CN103113532B - Preparation method of normal-temperature self-crosslinking water-based polyurethane emulsion - Google Patents
Preparation method of normal-temperature self-crosslinking water-based polyurethane emulsion Download PDFInfo
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Abstract
The invention relates to a preparation method of a normal-temperature self-crosslinking water-based polyurethane emulsion. Water-based polyurethane can only be of a linear structure and often has the defects of poor water resistance, solvent resistance and mechanical property. The preparation method comprises the following steps: mixing an inert vinyl monomer, polymer polyalcohol, a diisocyanate compound, anionic mixed hydrophilic chain extender and a catalyst to perform reaction, adding a hydrophilic vinyl monomer to perform end capping, adding volatile alkali to perform neutralization, adding water and stirring, adding diacetone acrylamide and an initiator water solution to prepare a water-based polyurethane emulsion, and adding dihydrazide into the emulsion to prepare the target product. The normal-temperature self-crosslinking water-based polyurethane emulsion prepared by the invention can be cured to form a film at room temperature along with the drying of the emulsion; and compared with a water-based polyurethane latex film which does not have a self-crosslinking structure, the water absorption rate and the acetone absorption rate of the coated film are greatly reduced, and the water resistance and the solvent resistance are greatly enhanced.
Description
Technical field
the invention belongs to chemical field, be specifically related to a kind of preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature.
Background technology
Aqueous polyurethane is taking water as medium, and safety and environmental protection is free from environmental pollution, has good physical and mechanical properties simultaneously, and the excellent performance such as low temperature resistant, weather-proof is widely used in that coating, tackiness agent, textile finishing, leather, synthetic leather are covered with paint, lacquer, colour wash, etc. and the field such as ink.But relatively solvent type urethane, aqueous polyurethane is because the restriction of synthesis technique can only obtain linear structure, and due to the introducing of hydrophilic radical, often has water-fast, solvent resistance and the poor shortcoming of mechanical property.Because mono-component polyurethane emulsion is the linear thermoplastic's urethane being dispersed in water, can not reach the cross-linking density and relative high relative molecular mass of conventional solvent borne polyurethane, therefore the aspect such as water tolerance, solvent resistance, chemical-resistant, wear resistance, hardness still can not reach the performance of solvent borne urethane, and overall performance and solvent borne polyurethane also have certain gap.Crosslinked is the effective ways that improve Property of Waterborne Polyurethane, and the aqueous polyurethane of exploitation cold cross-linking has become an important directions.Conventional cold cross-linking agent has aziridine, formaldehyde, polycarbodiimide, epoxies and isocyanates etc., but owing to existing, some shortcoming is as large in toxicity, validity period is short, expensive etc., is restricted in the use.
Summary of the invention
The object of this invention is to provide the preparation method of the waterborne polyurethane emulsion capable of self-crosslinking at normal temperature that a kind ofly there is high crosslink density, can improve product application performance, can environment and operator not polluted and be damaged simultaneously.
The technical solution adopted in the present invention is:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is characterized in that:
Realized by following steps:
Step 1: add the inertia vinyl monomer of 4-18 weight part, polymer polyatomic alcohol, the diisocyanate cpd of 8.5-14 weight part and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.66-2.95 weight part of 9.48-13.35 weight part in dry reactor, temperature of reaction is 70-90 DEG C, and the reaction times is 1-4 hour;
Step 2: add again the hydrophilic ethylene base monomer of 1-4 weight part to carry out end-blocking, reaction 0.5-1 hour, again system temperature is cooled to 30-50 DEG C, add again the volatile alkali of 1.3-3.2 weight part, neutralization reaction 20-30 minute, add 60-100 weight parts water, high-speed stirring is disperseed 10-30 minute, then is warming up to 70-90 DEG C again;
Step 3: be under the condition of 70-90 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.25-1 weight part in reactor, initiator solution was evenly splashed in reactor in 1-3 hour, after dropwising, continue insulation reaction 1-3 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.1-0.5 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
In step 1, in dry reactor, also added catalyzer, be selected from dibutyl tin laurate, dibutyltin diacetate, stannous octoate, its weight part is 0 < m≤0.095 part.
