CN101085860A - Method of preparing water polyurethane urea/modified nano CaCO3 organic-inorganic hybridization material - Google Patents
Method of preparing water polyurethane urea/modified nano CaCO3 organic-inorganic hybridization material Download PDFInfo
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Abstract
The invention relates to a method for preparing water- borne polyurethane urea (PUU)/ silicasol modified nanometer CaCO3 hybridized aqueous dispersion liquid. It is characterized in that the silicasol modified nanometer CaCO3 hybridized aqueous dispersion liquid with grain size being 10- 100 nm is uesd to replace part of water, and employs origianl position method to disperse polyurethane urea prepolymer, and gets high solid content (25- 30%) organic- inorganic hybridized matgerial. The stability of said hybridized material is very good, the high solid content is favoable for energy save, and the adhesive force of hybridized material to various base materials after filming is strong. The film coating is characterized by high hardness, strong force strength, good water- proof, disslovant- resistant and hard- wearing property.
Description
Technical field
The present invention relates to water tolerance and good aqueous polyurethaneurea and the modified Nano CaCO of mechanical property after a kind of solid content height, shelf-stable and the film forming
3The preparation method of hybrid inorganic-organic materials.
Background technology
Hybrid inorganic-organic materials, as the combination product between the totally different component of two kinds of performances, it is generally acknowledged and to satisfy two conditions simultaneously, promptly wherein have at least the size of a phase to have a dimension at least in nanometer scale, nanophase is alternate with other chemistry (covalent linkage, chelate bond) or physics (hydrogen bond) effect, compound on nanometer level, therefore hybrid inorganic-organic materials has had the characteristic of organic polymer and inorganic materials concurrently, just becoming the focus of research, also is the effective means of development of new material.
Aqueous polyurethaneurea is as a kind of environment-friendly materials, and research at present is a lot, but with itself and nanometer CaCO
3The research work of aqueous dispersions formation hybrid material seldom.Macromol.Symp.2005,221,33-41 has reported with polyurethane aqueous dispersion and micron CaCO
3Blend prepares hybrid inorganic-organic materials.Because the limitation of preparation process, the particle diameter of prepared hybrid material is bigger, and less stable has reduced industrial use value.In addition, mechanical property and the water resistance of this research after to prepared hybrid material film forming do not mentioned.
Summary of the invention
The aqueous polyurethaneurea and the modified Nano CaCO that the purpose of this invention is to provide a kind of high solids content
3The preparation method of aqueous dispersions hybrid inorganic-organic materials, it has good stability simultaneously, and has excellent in water resistance, mechanical property after the film forming and to the sticking power of metal.
Aqueous polyurethaneurea provided by the present invention and modified Nano CaCO
3Hybrid inorganic-organic materials mainly comprises:
(1) Ionized aqueous polyurethane performed polymer (2) silica sol modified nanometer CaCO
3Aqueous dispersions.
Preparation method of the present invention is:
At first preparation contains the aqueous polyurethane performed polymer of carboxyl and different sorts polyisocyanates and high molecular weight polyols, with in the neutralizing agent and behind the salify, does not formerly add under the condition of water-dispersion, adds a certain amount of silica sol modified nanometer CaCO
3Aqueous dispersions carries out pre-dispersed, adds a certain amount of water at last again and further disperses fully, promptly obtains aqueous polyurethaneurea/modified Nano CaCO behind the chainextender chain extension
3Hybrid inorganic-organic materials is called for short the PUU-Ca-X aqueous dispersions, and wherein X represents the percentage composition of modified Nano CaCO3 in the hybrid water dispersion solid ingredient.This modified Nano CaCO that directly uses
3Aqueous dispersions instead of part water carries out pre-dispersed benefit, has been to improve the solid content in the hybrid material, has increased organic phase and inorganic alternate consistency.Prepared aqueous polyurethaneurea and modified Nano CaCO
3The solid content of hybrid inorganic-organic materials can be 8%～80%, is preferably between 20%～30%.
