CN102516466B - Water-resistant and weather-resistant polyester polyurethane-polyacrylate aqueous dispersion and preparation method thereof - Google Patents
Water-resistant and weather-resistant polyester polyurethane-polyacrylate aqueous dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-resistant and weather-resistant polyester polyurethane-polyacrylate aqueous dispersion for a surface coating and a preparation method for the aqueous dispersion. The method comprises the following steps of: adding dihydric alcohol and dibasic acid into a reactor to synthesize polyester, adding acetone and dissolving, introducing nitrogen, sequentially adding isocyanate, dyhydroxy acid, polyol with a branched chain, an organotin catalyst and a chain extender dimethylethanolamine and reacting, and evaporating the acetone under reduced pressure to obtain a polyester-polyurethane aqueous dispersion; and adding water into the polyester-polyurethane aqueous dispersion, adding a small molecular emulsifier, sodium bicarbonate and persulfate, dripping a pre-emulsified acrylic monomer, supplementing the persulfate and continuing to react, and regulating the pH value to be 6 to 8 when the amount of the residual acrylic monomer is less than or equal to 0.5 percent to obtain the water-resistant and weather-resistant polyester polyurethane-polyacrylate aqueous dispersion. After the water-resistant and weather-resistant polyester polyurethane-polyacrylate aqueous dispersion is used for film formation, a coating has high hardness and toughness and excellent water resistance.
Description
Technical field
The present invention relates to a kind of little dispersion of polymkeric substance for top coats such as metal, plastics, woodenware.
Background technology
Metal, plastics, woodwork coating are subject to the restriction of environmental factors with coating, tend to gradually Water-borne modification, and the key of coating Water-borne modification is the Water-borne modification of film-forming resin.The water-base resin that is used at present coating has polyacrylic ester, polyurethane aqueous dispersion body, water-base epoxy, water-based fluorocarbon etc.; yet have ornamental and resin protectiveness concurrently and be mainly waterborne polyurethane modified water-and acrylate; existing aqueous polyurethane is owing to containing a large amount of hydrophilic radicals on main chain; water-fast undesirable, be difficult to satisfy the requirement of the performance such as water-fast, anticorrosion.And pure water-and acrylate film forming also has inborn defective, and as when softening temperature is higher, film process needs a large amount of film coalescence aid, and the easily cracking of filming; Filmed when softening temperature is too low soft, general uncomfortable as the external surface coating film-forming resin, and the polyacrylic ester of high and low low softening point becomes fragile, coating hardness is difficult to promote, moreover it is very limited to rely on the softening temperature that improves emulsion to improve hardness, because the softening temperature design is higher, the stability of emulsion is poorer.
Summary of the invention
The object of the invention is to overcome the defective of above-mentioned prior art and a kind of have good hardness, toughness, water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion are provided, the present invention also provides the preparation method of this water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion simultaneously.
the technical solution used in the present invention is to comprise the steps: that dibasic alcohol and diprotic acid that (1) is 1:1.5～3 with weight ratio add in reactor, add again the butyl stannonic acid catalyzer, pass into nitrogen, be warming up to 80-150 ℃ of reaction, then dewater under 200-240 ℃ of condition, until acid value≤3mgKOH/g, the hydroxyl of synthetic polyester account for 3.0 ~ 4.0%, effectively solid part be 100%, till weight-average molecular weight≤2000, (2) the polyester bottoming to synthesize in reactor, adding acetone solution to become weight solid part is the solution of 45-55%, pass into nitrogen, add successively isocyanic ester, dihydroxylated acid, branched polyvalent alcohol, organotin catalysts and chainextender dimethylethanolamine, control isocyanate index between 1.5-2.5, reacted 3-4 hour under 60 ~ 90 ℃ of conditions, be cooled to 40-60 ℃ after the hydroxyl completely dissolve, then add the organic amine neutralization to be scattered in water, decompression at last steams acetone, obtains the polyester-polyurethane ester aqueous dispersion, (3) with small-molecular emulsifier pre-emulsification Acrylic Acid Monomer, pre-emulsification Acrylic Acid Monomer total amount be described polyester-polyurethane solid part 3-10 doubly, in reactor with the bottoming of described polyester-polyurethane ester aqueous dispersion, adding weight is polyester-polyurethane ester aqueous dispersion weight 3-10 water doubly, add again small-molecular emulsifier, sodium bicarbonate and the persulphate that accounts for persulphate total amount 90-95%, then drip 10 ~ 30% the pre-emulsification Acrylic Acid Monomer 2 ~ 3 hours that consumption is equivalent to the Acrylic Acid Monomer total amount under 70 ~ 90 ℃ of conditions, react and use again 3 ~ 5 hours after 3-6 hour and drip remaining Acrylic Acid Monomer, be incubated 2 ~ 4 hours, add at last remaining persulphate and continue reaction, get final product to 6-8 until the amount of residual Acrylic Acid Monomer when being less than or equal to 0.5%, is regulated the pH value.
