonate and sodium 1, 2-dihydroxy-3-propane sulfonate, more preferably sodium 2- (2-aminoethyl) aminoethane sulfonate;
preferably, the neutralizing agent is selected from one or more of triethanolamine, triethylamine, sodium hydroxide and dimethylethanolamine;
preferably, the diamine chain extender is selected from one or more of ethylenediamine, hydrazine hydrate, isophoronediamine, hydroxyethylethylenediamine and 2-methyl-1, 5-pentanediamine, preferably ethylenediamine.
Further, the compound having a hydrophilic potential is a carboxylic acid type compound, preferably one or more of 3-hydroxypropionic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, trihydroxysulfonic acid and dihydroxysuccinic acid, more preferably dimethylolpropionic acid.
Further, the catalyst is selected from dibutyl tin dilaurate, organobismuth or organozinc, preferably dibutyl tin dilaurate or organobismuth 8108 from the leading company in the united states.
The preparation method of the self-extinction waterborne polyurethane resin comprises the following two steps:
the method comprises the following steps:
A. mixing S1 isocyanate, S3 macromolecular polyol, monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain of S4 contains polyoxyethylene chain segments, S5 micromolecular polyol chain extender, S6 compound with hydrophilic potential and catalyst in a solvent, and reacting at 70-85 ℃ until NCO reaches a theoretical value to generate diisocyanate-terminated prepolymer;
B. cooling the diisocyanate-terminated prepolymer obtained in the step A to 40-60 ℃, adding a solvent for dissolving and diluting, adding an S7 neutralizing agent, reacting for 5-10min at 30-45 ℃, adding S2 diamine with a plurality of hydroxyl groups or a mixture of the diamine and an S8 small-molecular diamine chain extender (the diamine can be diluted by adding a proper amount of water according to the viscosity of the system), reacting for 15-30min at 45-50 ℃, and adding deionized water for shearing and dispersing to obtain an emulsion;
C. adding an S8 micromolecule diamine chain extender into the emulsion B, carrying out chain extension reaction for 5-15min at the temperature of 20-45 ℃, and removing the solvent to obtain the aqueous polyurethane dispersion;
preferably, the amount of the S8 small-molecule diamine chain extender added in the step B accounts for 50-100% of the total mass of the S8 component, and more preferably, the types of the S8 small-molecule diamine chain extender in the step B, C can be the same or different.
The second method comprises the following steps:
I. mixing S1 isocyanate, S3 macromolecular polyol, monohydric alcohol and/or dihydric alcohol of which the main chain and/or the side chain of S4 contains polyoxyethylene chain segments, S5 micromolecular polyol chain extender and catalyst in a solvent, and reacting at 75-85 ℃ until NCO reaches a theoretical value to generate a diisocyanate-terminated prepolymer;
II. Cooling the diisocyanate-terminated prepolymer obtained in the step I to 40-60 ℃, adding a solvent for dissolving and diluting, then adding an S6 hydrophilic compound, S2 diamine with a plurality of hydroxyl groups or a mixture of the diamine with S8 micromolecule diamine chain extender (a proper amount of water can be added for diluting according to the system viscosity), reacting for 20-30min at 45-50 ℃, adding deionized water for shearing and dispersing to obtain an emulsion;
III, adding an S8 micromolecule diamine chain extender into the emulsion obtained in the step II, carrying out chain extension reaction for 5-25min at the temperature of 30-45 ℃, and removing the solvent to obtain the aqueous polyurethane dispersion.
In the above-mentioned first or second process, the total amount of the solvent used is 1.1 to 2.0 times, preferably 1.36 to 1.87 times, the total mass of the components S1 to S8. The solvent removal method may be, for example, distillation under reduced pressure.
Preferably, the solvent is selected from ketone solvents, preferably one of butanone, acetone and cyclohexanone, more preferably butanone, acetone, most preferably acetone.
Preferably, the self-extinction aqueous polyurethane resin prepared by the method has a solid content of 30-40%.
The invention also provides an application of the self-extinction waterborne polyurethane resin in low-gloss paint, in particular to the application in the fields of leather finishing, woodware plastic finishing, paper printing, printing and dyeing ink, printing coating, packaging coating and extinction methyl varnish.