In step 1, described inertia vinyl monomer is selected from methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, vinylformic acid n-octyl, n octyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, vinylbenzene, alpha-methyl styrene.
In step 1, described polymer polyatomic alcohol is selected from poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate diol, the polytetrahydrofuran diol of molecular weight between 1000 ~ 2000.
In step 1, described diisocyanate cpd is selected from isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate.
In step 1, described negatively charged ion mixing hydrophilic chain extender is selected from the one in dimethylol propionic acid, dimethylolpropionic acid, or is that one in a kind of and dihydroxyl propanesulfonate in dimethylol propionic acid, dimethylolpropionic acid, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium is with 1:(0.2-4) the mixture that mixes of mass ratio.
In step 2, described hydrophilic ethylene base monomer is selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, acrylamide, n-methylolacrylamide.
In step 2, described volatile alkali is selected from Trimethylamine 99, triethylamine, ammoniacal liquor.
In step 3, described initiator is selected from Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride, and described initiator solution refers to the initiator of 0.5-1 weight part is dissolved in to the aqueous solution obtaining in the water of 10-40 weight part.
In step 3, two described hydrazides are selected from succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, phenylbenzene phosphinylidyne two hydrazines.
The present invention has the following advantages:
The present invention utilizes ketone hydrazine crosslinking reaction, utilizes ketone carbonyl and diazanyl, hydrazides under micro-acid environment, and easily dehydrating condensation becomes hydrazone, is applied to aqueous polyurethane self-crosslinking system.In urethane synthetic, employing volatile alkali makees neutralizing agent, in the time that emulsion is stored, be under neutral and alkali environment, crosslinking reaction does not occur, in the time using, along with the volatilization of volatile alkali, emulsion meets ketone hydrazine crosslinking reaction condition in micro-acid environment, there is crosslinking reaction, aqueous polyurethane cross-linking density is increased, and the mechanical property of polyurethane material improves, and water resistance and solvent resistance improve.And in whole preparation technology, do not need to add hazardous solvent and emulsifying agent, so both eliminated the pollution and harm to environment and operator, also having improved the effect of product, is VOC free (volatilizable organism) environment-friendly material truly; The polymerization that simultaneously contains active group monomer by initiation has improved the over-all properties of urethane; The present invention has good package stability, and under normal temperature, self-crosslinking reaction can occur the drying and forming-film along with emulsion, has effectively improved water tolerance, solvent resistance and the mechanical property etc. of aqueous polyurethane.The present invention can be used for aqueous coating, the features such as that film has is nontoxic, safety, high gloss uniformity coefficient, high rigidity, transparency is good, fullness ratio is good, good hand touch, and the preparation technology of product is simple, production cost is lower.
Experiment confirms: waterborne polyurethane emulsion capable of self-crosslinking at normal temperature prepared by the present invention is at room temperature along with the dry of emulsion is curable film-forming, compared with not containing the aqueous polyurethane latex film of self-crosslinking structure, the water-intake rate of film is reduced to 18.92% from 39.36%, inhale acetone rate and be reduced to 33.93% by 50.11%, illustrate that the water tolerance of the urethane after modification, solvent resistance are greatly improved.Simultaneously the degree of crosslinking of polyurethane film rises to 90.23% from 51.49%, and tensile strength increases to 28.26MPa from 20.09MPa, and pencil hardness reaches 2H.Thermogravimetic analysis (TGA) shows that the thermostability of film is also improved.
Brief description of the drawings
fig. 1 contains and the thermogravimetric curve that does not contain the aqueous polyurethane glued membrane of self-crosslinking structure.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature of the present invention, is realized by following steps:
Step 1: add the inertia vinyl monomer of 4-18 weight part, polymer polyatomic alcohol, the diisocyanate cpd of 8.5-14 weight part and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.66-2.95 weight part of 9.48-13.35 weight part in dry reactor, temperature of reaction is 70-90 DEG C, and the reaction times is 1-4 hour;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is selected from dibutyl tin laurate, dibutyltin diacetate, stannous octoate, and its weight part is 0 < m≤0.095 part.