The invention has the beneficial effects as follows:
1, after water dispersion film forming of the present invention, coating has good hardness and toughness, and hardness reaches the Chinese pencil of 1 ~ 2H(), toughness can arrive 1mm, also has fabulous water tolerance simultaneously, just light discolouration in 240 hours in 40 ℃ of water.Can be used as woodenware, metal, frosting application film forming base-material.
2, the present invention be with water as dispersion medium, under Construction State, contain hardly any volatilizable organic composition, energy-conservation, environmental friendliness.
3, in the present invention, resin body replaces traditional polyether-modifiedly with polyester modification, and weathering resistance, ornamental good can be used for the base-material of the external coatings use coating such as iron and steel, ABS plastic, synthetic glass, timber, as the film forming base-material of outdoor coating.
4, the composite modified self-crosslinking feature of organosilicon can further promote the water-proofing performance of resin film forming matter.
Embodiment
Polyester-polyurethane-polyacrylate aqueous dispersion of the present invention is comprised of polyester-polyurethane, polyacrylic ester and three kinds of components of water, and by weight: polyester-polyurethane accounts for 2.5 ~ 10%, polyacrylic ester accounts for 30 ~ 37.5%, water accounts for 60%.Wherein, polyester-polyurethane is comprised of polyester, urethane and three kinds of components of water, and by weight, polyester accounts for 10 ~ 20%, urethane accounts for 15 ~ 23%, water accounts for 57 ~ 65%.
When preparing above-mentioned polyester-polyurethane-polyacrylate aqueous dispersion, at first synthesizing polyester, the recycling polyester is done raw material, utilize acetone in conjunction with the aqueous polyurethane water dispersion, recycling changes polyurethane aqueous dispersion body and does internal emulsifying agent at last, adopt the synthetic polyester-polyurethane-polyacrylate aqueous dispersion with inierpeneirating network structure of method of radical polymerization, concrete preparation method is as follows:
The first step: the synthetic linear polyester oligomer that has good hydrophobicity, has terminal hydroxy group.The raw material that synthesizing polyester adopts is dibasic alcohol and diprotic acid, is composited by dibasic alcohol and diprotic acid, and the weight ratio of dibasic alcohol and diprotic acid is 1:1.5～3.Wherein, in dibasic alcohol, neopentyl glycol accounts for 30%, and all the other are ethylene glycol, 1,3 propylene glycol, and one or more in diethylene glycol cyclohexanediol etc. are compound.In diprotic acid, phthalic anhydride accounts for 30%, and all the other are that one or more in succinic acid, pentanedioic acid, hexanodioic acid etc. are compound.Dibasic alcohol and diprotic acid are added in reactor, add again butyl stannonic acid catalyzer (catalyzer 4100), pass into nitrogen, be warming up to reaction between 80-150 ℃, synthesizing polyester, dehydration at last, dehydration temperaturre is between 200-240 ℃, dewatering time is generally at 4-8 hour, and is final, when acid value≤3mgKOH/g, hydroxyl (OH) account for 3.0 ~ 4.0%, effectively solid part is 100%, finishes during weight-average molecular weight≤2000.Synthetic polyester is in a liquid state, and the molar mass number of carboxyl is less than the molar mass number of hydroxyl, and the length of chain directly affects the hardness of a final moisture prose style free from parallelism.
Second step: utilize synthetic polyester bottoming, add the acetone solution polyester, being dissolved into weight solid part is the solution of 45-55%, passes into nitrogen, adds successively isocyanic ester, dihydroxylated acid, branched polyvalent alcohol, organotin catalysts and chainextender dimethylethanolamine in reactor.Before chain extension, isocyanate index is controlled between 1.5-2.5, namely the isocyanic ester mole number is 1.5-2.5 with the ratio of hydroxyl mole number.Be reaction 3-4 hour under the condition of 60 ~ 90 ℃ in temperature, treat-the OH completely dissolve, be cooled to 40-60 ℃, and then add the neutralization of the organic amine such as triethylamine to be scattered in water, degree of neutralization is controlled at 85-110%, then the decompression steam acetone, obtain the polyester-polyurethane ester aqueous dispersion of stable dispersion in water.This polyester-polyurethane polyether(poly)urethane relatively has better hardness and photostabilization.