The invention has the following technical effects:
1) the novel self-extinction resin provided by the invention does not contain VOC, is safe and environment-friendly, and is simple in production process and convenient to operate;
2) the side chain of the novel self-extinction resin provided by the invention has a plurality of hydroxyl groups, the content of the hydroxyl groups is more than 2.5%, and the novel self-extinction resin can be fully crosslinked with an isocyanate curing agent, so that the chemical resistance and the scratch resistance of the product are greatly improved;
3) according to the novel self-extinction resin provided by the invention, hydroxyl is introduced to a side group of a molecular chain through diamine with polyhydroxy during chain extension, and is not introduced through blocking of polyol or monoamine (such as diethanolamine) containing two or more hydroxyl groups in the traditional process, so that a larger molecular weight can be obtained while hydroxyl is introduced. When the film is formed, because the molecular weight is large enough, the polyurethane colloidal particles can form 1-2um spheres, and the extinction effect can be well achieved;
4) the novel self-extinction resin provided by the invention has the advantages that the molecular chain has the side group with high hydroxyl content, so that a hydrogen bond can be formed with the surface of the base material, and the adhesive force of the resin to the base material is improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
First, embodiment main raw material source:
polycaprolactone diol: functionality of 2, molecular weight 1000g/mol, Dailco, Inc.;
poly adipic acid-neopentyl glycol ester diol: functionality of 2, molecular weight 1000g/mol, technical grade, Vanhua chemical group GmbH;
poly 1, 6-hexanediol-neopentyl glycol adipate diol: industrial grade, wanhua chemical group, inc;
polytetrahydrofuran ether diol: functionality of 2, molecular weight 1000g/mol, basf ltd;
catalyst: bi @8108, advanced USA Inc.;
1, 2-propylene glycol: industrial grade, national pharmaceutical chemicals, ltd;
dimethylolpropionic acid (DMPA): technical grade, boston chemical company;
dimethylol butyric acid (DMBA): industrial grade, Shandonghao Shuihu chemical Co., Ltd;
neopentyl glycol: industrial grade, wanhua chemical group, inc;
acetone: industrial grade, wanhua chemical group, inc;
polypropylene glycol: functionality of 2, molecular weight of 1000g/mol, Vanhua chemical group GmbH;
isophorone diamine: industrial grade, wanhua chemical group, inc;
hexamethylene Diisocyanate (HDI): industrial grade, wanhua chemical group, inc;
isophorone diisocyanate (IPDI): industrial grade, wanhua chemical group, inc;
dicyclohexylmethane diisocyanate (HMDI): industrial grade, wanhua chemical group, inc;
1, 4-butanediol: analytically pure, national chemical reagents ltd;
dimethylethanolamine: analytically pure, national chemical reagents ltd;
1, 4-cyclohexanedimethanol: analytically pure, national chemical reagents ltd;
ethylene diamine: analytically pure, national chemical reagents ltd;
triethylamine: analytically pure, national chemical reagents ltd;
polyethylene glycol monomethyl ether (MPEG 1200): technical grade, molecular weight 1200, korea le day company;
polyethylene glycol (N120): technical grade, molecular weight 1000, boston corporation;
2- (2-aminoethyl) aminoethanesulfonic acid sodium saltAminoalkyl sulfonate hydrophilic chain extender, winning from chemical Limited;
sodium 3- (2-aminoethyl) aminopropanesulfonate: aminoalkyl sulfonate hydrophilic chain extenders, golden brocade chemical ltd;
other raw materials are purchased from the market unless otherwise specified.
Secondly, an analytical instrument and a test method are provided:
hydroxyl value calculation method: calculating a resin hydroxyl value according to the formula 1700n M/M, wherein n refers to the hydroxyl functionality of a diamine having a plurality of hydroxyl groups, M refers to the number of moles of a diamine having a plurality of hydroxyl groups, and M refers to the total mass of the resin;
the swing rod hardness testing method comprises the following steps: TQC pendulum hardometer, SP 0500;
the solid content testing 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 30min, and calculating the solid content.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
Ethanol resistance test method: the method comprises the steps of preparing plastic paint by taking waterborne polyurethane resin as a raw material, brushing the prepared plastic paint on a plastic substrate, wiping the plastic substrate by using a disposable cotton stick stained with ethanol, and testing the wiping frequency of the leaked substrate.
Gloss: brushing the prepared plastic paint on a plastic substrate, drying for about 1min at 100 ℃, and testing the glossiness by a gloss meter.