Selected polyisocyanates can be an aliphatic polyisocyante in the preparation process of aqueous polyurethane performed polymer, as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) etc.; And aromatic diisocyanate, as tolylene diisocyanate (TDI), 4,4 '-methylenebis phenyl isocyanate (MDI) etc.Used high molecular weight polyols is polyester polyol such as polyneopentyl glycol adipate, polycarbonate etc., or polyether glycol such as polyoxytrimethylene dibasic alcohol, polyethylene oxide, polytetrahydrofuran etc., and molecular weight is 350～20, between 000, be preferably in 1,000-7,000.Wherein the consumption of polyisocyanates can be preferably 1.4～1.9 (mol ratios) for 1.1～3.5 (mol ratios) of polyvalent alcohol consumption.
Used catalyzer can be that organic tin is as two lauric acid diisobutyl tin, stannous octoate etc. in the preparation process of aqueous polyurethane performed polymer, or amine substance such as tetramethyl butane diamine, triethylenediamine etc., catalyst consumption can be 0～0.5% of total solids level in the product, preferably 0.01%～0.05%.
The used carboxylic monomer that contains can be carboxylic polyvalent alcohol and carboxylated polyisocyanates when preparing carboxylic aqueous polyurethane performed polymer, also can be the small molecules dibasic alcohol chainextender that contains carboxyl, as dimethylol propionic acid etc.The consumption that wherein contains carboxylic monomer is 0.1～5 (mol ratio) of high molecular weight polyols consumption, is preferably 0.8～1.2 (mol ratio).
Containing the used neutralizing agent of the aqueous polyurethane performed polymer of carboxyl can be with trialkyl or alkyl amine, pyridines, pyroles and their mixture, preferably adopt N, N～dimethylethanolamine or triethylamine, its consumption is preferably 0.6～1.1 (mol ratio) for containing 0.1～2.5 (mol ratio) of carboxylic monomer (as dimethylol propionic acid) consumption.
Preparation aqueous polyurethaneurea and modified Nano CaCO
3Used small molecule chain extender can be small molecules polyvalent alcohol such as ethylene glycol, 1 in the hybrid inorganic-organic materials process, the 4-butyleneglycol, also can be the polynary amine of small molecules such as quadrol and hexanediamine, or hydrazine class such as hydrazine hydrate and their mixture, preferably adopt hydrazine hydrate or quadrol, its consumption is 0.01～2.5 (mol ratio) of polyisocyanates consumption, is preferably 0.36～0.81 (mol ratio).
The preparation of aqueous polyurethane performed polymer, can obtain by the one-step polymerization reaction that polyisocyanates, polyvalent alcohol and small molecule chain extender add simultaneously, also can in the presence of catalyzer, form performed polymer earlier, realize with the step polymerization of small molecule chain extender chain extension again by polyisocyanates and high molecular weight polyols.
Used modified Nano CaCO in the preparation process of the present invention
3Aqueous dispersions is a kind of nanometer CaCO by the in-situ method preparation
3Aqueous dispersions, particle diameter are 10～100nm, wherein modified Nano CaCO
3Content can be 1-80%, is preferably 5-20%.Wherein the quality of modified Nano CaCO3 accounts for 1～50% of aqueous polyurethaneurea, is preferably between 5%～20%.
The preparation feedback temperature of aqueous polyurethane performed polymer can be preferably in 80-100 ℃ between 30-110 ℃.
The hybrid material of the present invention preparation can be under normal pressure 60 ℃ of film forming, also can be under vacuum 40 ℃ of film forming.
The hybrid material of the present invention's preparation has good stability when room temperature, and high solids content makes it have advantages such as energy-conservation.After this class hybrid material film forming all kinds of base materials had excellent sticking power; In addition, the hardness height of filming, mechanical strength is good, and has excellent water-fast, anti-solvent, characteristic such as wear-resisting, in paint field extensive use is arranged.
Embodiment
The present invention is described in detail below in conjunction with example, but the present invention is not limited to following example.