Wherein, inertia vinyl monomer is selected from methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, vinylformic acid n-octyl, n octyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, vinylbenzene, alpha-methyl styrene;
Polymer polyatomic alcohol is selected from poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate diol, the polytetrahydrofuran diol of molecular weight between 1000 ~ 2000;
Diisocyanate cpd is selected from isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate;
Negatively charged ion mixing hydrophilic chain extender is selected from the one in dimethylol propionic acid, dimethylolpropionic acid, or is that one in a kind of and dihydroxyl propanesulfonate in dimethylol propionic acid, dimethylolpropionic acid, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium is with 1:(0.2-4) the mixture that mixes of mass ratio.
Step 2: add again the hydrophilic ethylene base monomer of 1-4 weight part to carry out end-blocking, reaction 0.5-1 hour, again system temperature is cooled to 30-50 DEG C, add again the volatile alkali of 1.3-3.2 weight part, neutralization reaction 20-30 minute, add 60-100 weight parts water, high-speed stirring is disperseed 10-30 minute, then is warming up to 70-90 DEG C again.
Wherein, hydrophilic ethylene base monomer is selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, acrylamide, n-methylolacrylamide;
Volatile alkali is selected from Trimethylamine 99, triethylamine, ammoniacal liquor.The mass percentage concentration of ammoniacal liquor is generally 25%～28%.
Step 3: be under the condition of 70-90 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.25-1 weight part in reactor, initiator solution was evenly splashed in reactor in 1-3 hour, after dropwising, continue insulation reaction 1-3 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.1-0.5 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is selected from Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride, and described initiator solution refers to the initiator of 0.5-1 weight part is dissolved in to the aqueous solution obtaining in the water of 10-40 weight part;
Two hydrazides are selected from succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, phenylbenzene phosphinylidyne two hydrazines.
Embodiment 1:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 4 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 8.5 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.66 weight parts of 9.48 weight parts in dry reactor, temperature of reaction is 70 DEG C, and the reaction times is 1 hour;
Wherein, inertia vinyl monomer is selected from methyl acrylate, methyl methacrylate;
Polymer polyatomic alcohol is that molecular weight is 1000 poly-hexanodioic acid hexylene glycol ester;
Diisocyanate cpd is chosen isophorone diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is chosen dimethylol propionic acid.
Step 2: add again the hydrophilic ethylene base monomer of 1 weight part to carry out end-blocking, react 0.5 hour, then system temperature is cooled to 30 DEG C, add again the volatile alkali of 1.3 weight parts, neutralization reaction 20 minutes, then add 60 weight parts waters, high-speed stirring is disperseed 10 minutes, then is warming up to 70 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen Hydroxyethyl acrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 70 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.25 weight part in reactor, initiator solution was evenly splashed in reactor in 1 hour, after dropwising, continue insulation reaction 1 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.1 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen Potassium Persulphate, and initiator solution refers to the initiator of 0.5 weight part is dissolved in to the aqueous solution obtaining in the water of 10 weight parts;
Two hydrazides are chosen succinic acid hydrazide ii.
Embodiment 2:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 6 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 9.3 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.84 weight parts of 10.03 weight parts in dry reactor, temperature of reaction is 75 DEG C, and the reaction times is 1 hour;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen dibutyl tin laurate, and its weight part is 0.022 part.
Wherein, inertia vinyl monomer is selected from methyl acrylate, methyl methacrylate;
It is 1000 poly adipate succinic acid ester that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen isophorone diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is chosen dimethylolpropionic acid.
Step 2: add again the hydrophilic ethylene base monomer of 1 weight part to carry out end-blocking, react 0.5 hour, then system temperature is cooled to 30 DEG C, add again the volatile alkali of 1.6 weight parts, neutralization reaction 20 minutes, then add 65 weight parts waters, high-speed stirring is disperseed 15 minutes, then is warming up to 75 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen Hydroxyethyl acrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 75 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.25 weight part in reactor, initiator solution was evenly splashed in reactor in 1 hour, after dropwising, continue insulation reaction 1 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.1 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen Potassium Persulphate, and initiator solution refers to the initiator of 0.5 weight part is dissolved in to the aqueous solution obtaining in the water of 10 weight parts;
Two hydrazides are chosen succinic acid hydrazide ii.