The scratch resistance test method comprises the following steps: brushing the prepared plastic paint on a plastic substrate, drying for about 1min at 100 ℃, then scratching with a fingernail, observing whether the surface has scars or not, wherein the scoring range is 1-5 points, and the performance is the best when the scoring is 5 points.
Example 1 was prepared: preparation of 1, 3-bis ((trimethylol) methylamino) propane
Mixing 1, 3-dibromopropane and tris (hydroxymethyl) aminomethane in an ethanol solvent according to a molar ratio of 1:4, reacting for 8 hours under a reflux condition, carrying out cryogenic crystallization at-5 ℃ after the reaction is finished, filtering, adding HBr into filtrate to acidify the filtrate until the pH value is 2, carrying out cryogenic crystallization at-5 ℃, carrying out suction filtration, dissolving a filter cake in absolute ethanol, adjusting the pH value to 10 by using a sodium hydroxide solution, carrying out cryogenic crystallization at-5 ℃, carrying out suction filtration, and drying to obtain a crude product. Dissolving the crude product in hot absolute ethyl alcohol, naturally cooling for 30min, vacuum filtering to remove insoluble substances, recrystallizing at room temperature, and filtering to obtain the pure product.
Nuclear magnetic characterization was as follows:
1H NMR(CDCl3,400MHz,TMS):δ1.58(m,2H),2.55(t,4H),3.38(m，12H).
example 2 was prepared: preparation of 1, 4-bis ((trihydroxymethyl) methylamino) butane
1, 4-bis ((trimethylol) methylamino) butane was prepared according to the above method except that the starting material 1, 3-dibromopropane was replaced with 1, 4-dibromobutane.
Nuclear magnetic characterization was as follows:
1H NMR(CDCl3,400MHz,TMS):δ1.4(m,4H),2.45(m,4H),3.48(m，12H).
example 3 was prepared: preparation of 1, 5-bis ((trimethylol) methylamino) pentane
1, 5-bis ((trimethylol) methylamino) pentane was prepared according to the above method, except that the starting material 1, 3-dibromopropane was replaced with 1, 5-dibromopentane.
Nuclear magnetic characterization was as follows:
1H NMR(CDCl3,400MHz,TMS):δ1.19(m,2H),1.48(m,4H),2.55(t，4H),3.48(m，12H).
example 1
Adding 120 g of polycaprolactone diol, 2g of polyethylene glycol monomethyl ether, 3 g of dimethylolpropionic acid and 17.5 g of 1, 4-cyclohexanedimethanol into a four-neck flask with a condenser and a stirrer, adding 72 g of IPDI, 0.08 g of Bi @8108 and 50 g of acetone, and reacting at 70 ℃ for 3 hours, wherein the NCO value is 1.8%, and the theoretical value is 1.89%; cooling to 40 ℃, adding 300 g of acetone, then adding 1.9 g of dimethylethanolamine, reacting for 10 minutes at 35 ℃, then adding a mixed solution of 9 g of 1, 3-bis ((trihydroxymethyl) methylamino) propane and 36 g of deionized water, and reacting for 30 minutes at 45 ℃; and then adding 500 g of deionized water into the mixture at a high speed, adding a mixture of 1 g of hydroxyethyl ethylenediamine and 4 g of deionized water after dispersion is finished, reacting the mixture at 40 ℃ for 5 minutes, and removing the solvent acetone from the reaction product at 45 ℃ and under the vacuum condition of 0.01MPa to obtain the novel self-extinction waterborne polyurethane emulsion 1 with the particle size of 1800nm, the solid content of 35 percent and the hydroxyl value of 2.9 percent.
Example 2
Adding 92.4 g of polytetrahydrofuran ether dihydric alcohol, 0.5 g of polyethylene glycol monomethyl ether, 4.7 g of dimethylolpropionic acid and 22 g of 1, 4-cyclohexanedimethanol into a four-neck flask with a condenser and a stirrer, adding 100.1 g of IPDI, 0.124 g of Bi @8108 and 50 g of acetone, and reacting at 80 ℃ for 3 hours, wherein the NCO value is 5.0 percent and the theoretical value is 5.3 percent; cooling to 50 ℃, adding 305 g of acetone, then adding 4.0 g of dimethylethanolamine, reacting for 5 minutes at 45 ℃, then adding a mixed solution of 5.6 g of 1, 4-bis ((trihydroxymethyl) methylamino) butane, 9.2 g of hydroxyethyl ethylenediamine and 74 g of deionized water, and reacting for 30 minutes at 45 ℃; and then adding 500 g of deionized water into the mixture at a high speed, adding a mixture of 2g of ethylenediamine and 8 g of deionized water after dispersion is finished, reacting for 5 minutes at 40 ℃, and removing solvent acetone from a reaction product under the vacuum conditions of 45 ℃ and 0.01MPa to obtain the novel self-extinction waterborne polyurethane emulsion 2, wherein the particle size is 2300nm, the solid content is 35 percent, and the hydroxyl value is 2.86 percent.