Embodiment 1
Take by weighing 20 gram polyoxytrimethylene dibasic alcohol (GE220, hydroxyl value: 56mgKOH/g, molecular weight 2000) and 8.88 gram isophorone diisocyanates (IPDI), add 1.34 gram dimethylol propionic acids and 0.01 gram, two lauric acid diisobutyl tin (T-12) again, heating is also stirred, be warming up to about 80 ℃, 80 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 60 ℃ more then, add 1.01 gram triethylamines, after reacting about 30 minutes, under high-speed stirring, drip 45 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 60nm, modified Nano CaCO for aqueous dispersions
3Content is 10%), continue to drip 40 gram deionized waters and 1.2 gram quadrol chain extensions at last, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-15 aqueous dispersions of white band blue light, its solid content about 30% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea 15%).
Embodiment 2
Take by weighing 20 gram polyoxytrimethylene dibasic alcohol (GE220, hydroxyl value: 56mgKOH/g, molecular weight 2000) and 12.18 gram isophorone diisocyanates (IPDI), add 1.34 gram dimethylol propionic acid and 0.18g (0.5%) tetramethyl butane diamines again, heating is also stirred, be warming up to about 30 ℃, 30 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 20 ℃ more then, add 0.1 gram triethylamine neutralization, after reacting about 30 minutes, under high-speed stirring, drip 45 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 60nm, modified Nano CaCO for aqueous dispersions
3Content is 10%), continue to drip 321 gram deionized waters and the 0.026 diamines chain extension of restraining oneself at last, after dropwising, continue stir about discharging in 1 hour down at 40～50 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-17 aqueous dispersions of white band blue light, its solid content about 80% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea about 17%).
Embodiment 3
Take by weighing 20 gram polyoxytrimethylene dibasic alcohol (GE220, hydroxyl value: 56mgKOH/g, molecular weight 2000) and 6.7 gram tolylene diisocyanates (TDI), add 0.134 gram dimethylol propionic acid and 0.009 gram, two lauric acid diisobutyl tin (T-12) again, heating is also stirred, be warming up to about 60 ℃, 60 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 40 ℃ more then, add 0.1 gram diethanolamine neutralization, after reacting about 30 minutes, under high-speed stirring, drip 6.8 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 100nm, modified Nano CaCO for aqueous dispersions
3Content is 80%), continue to drip 6.75 gram deionized waters and 6.15 grams 1 at last, the 4-chain expansion of succinic acid, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-20 aqueous dispersions of white band blue light, its solid content about 80% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea about 20%).
Embodiment 4
Take by weighing 200 gram polyoxytrimethylene dibasic alcohol (hydroxyl values: 560mgKOH/g, molecular weight 20000), 5.36 gram tolylene diisocyanates (TDI) (0% catalyzer), heating is also stirred, and is warming up to about 110 ℃, 110 ℃ of left and right sides isothermal reactions after 2.5～3 hours, add 1.34 gram dimethylol propionic acids again, continue reaction 1～2 hour, be cooled to 60 ℃ again, add 3 gram N, N-dimethylethanolamine neutralization, react about 30 minutes after, under high-speed stirring, drip 131 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 100nm, modified Nano CaCO for aqueous dispersions
3Content is 80%), continue to drip 341 gram deionized waters and 0.48 gram hydrazine hydrate chain extension at last, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-50 aqueous dispersions of white band blue light, its solid content is (modified Nano CaCO wherein about 50%
3Quality account for aqueous polyurethaneurea 50%).
Embodiment 5
Take by weighing 20 gram polyneopentyl glycol adipate (P756, hydroxyl value: 56mgKOH/g, molecular weight 2000) and 8.88 gram isophorone diisocyanates (IPDI), add 1.34 gram dimethylol propionic acids and 0.01 gram, two lauric acid diisobutyl tin (T-12) again, heating is also stirred, be warming up to about 85 ℃, 85 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 60 ℃ more then, add 0.3 gram pyridine, after reacting about 30 minutes, under high-speed stirring, drip 20 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 10nm, modified Nano CaCO for aqueous dispersions
3Content is 3%), continue to drip 70 gram deionized water and quadrol chain extensions at last, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-2 aqueous dispersions of white band blue light, its solid content about 25% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea 2%).
