CN103113532A - 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 take water as medium, and safety and environmental protection is free from environmental pollution, has simultaneously good physical and mechanical properties, and the excellent performance such as low temperature resistant, weather-proof is widely used in coating, tackiness agent, textile finishing, leather, synthetic leather is covered with paint, lacquer, colour wash, etc. and the field such as printing ink.But relatively solvent type urethane, aqueous polyurethane be 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 relatively poor shortcoming of mechanical property.The linear thermoplastic's urethane that is dispersed in water due to the mono-component polyurethane emulsion, can not reach the cross-linking density and relative high-molecular weight of conventional solvent borne polyurethane, therefore the aspects 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.Cold cross-linking agent commonly used has aziridine, formaldehyde, polycarbodiimide, epoxies and isocyanates etc., but due to have some shortcoming such as toxicity is large, validity period is short, expensive etc., be restricted in the use.
Summary of the invention
The preparation method who the purpose of this invention is to provide the waterborne polyurethane emulsion capable of self-crosslinking at normal temperature that a kind ofly has high crosslink density, can improve the product application performance, can not pollute and damage environment and operator 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, the polymer polyatomic alcohol of 9.48-13.35 weight part, 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 in dry reactor, temperature of reaction is 70-90 ℃, 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, reacted 0.5-1 hour, system temperature is cooled to 30-50 ℃ again, the volatile alkali that adds again the 1.3-3.2 weight part, neutralization reaction 20-30 minute, add the 60-100 weight parts water, high-speed stirring was disperseed 10-30 minute, then was warming up to 70-90 ℃ again;
Step 3: be under the condition of 70-90 ℃ in temperature, the diacetone-acryloamide(DAA) that adds the 0.25-1 weight part in the reactor, initiator solution was evenly splashed into reactor in 1-3 hour in, after dropwising, continued insulation reaction 1-3 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.1-0.5 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
In step 1, also added catalyzer in dry reactor, 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 a kind of in dimethylol propionic acid, dimethylolpropionic acid, or is a kind of with 1:(0.2-4 in a kind of and dihydroxyl propanesulfonate, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium in dimethylol propionic acid, dimethylolpropionic acid) 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 the aqueous solution that obtains in the water of 10-40 weight part.
In step 3, described two 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, namely utilizes ketone carbonyl and diazanyl, hydrazides under little acid environment, and easily dehydrating condensation becomes hydrazone, is applied to aqueous polyurethane self-crosslinking system.The employing volatile alkali is made neutralizing agent in urethane synthetic, under the neutral and alkali environment when emulsion is stored, crosslinking reaction does not occur, when using, along with the volatilization of volatile alkali, emulsion is in little acid environment and satisfies ketone hydrazine crosslinking reaction condition, crosslinking reaction occurs, make the aqueous polyurethane cross-linking density increase, the mechanical property of polyurethane material improves, and water resistance and solvent resistance improve.And do not need to add hazardous solvent and emulsifying agent in whole preparation technology, 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 contains the active group monomer by initiation has simultaneously 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, film have nontoxic, safety, high gloss uniformity coefficient, high rigidity, the characteristics such as transparency is good, fullness ratio is good, good hand touch, and the preparation technology of product is simple, production cost is lower.
Experiment confirm: the waterborne polyurethane emulsion capable of self-crosslinking at normal temperature of the present invention's preparation is at room temperature along with the drying of emulsion is curable film-forming, compare with the aqueous polyurethane latex film that does not contain the self-crosslinking structure, the water-intake rate of filming is reduced to 18.92% from 39.36%, inhale the acetone rate and be reduced to 33.93% by 50.11%, illustrate that water tolerance, the solvent resistance of the urethane after modification is 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 filming also is improved.
Description of drawings
Fig. 1 is the thermogravimetric curve that contains with the aqueous polyurethane glued membrane that does not contain the self-crosslinking structure.
Embodiment
The present invention will be described in detail below in conjunction with embodiment.
The preparation method of waterborne polyurethane emulsion capable of self-crosslinking at normal temperature of the present invention, realized by following steps:
Step 1: add the inertia vinyl monomer of 4-18 weight part, the polymer polyatomic alcohol of 9.48-13.35 weight part, 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 in dry reactor, temperature of reaction is 70-90 ℃, and the reaction times is 1-4 hour;
Step 1 also can be added catalyzer in dry reactor, catalyzer is selected from dibutyl tin laurate, dibutyltin diacetate, stannous octoate, and its weight part is 0＜m≤0.095 part.