Embodiment 3:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 8 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 10.1 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.02 weight parts of 10.58 weight parts in dry reactor, temperature of reaction is 75 DEG C, and the reaction times is 2 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen dibutyl tin laurate, and its weight part is 0.034 part.
Wherein, inertia vinyl monomer is selected from ethyl propenoate, β-dimethyl-aminoethylmethacrylate;
It is 1000 poly adipate succinic acid ester that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen tolylene diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is the mixture that dimethylol propionic acid mixes with the mass ratio of 1:0.2 with dihydroxyl propanesulfonate.
Step 2: add again the hydrophilic ethylene base monomer of 2 weight parts to carry out end-blocking, react 0.5 hour, then system temperature is cooled to 35 DEG C, add again the volatile alkali of 1.9 weight parts, neutralization reaction 20 minutes, then add 70 weight parts waters, high-speed stirring is disperseed 15 minutes, then is warming up to 75 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen hydroxyethyl methylacrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 75 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.5 weight part in reactor, initiator solution was evenly splashed in reactor in 1 hour, after dropwising, continue insulation reaction 1 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.2 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen ammonium persulphate, and initiator solution refers to the initiator of 1 weight part is dissolved in to the aqueous solution obtaining in the water of 10 weight parts;
Two hydrazides are chosen adipic dihydrazide.
Embodiment 4:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 10 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 10.9 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.20 weight parts of 11.13 weight parts in dry reactor, temperature of reaction is 80 DEG C, and the reaction times is 2 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen dibutyl tin laurate, and its weight part is 0.046 part.
Wherein, inertia vinyl monomer is selected from butyl acrylate, butyl methacrylate;
It is 1500 polycaprolactone glycol that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen tolylene diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is the mixture that dimethylol propionic acid mixes with the mass ratio of 1:0.9 with 2-aminoethylamino ethyl sulfonic acid sodium.
Step 2: add again the hydrophilic ethylene base monomer of 2 weight parts to carry out end-blocking, react 0.5 hour, then system temperature is cooled to 35 DEG C, add again the volatile alkali of 2.2 weight parts, neutralization reaction 25 minutes, then add 75 weight parts waters, high-speed stirring is disperseed 20 minutes, then is warming up to 80 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen hydroxyethyl methylacrylate;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 80 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.5 weight part in reactor, initiator solution was evenly splashed in reactor in 2 hours, after dropwising, continue insulation reaction 2 hours, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.2 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen ammonium persulphate, and initiator solution refers to the initiator of 1 weight part is dissolved in to the aqueous solution obtaining in the water of 10 weight parts;
Two hydrazides are chosen adipic dihydrazide.
Embodiment 5:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 12 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 11.7 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.38 weight parts of 11.68 weight parts in dry reactor, temperature of reaction is 80 DEG C, and the reaction times is 3 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen dibutyltin diacetate, and its weight part is 0.058 part.
Wherein, inertia vinyl monomer is selected from butyl methacrylate, Ethyl acrylate;
It is 1500 polycaprolactone glycol that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen isophorone hexamethylene diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is dimethylol propionic acid and a kind of mixture mixing with the mass ratio of 1:1.6 in diamino benzene sulfonic acid sodium.
Step 2: add again the hydrophilic ethylene base monomer of 3 weight parts to carry out end-blocking, react 1 hour, then system temperature is cooled to 40 DEG C, add again the volatile alkali of 2.5 weight parts, neutralization reaction 25 minutes, then add 80 weight parts waters, high-speed stirring is disperseed 20 minutes, then is warming up to 80 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen Propylene glycol monoacrylate;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 80 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.75 weight part in reactor, initiator solution was evenly splashed in reactor in 2 hours, after dropwising, continue insulation reaction 2 hours, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.3 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen hydrogen peroxide, and initiator solution refers to the initiator of 0.5 weight part is dissolved in to the aqueous solution obtaining in the water of 40 weight parts;
Two hydrazides are chosen sebacic dihydrazide.
