CN101280061A - Synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion - Google Patents
Synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion Download PDFInfo
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- CN101280061A CN101280061A CNA2008100376993A CN200810037699A CN101280061A CN 101280061 A CN101280061 A CN 101280061A CN A2008100376993 A CNA2008100376993 A CN A2008100376993A CN 200810037699 A CN200810037699 A CN 200810037699A CN 101280061 A CN101280061 A CN 101280061A
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Abstract
The invention relates to a synthesis method of silicone-polyurethane-acrylate ternary composite ionomer emulsion as follows: first, hydroxy-terminated poly-dimethylsiloxane, N-methyl-diethanolamine, toluene diisocyanate, polypropylene glycol and others are used to prepare water-based silicone modified polyurethane; under the condition that the silicone modified polyurethane serves as emulsifier, the silicone modified polyurethane is polymerized and reacted with acrylic monomer to prepare stable silicone-polyurethane-acrylate ionomer emulsion. The silicone-polyurethane-acrylate ionomer emulsion is dried to obtain the silicone-polyurethane-acrylate coating. The synthesis method of the invention has simple process and low cost. The prepared ternary composite ionomer product combines the outstanding performances of the three components and can be applied to automobiles, household appliances, metal tools, buildings, textiles, paints and many other fields.
Description
Technical field
The present invention relates to a kind of synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion, belong to the polymer chemistry synthesis technical field.
Background technology
Organosilicon is alternately to be combined into the siloxane chain inorganic skeleton by silicone atom, and is connected with the polymkeric substance of organic groups such as methyl on Siliciumatom.The siloxane bond bond energy is more much bigger than carbon-carbon bond bond energy, and this is the major reason that siloxanes has heat-resistant stability and weather resisteant.Polysiloxane has a series of excellent properties because of its unique chemical structure composition, as has fabulous high and low temperature resistance, good insulativity and chemical stability, hydrophobic moistureproofness, physiology inertia and biocompatibility.Since the forties in 20th century industrial applications, extensive studies and application have been obtained.Silicoorganic compound (organosilicon compound) are a kind of special macromolecular compounds, they have the characteristic of mineral compound and organic compound concurrently, surface energy is low, have many excellent properties such as low temperature resistant, weather-resistant, hydrophobic, organic solvent-resistant, radiation hardness, and organosilicon polymer can also be given outstanding flexibility of coating and smooth silk feel.
Polyacrylic ester (PA) has advantages such as physical strength height, ageing-resistant, water-tolerant, acrylic resin is the macromolecular material that a kind of cementability is strong, film-forming properties is high, and it has obtained in the interior wall coating field using widely each other or with cinnamic multipolymer (be called for short pure third and phenylpropyl alcohol) at present.But there are toughness, wear-resisting, shortcomings such as chemical resistance is poor, high temperature is clamminess, low temperature embrittlement.But as exterior coating, must have good weathering resistance (high-low temperature resistant, resistance to oxidation, corrosion-resistant etc.), and acrylate resin low temperature becomes fragile, high temperature become sticky lose strong disadvantages affect it in the further utilization of exterior wall paint field.Use urethane (PU) that PA is carried out modification, can utilize the winter hardiness, elasticity of PU excellence, well performance such as thermal adaptation ability and PA have certain complementary action in nature.By both compound polyurethane-acrylate (PUA) composite emulsion that makes, can learn from other's strong points to offset one's weaknesses, the performance comprehensive advantage, make emulsion film performance be improved significantly.The polytropy of the structural unit of urethane own provides new opportunity for PUA and other material compound again.
It is a relatively more novel job that ionomer is made stable emulsion, also has in recent years to make the work report of polyurethane-acrylate (PUA) from aggressiveness, rarely has report but directly make ionomeric emulsion.Ionomer (ionomer) is meant and contains the polymkeric substance that ionic group is lower than 15mol%, these ionic groups can be gathered into multiple ion to or ion cluster, make macromolecular chain generation physical crosslinking form aggregate, cause character to play wide variation. for example under the normal temperature because of physical crosslinking has favorable elasticity, so and during high temperature physical crosslinking destroyed and have flowability. ionomer can be made thermoplastic elastomer.In the ionic polymerization objects system, the interaction that may exist has ion-ionic interaction; Ion pair-ion pair interacts; Ion-dipole interaction; Metal complex interacts; Interaction of hydrogen bond; Hydrophobic chain interaction etc.