Example 3
Adding 120 g of polypropylene glycol, 2g of polyethylene glycol monomethyl ether, 3.4 g of dimethylolpropionic acid and 14 g of neopentyl glycol into a four-neck flask with a condenser and a stirrer, adding 84 g of IPDI, 50 g of acetone and 0.045 g of Bi @8108, and reacting at 80 ℃ for 3 hours, wherein the NCO value is 2.8 percent and the theoretical value is 3.0 percent; cooling to 60 ℃, adding 400 g of acetone, then adding 2.5 g of triethylamine, reacting for 5 minutes at 45 ℃, then adding a mixed solution of 10 g of 1, 5-bis ((trihydroxymethyl) methylamino) pentane, 2g of isophorone diamine and 48 g of deionized water, and reacting for 15 minutes at 50 ℃; and then adding 500 g of deionized water into the mixture at a high speed, adding a mixture of 2g of ethylenediamine and 8 g of deionized water after dispersion is finished, reacting the mixture at 30 ℃ for 10 minutes, and removing the solvent acetone from the reaction product at 45 ℃ and under the vacuum condition of 0.01MPa to obtain the novel self-extinction waterborne polyurethane emulsion 3 with the particle size of 2100nm, the solid content of 35 percent and the hydroxyl value of 2.6 percent.
Example 4
180 g of poly (1, 6-hexanediol-neopentyl glycol) adipate diol, 2g of polyethylene glycol monomethyl ether, 2.0 g of dimethylolpropionic acid and 19 g of 1, 4-cyclohexanedimethanol were introduced into a four-neck flask with a condenser and a stirrer, and 42 g of IPDI and 31.8 g of HDI, 50 g of acetone and 0.06 g of Bi @8108 were added and reacted at 85 ℃ for 3 hours, the NCO value being 2.6% and the theoretical value being 2.85%; cooling to 40 ℃, adding 350 g of acetone, then adding 1.3 g of dimethylethanolamine, reacting for 5 minutes at 45 ℃, then adding a mixed solution of 12g of 1, 3-bis ((trihydroxymethyl) methylamino) propane, 1.3 g of ethylenediamine and 53.2 g of deionized water, and reacting for 20 minutes at 48 ℃; then 600 g of deionized water is added in the high-speed shearing, after the dispersion is finished, a mixture of 1.3 g of ethylenediamine and 5.2 g of deionized water is added, after the reaction is carried out for 5 minutes at 45 ℃, the solvent acetone is removed from the reaction product under the vacuum condition of 45 ℃ and 0.01MPa, and the novel self-extinction aqueous polyurethane emulsion 4 with the particle size of 2500nm, the solid content of 35 percent and the hydroxyl value of 3.4 percent is obtained.
Example 5
Adding 92.4 g of poly (neopentyl glycol adipate) -diol, 3.1 g of polyethylene glycol monomethyl ether and 20 g of 1, 2-propylene glycol into a four-neck flask with a condenser and a stirrer, adding 100.1 g of IPDI, 0.1 g of Bi @8108 and 46 g of acetone, and reacting at 80 ℃ for 3 hours, wherein the NCO value is 3.0 percent, and the theoretical value is 3.02 percent; the temperature is reduced to 40 ℃, 350 g of acetone are added, then 10 g of 1, 3-bis ((trimethylol) methylamino) propane and 2g are addedReacting the mixed solution with 48 g of deionized water at 45 ℃ for 30 min; and then 423 g of deionized water is added in the high-speed shearing process, a mixture of 3 g of isophorone diamine and 12g of deionized water is added after the dispersion is finished, the mixture reacts for 5 minutes at 40 ℃, and then the solvent acetone is removed from the reaction product under the vacuum conditions of 45 ℃ and 0.01MPa, so that the novel self-extinction waterborne polyurethane emulsion 5 is obtained, wherein the particle size is 2800nm, the solid content is 35%, and the hydroxyl value is 3.1%.