Embodiment 6:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 14 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 12.5 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.56 weight parts of 12.23 weight parts in dry reactor, temperature of reaction is 85 DEG C, and the reaction times is 3 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen dibutyltin diacetate, and its weight part is 0.070 part.
Wherein, inertia vinyl monomer is selected from N-Hexyl methacrylate, vinylformic acid n-octyl;
It is 1500 polycarbonate diol that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen hexamethylene diisocyanate;
Negatively charged ion mixing hydrophilic chain extender is the mixture that dimethylolpropionic acid mixes with the mass ratio of 1:2.3 with dihydroxyl propanesulfonate.
Step 2: add again the hydrophilic ethylene base monomer of 3 weight parts to carry out end-blocking, react 1 hour, then system temperature is cooled to 40 DEG C, add again the volatile alkali of 2.8 weight parts, neutralization reaction 25 minutes, then add 85 weight parts waters, high-speed stirring is disperseed 25 minutes, then is warming up to 85 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen Rocryl 410;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 85 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.75 weight part in reactor, initiator solution was evenly splashed in reactor in 2 hours, after dropwising, continue insulation reaction 2 hours, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.3 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen hydrogen peroxide, and initiator solution refers to the initiator of 0.5 weight part is dissolved in to the aqueous solution obtaining in the water of 40 weight parts;
Two hydrazides are chosen sebacic dihydrazide.
Embodiment 7:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 16 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 13.3 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.74 weight parts of 12.78 weight parts in dry reactor, temperature of reaction is 85 DEG C, and the reaction times is 4 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen stannous octoate, and its weight part is 0.082 part.
Wherein, inertia vinyl monomer is selected from 2-EHA, 2-Ethylhexyl Methacrylate;
It is 2000 polycarbonate diol that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen diphenylmethanediisocyanate;
Negatively charged ion mixing hydrophilic chain extender is the mixture that dimethylolpropionic acid mixes with the mass ratio of 1:3.0 with 2-aminoethylamino ethyl sulfonic acid sodium.
Step 2: add again the hydrophilic ethylene base monomer of 4 weight parts to carry out end-blocking, react 1 hour, then system temperature is cooled to 45 DEG C, add again the volatile alkali of 3.0 weight parts, neutralization reaction 30 minutes, then add 90 weight parts waters, high-speed stirring is disperseed 25 minutes, then is warming up to 85 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen acrylamide;
Volatile alkali is chosen ammoniacal liquor.The mass percentage concentration of ammoniacal liquor is generally 25%～28%.
Step 3: be under the condition of 85 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 1 weight part in reactor, initiator solution was evenly splashed in reactor in 3 hours, after dropwising, continue insulation reaction 3 hours, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.4 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen azo diisobutyl amidine hydrochloride, and initiator solution refers to the initiator of 1 weight part is dissolved in to the aqueous solution obtaining in the water of 40 weight parts;
Two hydrazides are chosen phenylbenzene phosphinylidyne two hydrazines.
Embodiment 8:
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is realized by following steps:
Step 1: add the inertia vinyl monomer of 18 weight parts, polymer polyatomic alcohol, the diisocyanate cpd of 14 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.95 weight parts of 13.35 weight parts in dry reactor, temperature of reaction is 90 DEG C, and the reaction times is 4 hours;
Step 1 also can be added catalyzer in dry reactor, and catalyzer is chosen stannous octoate, and its weight part is 0.095 part.
Wherein, inertia vinyl monomer is selected from vinylbenzene, alpha-methyl styrene;
It is 2000 polytetrahydrofuran diol that polymer polyatomic alcohol is chosen molecular weight;
Diisocyanate cpd is chosen diphenylmethanediisocyanate;
Negatively charged ion mixing hydrophilic chain extender is the mixture that dimethylolpropionic acid mixes with the mass ratio of 1:4 with diamino benzene sulfonic acid sodium.