Between blend components, introduce some special interaction, thereby make inconsistent blend become compatible even consistency improves greatly.By introducing ionic linkage, utilize the ionic bonding effect can make the organosilicon polyurethane-acrylic ester emulsion of excellent property.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, low-cost, the synthetic method of high performance preparation organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion.
The objective of the invention is to realize by following technique means.
A kind of synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion, it is characterized in that, with having introduced the organosilyl urethane (PU) and polyacrylic ester (PA) effect that has tertiary amino group, made the organic-silicon-modified PUA emulsion that contains the ionic linkage effect; Concrete synthetic method is as follows:
1) the organic silicon polyurethane performed polymer is synthetic
Appropriate amount of organic is mixed with tolylene diisocyanate (TDI) in the reactor of back adding nitrogen protection, and dropping appropriate amount of catalysts dibutyltin dilaurate (DBT), be raised to 50-80 ℃, slowly drip hydroxyl-terminated injecting two methyl siloxane, the mass percent that the content of hydroxyl-terminated injecting two methyl siloxane accounts for tolylene diisocyanate is 1-52%, in about 1.5h, drip, dropwise the back and continue reaction 1.5h; Drip poly-Isopropanediol then, the molar ratio of tolylene diisocyanate and poly-Isopropanediol is 1: 1, drips in about 1.5h, dropwises the back and continues reaction 1.5h;
2) positively charged ion organic silicon polyurethane performed polymer is synthetic
With the product cool to room temperature of step 1), in reactor, drip the acetone soln of the N methyldiethanol amine (MDEA) of 0.02-0.20mol, be raised to 50-80 ℃ of reaction 1h and get head product; With the head product distilled water wash, the flush away solvent re-uses mass percentage concentration for the neutralization of 10%NaOH solution, obtains positively charged ion organic silicon polyurethane performed polymer;
3) the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion is synthetic
With mass percentage concentration is 10%HCl solution regulating step 2) performed polymer made becomes neutral, under 65-85 ℃, slowly add Acrylic Acid Monomer and initiator, the mass ratio of positively charged ion organic silicon polyurethane performed polymer and Acrylic Acid Monomer is 1: 3-3: 3, the mass percent that initiator amount accounts for the Acrylic Acid Monomer consumption is 1%, in about 2h, add, continue reaction 1.5h then, make the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion.
Organic solvent used in the synthetic method step 1) of above-mentioned organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion is: acetone, butanone, toluene etc.; Initiator used in the step 3) is: Potassium Persulphate, Ammonium Persulfate 98.5, Diisopropyl azodicarboxylate etc.
The hardness and the sticking power of synthetic method middle-jiao yang, function of the spleen and stomach ionic organosilicon base polyurethane prepolymer for use as quality percentage composition of the present invention copolymer emulsion in 40% reach optimum value.When the ratio of vinylformic acid (AA)/N methyldiethanol amine (MDEA) is near 0.8: 1 (mol ratio), ionomeric performance the best.
The present invention adopts hydroxyl-terminated injecting two methyl siloxane (C
32H
92O
14Si
13), N methyldiethanol amine, tolylene diisocyanate, poly-Isopropanediol etc. have made the organic silicon modified polyurethane of water-based, are under the emulsifying agent condition at this organic silicon modified polyurethane, and polymerizable acrylic monomer.Reaction makes stable organosilicon polyurethane-acrylic ester ionomer emulsion.Its oven dry is obtained organic-silicon-modified PUA films.Heat analysis (DSC) records to film has only a second-order transition temperature, illustrates that paint film is the compatible ionomer of blend.The group of two kinds of oppositely chargeds in the ionomer (uncle's amino and carboxyl) can form ionic linkage, has improved the comixing compatibility of polymkeric substance widely.Vinylformic acid (AA)/N methyldiethanol amine (MDEA) molar ratio is near 0.8: 1 the time, the better heat stability of filming, and every mechanical property all satisfies the technical feature requirement.Organosilyl adding makes the surface tension of film descend, and greatly reduces the surface energy of film, and along with the raising of organosilicon additional proportion, water contact angle obviously improves.Along with the increase of organosilicon content, the heat decomposition temperature of filming increases thereupon, and Tg is along with first rising of the increase of organosilicon content afterwards descends, and the water tolerance of filming also is greatly improved, and this ternary ionic copolymer has good ageing-resistant ability.