Embodiment 6
Take by weighing 3.5 gram polycarbonate (hydroxyl values: 9.8mgKOH/g, molecular weight 350) and 8.88 the gram isophorone diisocyanates (IPDI), add 1.34 gram dimethylol propionic acids and 0.008 gram triethylenediamine again, heating is also stirred, and is warming up to about 85 ℃, then 85 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 60 ℃ again, add 0.4 gram pyrroles, react about 30 minutes after, under high-speed stirring, drip 45 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 10nm, modified Nano CaCO for aqueous dispersions
3Content is 3%), continue to drip 17 gram deionized water and quadrol chain extensions at last, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-10 aqueous dispersions of white band blue light, its solid content about 20% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea 10%).
Embodiment 7
Take by weighing 40 gram polytetrahydrofuran dibasic alcohol (PTMG, hydroxyl value: 28mgKOH/g, molecular weight 4000) and 5.36 gram tolylene diisocyanates (TDI), add 1.34 gram dimethylol propionic acids and 0.015 gram stannous octoate again, heating is also stirred, be warming up to about 110 ℃, 110 ℃ of left and right sides isothermal reactions 3～4 hours, be cooled to 60 ℃ more then, add 1 gram triethylamine, after reacting about 30 minutes, under high-speed stirring, drip 47 gram modified Nano CaCO
3(this laboratory is synthetic, and particle diameter is 80nm, modified Nano CaCO for aqueous dispersions
3Content is 8%), continue to drip 87 gram deionized water and quadrol chain extensions at last, after dropwising, continue stir about discharging in 1 hour down at 40 ℃, can obtain the hybrid inorganic-organic materials PUU-Ca-8 aqueous dispersions of white band blue light, its solid content about 28% (wherein the quality of modified Nano CaCO3 account for aqueous polyurethaneurea 8%).
Embodiment 8
Take by weighing hybrid material 100 grams of embodiment 1 preparation, be coated on the polyfluortetraethylene plate, put into 40 ℃ of vacuum drying ovens again and be dried to constant weight, promptly get hydridization PUU film.Table 1 has been listed the performance of film, demonstrates excellent in water resistance, solvent resistance, shock strength, sticking power and hardness.
Physicals after the table 1 hybrid material PUU-Ca-15 film forming
| Water the film surface contact angle (°) | 100 |
| Water tolerance 1 | Good |
| Solvent resistance 2 | Good |
| Shock strength (cm) | 50 |
| Sticking power (level) | 1 |
| Pendulum-rocker hardness | 0.96 |
Annotate: soaked 48 hours in the water under 1 room temperature, observe the variation on film surface.The surface do not have turn white, the foaming phenomenon is then for well, otherwise then poor.
2 to dip in the cotton of acetone, behind the Wiping film surface ten times, observes the film surface and change repeatedly.The surface does not have and to turn white, to peel off phenomenon then for well, otherwise then poor.
Test-results shows, product aqueous polyurethaneurea of the present invention and modified Nano CaCO
3Hardness height after hybrid water dispersion is filmed, mechanical strength is good, and has excellent water-fast, anti-solvent, characteristic such as wear-resisting, in paint field extensive use is arranged.