Wherein, the 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 a kind of in dimethylol propionic acid, dimethylolpropionic acid, or is a kind of with 1:(0.2-4 in a kind of and dihydroxyl propanesulfonate, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium in dimethylol propionic acid, dimethylolpropionic acid) 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, reacted 0.5-1 hour, system temperature is cooled to 30-50 ℃ again, the volatile alkali that adds again the 1.3-3.2 weight part, neutralization reaction 20-30 minute, add the 60-100 weight parts water, high-speed stirring was disperseed 10-30 minute, then was warming up to 70-90 ℃ 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 ℃ in temperature, the diacetone-acryloamide(DAA) that adds the 0.25-1 weight part in the reactor, initiator solution was evenly splashed into reactor in 1-3 hour in, after dropwising, continued insulation reaction 1-3 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.1-0.5 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
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 the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 4 weight parts, the polymer polyatomic alcohol of 9.48 weight parts, the diisocyanate cpd of 8.5 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.66 weight parts in dry reactor, temperature of reaction is 70 ℃, and the reaction times is 1 hour;
Wherein, the 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, reacted 0.5 hour, then system temperature is cooled to 30 ℃, the volatile alkali that adds again 1.3 weight parts, neutralization reaction 20 minutes, then add 60 weight parts waters, high-speed stirring was disperseed 10 minutes, then was warming up to 70 ℃.
Wherein, hydrophilic ethylene base monomer is chosen Hydroxyethyl acrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 70 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.25 weight part in the reactor, initiator solution was evenly splashed into reactor in 1 hour in, after dropwising, continued insulation reaction 1 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.1 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen Potassium Persulphate, and initiator solution refers to the initiator of 0.5 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 6 weight parts, the polymer polyatomic alcohol of 10.03 weight parts, the diisocyanate cpd of 9.3 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 1.84 weight parts in dry reactor, temperature of reaction is 75 ℃, and the reaction times is 1 hour;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen dibutyl tin laurate, and its weight part is 0.022 part.
Wherein, the 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, reacted 0.5 hour, then system temperature is cooled to 30 ℃, the volatile alkali that adds again 1.6 weight parts, neutralization reaction 20 minutes, then add 65 weight parts waters, high-speed stirring was disperseed 15 minutes, then was warming up to 75 ℃.
Wherein, hydrophilic ethylene base monomer is chosen Hydroxyethyl acrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 75 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.25 weight part in the reactor, initiator solution was evenly splashed into reactor in 1 hour in, after dropwising, continued insulation reaction 1 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.1 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen Potassium Persulphate, and initiator solution refers to the initiator of 0.5 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 8 weight parts, the polymer polyatomic alcohol of 10.58 weight parts, the diisocyanate cpd of 10.1 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.02 weight parts in dry reactor, temperature of reaction is 75 ℃, and the reaction times is 2 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen dibutyl tin laurate, and its weight part is 0.034 part.
Wherein, the 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;
The negatively charged ion mixing hydrophilic chain extender mixture that to be dimethylol propionic acid mix with the mass ratio of 1:0.2 with the dihydroxyl propanesulfonate.
Step 2: add again the hydrophilic ethylene base monomer of 2 weight parts to carry out end-blocking, reacted 0.5 hour, then system temperature is cooled to 35 ℃, the volatile alkali that adds again 1.9 weight parts, neutralization reaction 20 minutes, then add 70 weight parts waters, high-speed stirring was disperseed 15 minutes, then was warming up to 75 ℃.
Wherein, hydrophilic ethylene base monomer is chosen hydroxyethyl methylacrylate;
Volatile alkali is chosen Trimethylamine 99.
Step 3: be under the condition of 75 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.5 weight part in the reactor, initiator solution was evenly splashed into reactor in 1 hour in, after dropwising, continued insulation reaction 1 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.2 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen ammonium persulphate, and initiator solution refers to the initiator of 1 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 10 weight parts, the polymer polyatomic alcohol of 11.13 weight parts, the diisocyanate cpd of 10.9 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.20 weight parts in dry reactor, temperature of reaction is 80 ℃, and the reaction times is 2 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen dibutyl tin laurate, and its weight part is 0.046 part.