The inventive method has following characteristics and advantage:
1, use hydroxyl-terminated injecting two methyl siloxane, N methyldiethanol amine, poly-Isopropanediol etc. to make the backbone chain type positively charged ion organosilicon/polyurethane/acrylate ternary composite ionomer emulsion that contains the ionic linkage effect, combine urethane, acrylate, the advantage of three kinds of resin materials of organosilicon, preparation technology is simple, and organosilicon, urethane, polyacrylic ester consistency are better.And with water as dispersion medium, met environmental requirement.Also provide reference for synthetic polynary composite ionomer.
2, the ratio of vinylformic acid (AA)/N methyldiethanol amine (MDEA) has certain influence for the thermostability of organosilicon polyurethane-acrylic ester ionomer emulsion, when ratio is near 0.8: 1, organic-silicon-modified PUA ionomer emulsion heat decomposition temperature is the highest, and promptly the thermal stability of PUA is best at this moment.
3, obtain good performance by introducing ionic linkage, utilize the ionic bonding effect to make to film, the water tolerance of filming is greatly improved.Along with the increase of organosilicon content, the water tolerance of filming has also obtained reinforcement simultaneously, and water contact angle obviously improves.Especially organosilyl adding can significantly improve the hydrophobic nature of filming after content reaches 25%.
4, organosilicon polymer can be given outstanding flexibility of coating and smooth silk feel, and acrylate has excellent fast light weathering resistance, fabulous snappiness etc., and resistant polyurethane low temperature, wear resisting property are good, and strong adhesion.
The invention provides a kind of stable performance, with water as dispersion medium, the synthetic method of the preparation organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion of compliance with environmental protection requirements.Product of the present invention combines three's excellent properties, and prepared organic silicon-polyurethane-acrylate ternary composite ionomer can be applied in various fields such as automobile, household electrical appliances, metal tools, building, textiles, coating.
Embodiment
After now embodiments of the invention being described in.
Embodiment 1
Below be that the present invention prepares organosilicon polyurethane-acrylic ester ionomer emulsion example, have following technological process and step:
(1) the organic silicon polyurethane performed polymer is synthetic
The butanone solvent of 90ml is mixed with the tolylene diisocyanate of 0.1mol (TDI) in the there-necked flask of back adding nitrogen protection; and drip three catalyzer dibutyltin dilaurates (DBT); be warming up to 60 ℃; slowly drip hydroxyl-terminated injecting two methyl siloxane; the mass percent that the content of hydroxyl-terminated injecting two methyl siloxane accounts for tolylene diisocyanate is 22%; in about 1.5h, drip off, dropwise the back and continue reaction 1.5 hours.Drip poly-Isopropanediol (PPG1000) then, tolylene diisocyanate (TDI) is 1: 1 with the molar ratio of poly-Isopropanediol, drips off in about 1.5h, dropwises the back and continues reaction 1.5 hours.
(2) positively charged ion organic silicon polyurethane performed polymer is synthetic
Cool to room temperature then drips the acetone soln of the N methyldiethanol amine (MDEA) of 0.05mol in reactor, be warming up to 60 ℃ of insulation 1h and get head product.With the head product distilled water wash, the flush away solvent, re-using massfraction is the neutralization of 10%NaOH solution, gets positively charged ion organic silicon polyurethane performed polymer at last.
(3) the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion is synthetic
With massfraction is that the performed polymer that 10%HCl regulating step (2) is made becomes neutral, warming-in-water to 75 ℃, (mass ratio of positively charged ion organic silicon polyurethane performed polymer and Acrylic Acid Monomer is 2: 3 to add Acrylic Acid Monomer and initiator Diisopropyl azodicarboxylate, the mass percent that initiator amount accounts for the Acrylic Acid Monomer consumption is 1%), in about 2h, drip off, continue reaction 1.5h then.Reaction makes stable organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion.
Embodiment 2
The synthetic method of the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion of present embodiment is substantially the same manner as Example 1, different is positively charged ion organic silicon polyurethane performed polymer (PU) quality percentage composition, see Table 1 and listed different positively charged ion organic silicon polyurethane performed polymers (PU) quality percentage composition the copolymer emulsion Effect on Performance, by table as can be seen along with the color of the increase emulsion of PU content shoals, the gel content of copolyreaction reduces, and copolymer emulsion is also more stable.Because the PU performed polymer contains a large amount of ionic linkages and comprises the hydrophilic and oleophilic group simultaneously, can play good emulsifying effect to emulsion polymerization.Therefore the increase of PU content is helpful to this emulsion polymerization, so the synthetic emulsion is stable more and gel content reduces, has played the effect of macromolecule emulsifier.