Claims (10)
1. the preparation method of aqueous polyurethaneurea and modified Nano CaCO3 hybrid inorganic-organic materials, it is characterized in that at first preparing the aqueous polyurethane performed polymer that contains carboxyl and different sorts polyisocyanates and high molecular weight polyols, with in the neutralizing agent and behind the salify, formerly do not add under the condition of water-dispersion, adding silica sol modified nanometer CaCO3 aqueous dispersions carries out pre-dispersed, add entry at last again and further disperse fully, behind the chainextender chain extension, promptly obtain aqueous polyurethaneurea/modified Nano CaCO3 hybrid inorganic-organic materials; The solid content of prepared aqueous polyurethaneurea and modified Nano CaCO3 hybrid inorganic-organic materials is 8%～80%;
The preparation of aqueous polyurethane performed polymer, the one-step polymerization reaction that adds simultaneously by polyisocyanates, polyvalent alcohol and small molecule chain extender obtains, or in the presence of catalyzer, form performed polymer earlier by polyisocyanates and high molecular weight polyols, realize with the step polymerization of small molecule chain extender chain extension again; The preparation feedback temperature of aqueous polyurethane performed polymer is between 30-110 ℃;
Wherein selected polyisocyanates is an aliphatic polyisocyante: isophorone diisocyanate, hexamethylene diisocyanate; And aromatic diisocyanate: tolylene diisocyanate, 4,4 '-methylenebis phenyl isocyanate; Used high molecular weight polyols is a polyester polyol: polyneopentyl glycol adipate, polycarbonate, or polyether glycol: polyoxytrimethylene dibasic alcohol, polyethylene oxide, polytetrahydrofuran, molecular weight are 350～20,000, or are 1,000-7,000; Wherein the consumption of polyisocyanates is 1.1～3.5 of a polyvalent alcohol consumption mol ratio, or is 1.4～1.9;
The used carboxylic monomer that contains is carboxylic polyvalent alcohol and carboxylated polyisocyanates, or contains the small molecules dibasic alcohol chainextender of carboxyl: dimethylol propionic acid when preparing carboxylic aqueous polyurethane performed polymer; The consumption that wherein contains carboxylic monomer is 0.1～5 of a high molecular weight polyols consumption mol ratio, or is 0.8～1.2;
The used neutralizing agent of aqueous polyurethane performed polymer that contains carboxyl is trialkyl or alkyl amine, pyridines, pyroles and their mixture, and its consumption is to contain 0.1～2.5 of carboxylic monomer consumption mol ratio;
Preparation aqueous polyurethaneurea and modified Nano CaCO
3Used small molecule chain extender is the small molecules polyvalent alcohol in the hybrid inorganic-organic materials process: ethylene glycol, 1, the 4-butyleneglycol, or the polynary amine of small molecules: quadrol and hexanediamine, or hydrazine class: hydrazine hydrate and their mixture, its consumption are 0.01～2.5 of polyisocyanates consumption mol ratio;
Used modified Nano CaCO in the described preparation process
3Aqueous dispersions is a kind of nanometer CaCO by the in-situ method preparation
3Aqueous dispersions, particle diameter are 10～100nm, wherein modified Nano CaCO
3Content is 1-80%; Wherein the quality of modified Nano CaCO3 accounts for 1～50% of aqueous polyurethaneurea.
2. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials, it is characterized in that catalyzer used in the preparation process of aqueous polyurethane performed polymer is an organic tin: two lauric acid diisobutyl tin, stannous octoate, or amine substance: tetramethyl butane diamine, triethylenediamine, catalyst consumption be in the product total solids level 0～0.5%.
3. aqueous polyurethaneurea according to claim 2 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials, it is characterized in that catalyst consumption be in the product total solids level 0.01%～0.05%.
4. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials is characterized in that prepared aqueous polyurethaneurea and modified Nano CaCO
3The solid content of hybrid inorganic-organic materials is 20%～30%.
5. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials, the preparation feedback temperature that it is characterized in that the aqueous polyurethane performed polymer is 80-100 ℃.
6. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials is characterized in that the consumption of polyisocyanates in the preparation of aqueous polyurethane performed polymer is that polyvalent alcohol consumption mol ratio is 1.4～1.9; The consumption that contains carboxylic monomer is that high molecular weight polyols consumption mol ratio is 0.8～1.2.
7. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials, the used neutralizing agent of aqueous polyurethane performed polymer that it is characterized in that containing carboxyl is N, N～dimethylethanolamine or triethylamine, its consumption for the mol ratio that contains the carboxylic monomer consumption be 0.6～1.1.
8. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials is characterized in that described small molecule chain extender is hydrazine hydrate or quadrol, and its consumption is a polyisocyanates consumption mol ratio 0.36～0.81.
9. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials is characterized in that modified Nano CaCO
3Modified Nano CaCO in the aqueous dispersions
3Content is 5-20%.
10. aqueous polyurethaneurea according to claim 1 and modified Nano CaCO
3The preparation method of hybrid inorganic-organic materials is characterized in that modified Nano CaCO
3Quality account for 5%～20% of aqueous polyurethaneurea.
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