Example 6
Adding 120 g of polycaprolactone diol, 2g of polyethylene glycol, 3 g of dimethylolbutyric acid and 11 g of 1, 4-butanediol into a four-neck flask with a condenser and a stirrer, adding 85 g of HMDI, 0.08 g of Bi @8108 and 50 g of acetone, and reacting at 70 ℃ for 3 hours, wherein the NCO value is 1.79%, and the theoretical value is 1.89%; cooling to 40 ℃, adding 300 g of acetone, then adding 1.9 g of dimethylethanolamine, reacting for 10 minutes at 35 ℃, then adding a mixed solution of 9 g of 1, 3-bis ((trihydroxymethyl) methylamino) propane and 36 g of deionized water, and reacting for 30 minutes at 45 ℃; and then adding 500 g of deionized water into the mixture at a high speed, adding a mixture of 1 g of hydroxyethyl ethylenediamine and 4 g of deionized water after dispersion is finished, reacting the mixture at 40 ℃ for 5 minutes, and removing the solvent acetone from the reaction product at 45 ℃ and under the vacuum condition of 0.01MPa to obtain the novel self-extinction waterborne polyurethane emulsion 6 with the particle size of 1750nm, the solid content of 35 percent and the hydroxyl value of 2.84 percent.
Example 7
Adding 92.4 g of polytetrahydrofuran ether dihydric alcohol, 3.1 g of polyethylene glycol monomethyl ether and 20 g of 1, 4-butanediol into a four-neck flask with a condenser and a stirrer, adding 100.1 g of IPDI, 0.1 g of Bi @8108 and 46 g of acetone, and reacting at 80 ℃ for 3 hours, wherein the NCO value is 3.0 percent, and the theoretical value is 3.02 percent; cooling to 40 ℃, adding 350 g of acetone, then adding a mixed solution of 9.2 g of 1, 3-bis ((trihydroxymethyl) methylamino) propane, 3 g of sodium 3- (2-aminoethyl) aminopropanesulfonate and 48 g of deionized water, and reacting for 30min at 45 ℃; and then 423 g of deionized water is added in the high-speed shearing process, a mixture of 8 g of isophorone diamine and 12g of deionized water is added after the dispersion is finished, the mixture reacts for 5 minutes at 40 ℃, and then the solvent acetone is removed from the reaction product under the vacuum conditions of 45 ℃ and 0.01MPa, so that the novel self-extinction waterborne polyurethane emulsion 7 is obtained, wherein the particle size is 2700nm, the solid content is 35 percent, and the hydroxyl value is 4.52 percent.
Comparative example 1
Adding 120 g of polycaprolactone diol, 2g of polyethylene glycol monomethyl ether, 3 g of dimethylolpropionic acid and 17.5 g of 1, 4-cyclohexanedimethanol into a four-neck flask with a condenser and a stirrer, adding 72 g of IPDI, 0.08 g of Bi @8108 and 50 g of acetone, and reacting at 70 ℃ for 3 hours, wherein the NCO value is 1.8%, and the theoretical value is 1.89%; then adding 12g of trimethylolpropane, continuing to react until the NCO value is below 0.1%, cooling to 40 ℃, adding 300 g of acetone, then adding 1.9 g of dimethylethanolamine, reacting for 10 minutes at 35 ℃, adding 500 g of deionized water under high-speed shearing, and removing the solvent acetone from the reaction product under vacuum conditions of 45 ℃ and 0.01MPa to obtain emulsion 6 with the particle size of 1200nm, the solid content of 35% and the hydroxyl value of 1.36%.
Comparative example 2
Adding 120 g of polycaprolactone diol, 2g of polyethylene glycol monomethyl ether, 3 g of dimethylolpropionic acid and 17.5 g of 1, 4-cyclohexanedimethanol into a four-neck flask with a condenser and a stirrer, adding 72 g of IPDI, 0.08 g of Bi @8108 and 50 g of acetone, and reacting at 70 ℃ for 3 hours, wherein the NCO value is 1.8%, and the theoretical value is 1.89%; cooling to 40 ℃, adding 300 g of acetone, then adding 1.9 g of dimethylethanolamine, reacting for 10 minutes at 35 ℃, then adding a mixed solution of 11 g of diethanolamine and 44 g of deionized water, and reacting for 30 minutes at 45 ℃; then 500 g of deionized water is added in the high-speed shearing, and the solvent acetone is removed from the reaction product under the vacuum condition of 45 ℃ and 0.01MPa, thus obtaining the emulsion 6 with the grain diameter of 1700nm, the solid content of 35 percent and the hydroxyl value of 1.59 percent.