The different PU content of table 1 are to the Effect on Performance of PUA copolymer emulsion
The hardness and the sticking power of PU content copolymer emulsion in 40% reach optimum value as can be seen from Table 2, and the water tolerance of filming along with the increase of PU content descends simultaneously, and this is because brought a large amount of hydrophilic radicals among the PU.Comprehensive every mechanical property, later every experimental selection PU content is 40%.
The different PU content of table 2 is to the copolymer emulsion mechanical Effect on Performance of filming
Embodiment 3
The synthetic method of the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion of present embodiment is substantially the same manner as Example 1, and different is organosilyl quality percentage composition, sees Table 3 and has listed the variation of organosilicon content to the mechanical Effect on Performance of filming.By table as can be seen, every mechanical property of filming has all had very big improvement.The hardness of filming can both reach 2H at organosilicon content less than 52% o'clock, and sticking power can both reach zero level, and impact strength is all qualified.The water tolerance data that analysis is filmed draw, and make the water tolerance of filming be greatly improved by the ionic bonding between acrylate and the urethane.Along with the increase of organosilicon content, the water tolerance of filming has also obtained reinforcement simultaneously.
The variation that table 4 has been listed organosilicon content is to the influence of the ageing-resistant performance of filming. at the ultra violet lamp of 300w after 48 hours, every mechanical property of filming descends to some extent, the flavescence of filming.Reach at 42% o'clock and film at organosilicon content and still kept good hardness and sticking power and water tolerance.This performance improves a lot with filming to compare with organic silicon-acrylate with the organosilicon-urethane of organosilicon content, has proved absolutely between acrylic acid and the urethane to combine by ionic linkage and well compatible.
The variation of table 3 organosilicon content is to the mechanical Effect on Performance of filming
The mechanical property that table 4 300w ultra violet lamp was filmed after 48 hours
Organosilyl adding makes the surface tension of film descend, and greatly reduces the surface energy of film, and the viscosity of emulsion film is obviously descended.These performances are reflected on the water contact angle, and along with the raising of organosilicon additional proportion, water contact angle obviously improves.Especially organosilyl adding can significantly improve the hydrophobic nature of filming after content reaches 25%.
Claims (3)
1. the synthetic method of an organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion, it is characterized in that, with having introduced the organosilyl urethane (PU) and polyacrylic ester (PA) effect that has tertiary amino group, made the organic-silicon-modified PUA emulsion that contains the ionic linkage effect; Concrete synthetic method is as follows:
1) the organic silicon polyurethane performed polymer is synthetic
Appropriate amount of organic is mixed with tolylene diisocyanate (TDI) in the reactor of back adding nitrogen protection, and dropping appropriate amount of catalysts dibutyltin dilaurate (DBT), be raised to 50-80 ℃, slowly drip hydroxyl-terminated injecting two methyl siloxane, the mass percent that the content of hydroxyl-terminated injecting two methyl siloxane accounts for tolylene diisocyanate is 1-52%, in about 1.5h, drip, dropwise the back and continue reaction 1.5h; Drip poly-Isopropanediol then, the molar ratio of tolylene diisocyanate and poly-Isopropanediol is 1: 1, drips in about 1.5h, dropwises the back and continues reaction 1.5h;
2) positively charged ion organic silicon polyurethane performed polymer is synthetic
With the product cool to room temperature of step 1), in reactor, drip the acetone soln of the N methyldiethanol amine (MDEA) of 0.02-0.20mol, be raised to 50-80 ℃ of reaction 1h and get head product; With the head product distilled water wash, the flush away solvent re-uses mass percentage concentration for the neutralization of 10%NaOH solution, obtains positively charged ion organic silicon polyurethane performed polymer;
3) the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion is synthetic
With mass percentage concentration is 10%HCl solution regulating step 2) performed polymer made becomes neutral, under 65-85 ℃, slowly add Acrylic Acid Monomer and initiator, the mass ratio of positively charged ion organic silicon polyurethane performed polymer and Acrylic Acid Monomer is 1: 3-3: 3, the mass percent that initiator amount accounts for the Acrylic Acid Monomer consumption is 1%, in about 2h, add, continue reaction 1.5h then, make the organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion.
2. the synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion according to claim 1 is characterized in that organic solvent used in the step 1) is: acetone, butanone, toluene etc.
3. the synthetic method of organosilicon polyurethane-acrylic ester ternary composite ionomer emulsion according to claim 1 is characterized in that initiator used in the step 3) is: Potassium Persulphate, Ammonium Persulfate 98.5, Diisopropyl azodicarboxylate etc.
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