Step 2: add again the hydrophilic ethylene base monomer of 4 weight parts to carry out end-blocking, react 1 hour, then system temperature is cooled to 50 DEG C, add again the volatile alkali of 3.2 weight parts, neutralization reaction 30 minutes, then add 100 weight parts waters, high-speed stirring is disperseed 30 minutes, then is warming up to 90 DEG C.
Wherein, hydrophilic ethylene base monomer is chosen n-methylolacrylamide;
Volatile alkali is chosen ammoniacal liquor.The mass percentage concentration of ammoniacal liquor is generally 25%～28%.
Step 3: be under the condition of 90 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 1 weight part in reactor, initiator solution was evenly splashed in reactor in 3 hours, after dropwising, continue insulation reaction 3 hours, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.5 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
Wherein, initiator is chosen azo diisobutyl amidine hydrochloride, and described initiator solution refers to the initiator of 1 weight part is dissolved in to the aqueous solution obtaining in the water of 40 weight parts;
Two hydrazides are chosen phenylbenzene phosphinylidyne two hydrazines.
Be below product performance test:
(1) mensuration of the water tolerance of film, solvent resistance
Glued membrane is cut into the square sample of 30 × 30mm, accurately weighs its quality (m
1) after be immersed in deionized water or acetone, after 24 h, take out, dry rapidly surperficial liquid with filter paper, accurately weigh the quality (m of glued membrane
2), the water-intake rate of glued membrane or suction acetone rate (S) are: S=(m
2-m
1)/m
1× 100%.
(2) mensuration of film degree of crosslinking
Taking quality is W
1glued membrane, the 24h that refluxes in apparatus,Soxhlet's taking acetone as solvent, takes out the W that weighs after drying at room temperature
2, the method for calculation of degree of crosslinking are as follows: degree of crosslinking (%)=W
2/ W
1× 100%.
(3) tensile property test
Latex film is made to 45mm × 10mm dumbbell shaped, adopt the Taiwan GT-U55 of high ferro Science and Technology Co., Ltd. type multifunctional material experimental machine to test its tensile strength (σ/MPa).Sample clamping length is 30 mm, rate of extension 100 mm/min.Calculate tensile strength with formula below.Tensile strength (MPa)=breaking load value (N)/film thickness (mm) × film width (mm)
(4) pencil hardness of film
Pencil hardness is tested according to GB/T 6739-1996.
(5) thermogravimetic analysis (TGA)
Adopt German Netzsch company's T G-209 F1 type thermal analyzer to carry out thermogravimetic analysis (TGA), experiment condition: sample 10mg left and right, nitrogen atmosphere, 20 DEG C/min of temperature rise rate, 20 DEG C～600 DEG C of calefactive interzones.
Experiment confirms: waterborne polyurethane emulsion capable of self-crosslinking at normal temperature prepared by the present invention is at room temperature along with the dry of emulsion is curable film-forming, compared with not containing the aqueous polyurethane latex film of self-crosslinking structure, the water-intake rate of film is reduced to 18.92% from 39.36%, inhale acetone rate and be reduced to 33.93% by 50.11%, illustrate that the water tolerance of the urethane after modification, solvent resistance are greatly improved.Simultaneously the degree of crosslinking of polyurethane film rises to 90.23% from 51.49%, and tensile strength increases to 28.26MPa from 20.09MPa, and pencil hardness reaches 2H.Thermogravimetic analysis (TGA) shows that the thermostability of film is also improved.
It is cited that content of the present invention is not limited to embodiment, and the conversion of any equivalence that those of ordinary skill in the art take technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (10)
1. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature, is characterized in that:
Realized by following steps:
Step 1: add the inertia vinyl monomer of 4-18 weight part, polymer polyatomic alcohol, the diisocyanate cpd of 8.5-14 weight part and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.66-2.95 weight part of 9.48-13.35 weight part in dry reactor, temperature of reaction is 70-90 DEG C, and the reaction times is 1-4 hour;
Step 2: add again the hydrophilic ethylene base monomer of 1-4 weight part to carry out end-blocking, reaction 0.5-1 hour, again system temperature is cooled to 30-50 DEG C, add again the volatile alkali of 1.3-3.2 weight part, neutralization reaction 20-30 minute, add 60-100 weight parts water, high-speed stirring is disperseed 10-30 minute, then is warming up to 70-90 DEG C again;
Step 3: be under the condition of 70-90 DEG C in temperature, to the diacetone-acryloamide(DAA) that adds 0.25-1 weight part in reactor, initiator solution was evenly splashed in reactor in 1-3 hour, after dropwising, continue insulation reaction 1-3 hour, make aqueous polyurethane emulsion, in emulsion, add two hydrazides of 0.1-0.5 weight part to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent.
2. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 1, is characterized in that:
In step 1, in dry reactor, also added catalyzer, be selected from dibutyl tin laurate, dibutyltin diacetate, stannous octoate, its weight part is 0 < m≤0.095 part.
3. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 1 and 2, is characterized in that:
In step 1, described inertia vinyl monomer is selected from methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, Ethyl acrylate, N-Hexyl methacrylate, vinylformic acid n-octyl, n octyl methacrylate, 2-EHA, 2-Ethylhexyl Methacrylate, vinylbenzene, alpha-methyl styrene.
4. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 3, is characterized in that:
In step 1, described polymer polyatomic alcohol is selected from poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate diol, the polytetrahydrofuran diol of molecular weight between 1000 ~ 2000.
5. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 4, is characterized in that:
In step 1, described diisocyanate cpd is selected from isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate.
6. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 5, is characterized in that:
In step 1, described negatively charged ion mixing hydrophilic chain extender is selected from the one in dimethylol propionic acid, dimethylolpropionic acid, or is that one in a kind of and dihydroxyl propanesulfonate in dimethylol propionic acid, dimethylolpropionic acid, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium is with 1:(0.2-4) the mixture that mixes of mass ratio.
7. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 6, is characterized in that:
In step 2, described hydrophilic ethylene base monomer is selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, n-methylolacrylamide.
8. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 7, is characterized in that:
In step 2, described volatile alkali is selected from Trimethylamine 99, triethylamine, ammoniacal liquor.
9. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 8, is characterized in that:
In step 3, described initiator is selected from Potassium Persulphate, ammonium persulphate, hydrogen peroxide, azo diisobutyl amidine hydrochloride, and described initiator solution refers to the initiator of 0.5-1 weight part is dissolved in to the aqueous solution obtaining in the water of 10-40 weight part.
10. the preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature according to claim 9, is characterized in that:
In step 3, two described hydrazides are selected from succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, phenylbenzene phosphinylidyne two hydrazines.
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| CN109438654A (en) * | 2018-11-06 | 2019-03-08 | 天津科技大学 | A kind of preparation of new polyurethane film |
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| CN114032054B (en) * | 2021-11-12 | 2023-05-05 | 汉中聚智达远环能科技有限公司 | VOC-free waterborne polyurethane adhesive for medical packaging and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402714A (en) * | 2008-11-08 | 2009-04-08 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylic ester emulsion for watersoluble wood lacquer and method of producing the same |
| CN101759861A (en) * | 2010-02-02 | 2010-06-30 | 陕西科技大学 | Method for preparing waterborne polyurethane emulsion capable of self-crosslinking at normal temperature |
-
2013
- 2013-01-24 CN CN201310025513.3A patent/CN103113532B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402714A (en) * | 2008-11-08 | 2009-04-08 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylic ester emulsion for watersoluble wood lacquer and method of producing the same |
| CN101759861A (en) * | 2010-02-02 | 2010-06-30 | 陕西科技大学 | Method for preparing waterborne polyurethane emulsion capable of self-crosslinking at normal temperature |
Non-Patent Citations (2)
| Title |
|---|
| 室温交联水性聚氨酯施胶增强剂的合成及增强机理;王小荣等;《高分子材料科学与工程》;20120331;第28卷(第3期);25-28页 * |
| 王小荣等.室温交联水性聚氨酯施胶增强剂的合成及增强机理.《高分子材料科学与工程》.2012,第28卷(第3期),25-28页. * |
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