Comparative example 3
Adding 120 g of polycaprolactone diol, 2g of polyethylene glycol monomethyl ether, 3 g of dimethylolpropionic acid and 17.5 g of 1, 4-cyclohexanedimethanol into a four-neck flask with a condenser and a stirrer, adding 72 g of IPDI, 0.08 g of Bi @8108 and 50 g of acetone, and reacting at 70 ℃ for 3 hours, wherein the NCO value is 1.8%, and the theoretical value is 1.89%; cooling to 40 ℃, adding 300 g of acetone, then adding 1.9 g of dimethylethanolamine, reacting for 10 minutes at 35 ℃, then adding a mixed solution of 7.2 g of ethylenediamine butanol and 28 g of deionized water, and reacting for 30 minutes at 45 ℃; and then adding 500 g of deionized water into the mixture at a high speed, adding a mixture of 1 g of hydroxyethyl ethylenediamine and 4 g of deionized water after dispersion is finished, reacting the mixture at 40 ℃ for 5 minutes, and removing the solvent acetone from the reaction product at 45 ℃ and under the vacuum condition of 0.01MPa to obtain the self-extinction waterborne polyurethane emulsion 7 with the particle size of 1800nm, the solid content of 35 percent and the hydroxyl value of 1.09 percent.
[ application example ] preparation of aqueous Plastic paint Using the aqueous polyurethane resins in examples 1 to 7 and comparative examples 1 to 3
The water-based plastic paint is prepared according to the following method: according to the mass ratio, the components shown in the table 1 are sequentially added under the stirring of 1500r/min at room temperature, stirred for 30 minutes until the components are completely dispersed, and then the components shown in the table 2 are added, wherein the mass ratio of the component A to the component B is 5: 1.
TABLE 1 formulation of component A
Name of raw materials
Mass/%)
Description of the invention
Aqueous polyurethane resin
85
Deionized water
12.7
DPnB
0.5
Dow, film-Forming aid
DPM
0.5
Dow, film-Forming aid
Tego 810
0.1
Yinchang defoaming agent
BYK-7420ES
0.1
BYK, anti-settling agent
Tego 4100
0.4
Wound-healing and wetting agent
Vesmody u300
0.3
Wanhua polyurethane thickener
Vesmody u604
0.2
Wanhua polyurethane thickener
Vesmody u902
0.2
Wanhua polyurethane thickener
TABLE 2 formulation of component B
Name of raw materials
Mass/%)
Description of the invention
Aquolin 268
80
Wanhua water-based curing agent
PMA
20
DOW, propylene glycol methyl ether acetate
The water-based plastic paint prepared in each application example was subjected to a glossiness test, an ethanol resistance test and a scratch resistance test, and the test results are respectively shown in table 3:
TABLE 3 results of Performance test
Example 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Comparative example 1
Comparative example 2
Comparative example 3
Gloss degree/° C
0.2
0.3
0.5
0.4
0.6
0.4
0.5
50
60
0.8
Tolerance to ethanol/times
15
10
12
16
13
12
15
10
9
5
Scratch/score resistance
5
4
5
4
5
5
5
4
4
3
And (3) comparing and analyzing test results:
as can be seen from the test results in Table 3, the gloss of the plastic paint prepared from the aqueous polyurethane emulsion in each example of the invention is low, which indicates that the plastic paint has good self-extinction effect, while the molecular weight of the aqueous polyurethane resin in comparative examples 1 and 2 is low because the molecular chain is blocked, and the self-extinction function cannot be realized even if the particle size of the emulsion is large. In addition, the plastic paint prepared from the aqueous polyurethane emulsion in each embodiment of the invention also has excellent ethanol resistance and scratch resistance, and the aqueous polyurethane resin in the comparative example 3 has poor reactivity with a curing agent during preparation of the aqueous plastic paint due to a low hydroxyl value, so that the plastic paint has low ethanol resistance and scratch resistance, is poor in mechanical and chemical properties, and cannot meet the application requirements of products.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.