Wherein, the 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;
The negatively charged ion mixing hydrophilic chain extender mixture that to be dimethylol propionic acid mix 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, reacted 0.5 hour, then system temperature is cooled to 35 ℃, the volatile alkali that adds again 2.2 weight parts, neutralization reaction 25 minutes, then add 75 weight parts waters, high-speed stirring was disperseed 20 minutes, then was warming up to 80 ℃.
Wherein, hydrophilic ethylene base monomer is chosen hydroxyethyl methylacrylate;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 80 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.5 weight part in the reactor, initiator solution was evenly splashed into reactor in 2 hours in, after dropwising, continued insulation reaction 2 hours, namely make aqueous polyurethane emulsion, add two hydrazides of 0.2 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen ammonium persulphate, and initiator solution refers to the initiator of 1 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 12 weight parts, the polymer polyatomic alcohol of 11.68 weight parts, the diisocyanate cpd of 11.7 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.38 weight parts in dry reactor, temperature of reaction is 80 ℃, and the reaction times is 3 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen dibutyltin diacetate, and its weight part is 0.058 part.
Wherein, the 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 the isophorone hexamethylene diisocyanate;
Negatively charged ion mixing hydrophilic chain extender be dimethylol propionic acid with diamino benzene sulfonic acid sodium in a kind of mixture that mixes with the mass ratio of 1:1.6.
Step 2: add again the hydrophilic ethylene base monomer of 3 weight parts to carry out end-blocking, reacted 1 hour, then system temperature is cooled to 40 ℃, the volatile alkali that adds again 2.5 weight parts, neutralization reaction 25 minutes, then add 80 weight parts waters, high-speed stirring was disperseed 20 minutes, then was warming up to 80 ℃.
Wherein, hydrophilic ethylene base monomer is chosen Propylene glycol monoacrylate;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 80 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.75 weight part in the reactor, initiator solution was evenly splashed into reactor in 2 hours in, after dropwising, continued insulation reaction 2 hours, namely make aqueous polyurethane emulsion, add two hydrazides of 0.3 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen hydrogen peroxide, and initiator solution refers to the initiator of 0.5 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 14 weight parts, the polymer polyatomic alcohol of 12.23 weight parts, the diisocyanate cpd of 12.5 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.56 weight parts in dry reactor, temperature of reaction is 85 ℃, and the reaction times is 3 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen dibutyltin diacetate, and its weight part is 0.070 part.
Wherein, the 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;
The negatively charged ion mixing hydrophilic chain extender mixture that to be dimethylolpropionic acid mix with the mass ratio of 1:2.3 with the dihydroxyl propanesulfonate.
Step 2: add again the hydrophilic ethylene base monomer of 3 weight parts to carry out end-blocking, reacted 1 hour, then system temperature is cooled to 40 ℃, the volatile alkali that adds again 2.8 weight parts, neutralization reaction 25 minutes, then add 85 weight parts waters, high-speed stirring was disperseed 25 minutes, then was warming up to 85 ℃.
Wherein, hydrophilic ethylene base monomer is chosen Rocryl 410;
Volatile alkali is chosen triethylamine.
Step 3: be under the condition of 85 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 0.75 weight part in the reactor, initiator solution was evenly splashed into reactor in 2 hours in, after dropwising, continued insulation reaction 2 hours, namely make aqueous polyurethane emulsion, add two hydrazides of 0.3 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen hydrogen peroxide, and initiator solution refers to the initiator of 0.5 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 16 weight parts, the polymer polyatomic alcohol of 12.78 weight parts, the diisocyanate cpd of 13.3 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.74 weight parts in dry reactor, temperature of reaction is 85 ℃, and the reaction times is 4 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen stannous octoate, and its weight part is 0.082 part.
Wherein, the 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;
The negatively charged ion mixing hydrophilic chain extender mixture that to be dimethylolpropionic acid mix 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, reacted 1 hour, then system temperature is cooled to 45 ℃, the volatile alkali that adds again 3.0 weight parts, neutralization reaction 30 minutes, then add 90 weight parts waters, high-speed stirring was disperseed 25 minutes, then was warming up to 85 ℃.
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 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 1 weight part in the reactor, initiator solution was evenly splashed into reactor in 3 hours in, after dropwising, continued insulation reaction 3 hours, namely make aqueous polyurethane emulsion, add two hydrazides of 0.4 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen azo diisobutyl amidine hydrochloride, and initiator solution refers to the initiator of 1 weight part is dissolved in the aqueous solution that obtains 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, realized by following steps:
Step 1: add the inertia vinyl monomer of 18 weight parts, the polymer polyatomic alcohol of 13.35 weight parts, the diisocyanate cpd of 14 weight parts and the negatively charged ion mixing hydrophilic chain extender hybrid reaction of 2.95 weight parts in dry reactor, temperature of reaction is 90 ℃, and the reaction times is 4 hours;
Step 1 also can be added catalyzer in dry reactor, catalyzer is chosen stannous octoate, and its weight part is 0.095 part.
Wherein, the 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;
The negatively charged ion mixing hydrophilic chain extender mixture that to be dimethylolpropionic acid mix 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, reacted 1 hour, then system temperature is cooled to 50 ℃, the volatile alkali that adds again 3.2 weight parts, neutralization reaction 30 minutes, then add 100 weight parts waters, high-speed stirring was disperseed 30 minutes, then was warming up to 90 ℃.
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 ℃ in temperature, the diacetone-acryloamide(DAA) that adds 1 weight part in the reactor, initiator solution was evenly splashed into reactor in 3 hours in, after dropwising, continued insulation reaction 3 hours, namely make aqueous polyurethane emulsion, add two hydrazides of 0.5 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
Wherein, initiator is chosen azo diisobutyl amidine hydrochloride, and described initiator solution refers to the initiator of 1 weight part is dissolved in the aqueous solution that obtains in the water of 40 weight parts;
Two hydrazides are chosen phenylbenzene phosphinylidyne two hydrazines.
Below be the 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 its quality of weighing (m
1) after be immersed in deionized water or acetone, take out after 24 h, dry rapidly the liquid on surface with filter paper, accurately quality (the m of weighing 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 take 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 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 following formula.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: about sample 10mg, nitrogen atmosphere, 20 ℃/min of temperature rise rate, 20 ℃～600 ℃ of calefactive interzones.
Experiment confirm: the waterborne polyurethane emulsion capable of self-crosslinking at normal temperature of the present invention's preparation is at room temperature along with the drying of emulsion is curable film-forming, compare with the aqueous polyurethane latex film that does not contain the self-crosslinking structure, the water-intake rate of filming is reduced to 18.92% from 39.36%, inhale the acetone rate and be reduced to 33.93% by 50.11%, illustrate that water tolerance, the solvent resistance of the urethane after modification is 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 filming also is 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 skills 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, the polymer polyatomic alcohol of 9.48-13.35 weight part, 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 in dry reactor, temperature of reaction is 70-90 ℃, 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, reacted 0.5-1 hour, system temperature is cooled to 30-50 ℃ again, the volatile alkali that adds again the 1.3-3.2 weight part, neutralization reaction 20-30 minute, add the 60-100 weight parts water, high-speed stirring was disperseed 10-30 minute, then was warming up to 70-90 ℃ again;
Step 3: be under the condition of 70-90 ℃ in temperature, the diacetone-acryloamide(DAA) that adds the 0.25-1 weight part in the reactor, initiator solution was evenly splashed into reactor in 1-3 hour in, after dropwising, continued insulation reaction 1-3 hour, namely make aqueous polyurethane emulsion, add two hydrazides of 0.1-0.5 weight part namely to make waterborne polyurethane emulsion capable of self-crosslinking at normal temperature as linking agent in emulsion.
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, also added catalyzer in dry reactor, 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 a kind of in dimethylol propionic acid, dimethylolpropionic acid, or is a kind of with 1:(0.2-4 in a kind of and dihydroxyl propanesulfonate, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium in dimethylol propionic acid, dimethylolpropionic acid) 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, acrylamide, 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 the aqueous solution that obtains 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, described two hydrazides are selected from succinic acid hydrazide ii, adipic dihydrazide, sebacic dihydrazide, phenylbenzene phosphinylidyne two hydrazines.
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| CN104628981A (en) * | 2015-02-10 | 2015-05-20 | 新纶科技（常州）有限公司 | Method for preparing waterborne polyurethane adhesive |
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