The isocyanic ester that adopts can be hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI) or tolylene diisocyanate (TDI) etc.; Dihydroxylated acid can be dimethylol propionic acid, dihydroxypropionic acid or dihydroxyl butyric acid; Branched polyvalent alcohol is tetramethylolmethane; Organotin catalysts is dibutyl tin laurate.
The 3rd step: with small-molecular emulsifier pre-emulsification Acrylic Acid Monomer, the Acrylic Acid Monomer total amount be above-mentioned polyester-polyurethane solid part 3-10 doubly, the small-molecular emulsifier consumption accounts for the 2-3.5% of Acrylic Acid Monomer total amount.Small-molecular emulsifier is one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP series emulsifying agent (condenses of alkylphenol and oxyethane) etc.Acrylic Acid Monomer can be ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, (methyl) cyclohexyl acrylate, vinylbenzene, isobornyl acrylate, acrylamide, wherein one or several of methacryloxy trimethoxy organosilicon.
In reactor, utilize the bottoming of above-mentioned polyester-polyurethane ester aqueous dispersion, use water-dispersion, the addition of water is equivalent to 3-10 times of polyester-polyurethane ester aqueous dispersion weight, and add small-molecular emulsifier, then add persulphate and the sodium bicarbonate that accounts for persulphate total amount 90-95%.Wherein, small-molecular emulsifier used is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP series emulsifying agent etc., during the consumption of small-molecular emulsifier is equivalent to fill a prescription 1.2 ~ 2% of the Acrylic Acid Monomer total amount.Persulphate used is Potassium Persulphate or ammonium persulphate etc., utilizes persulphate to make initiator, and the persulphate total amount is equivalent to 0.1 ~ 0.5% of Acrylic Acid Monomer total amount.Sodium bicarbonate used is made buffer reagent, and sodium bicarbonate weight accounts for 0.2 ~ 1.0% of Acrylic Acid Monomer total amount.
Under 70 ~ 90 ℃ of conditions, dropping is through the pre-emulsified Acrylic Acid Monomer of small-molecular emulsifier, and the Acrylic Acid Monomer total amount is 3 ~ 10 times of polyester-polyurethane solid part, first drips 2 ~ 3 hours, the consumption of Acrylic Acid Monomer is equivalent to 10 ~ 30% of Acrylic Acid Monomer total amount, after dripping end, continue reaction and approximately made seed in 3-6 hour, then, drip again remaining Acrylic Acid Monomer, remaining Acrylic Acid Monomer divides and added in 3 ~ 5 hours, after adding, is incubated 2 ~ 4 hours under 70 ~ 90 ℃ of conditions.Then, then add remaining 5 ~ 10% persulfate initiator, continue reaction, until the amount of residual Acrylic Acid Monomer is when being less than or equal to 0.5%, with ammoniacal liquor or organic amine neutralization, regulate the pH value to 6-8, can obtain having the polyester-polyurethane-polyacrylate aqueous dispersion of interpenetrating structure.
Material purity related in the present invention all should be more than 99%.
Below provide 4 embodiment with further elaboration the present invention:
Embodiment 1
With phthalic anhydride 105g, succinic acid 245g, neopentyl glycol 60, ethylene glycol 140g and proper catalyst 4100 add in reactor, pass into nitrogen, temperature rise rate by 100 ℃/hour, be warming up to 200 ~ 220 ℃, dewater to acid value≤3mgKOH/g ,-OH accounts for 3%, effectively solid part is 100%, weight-average molecular weight≤2000 o'clock finish, cooling, the polyester discharging is standby.
With polyester 45.2g bottoming, disperse with 45g acetone, then add successively IPDI 70g, dimethylol propionic acid 7.8g, tetramethylolmethane 3.5g, dibutyl tin laurate 0.15g, dimethylethanolamine 19.7g is warming up to 85 ~ 90 ℃, is incubated 3 ~ 4 hours, treat the hydroxyl completely dissolve, be cooled to 50 ~ 60 ℃, add triethylamine 5g, in and 1 hour, cooling, with the discharging of polyester-polyurethane ester aqueous dispersion.
Water 120g, sodium lauryl sulphate 1g, OP-10(alkylphenol polyoxyethylene) 1.7g, acrylic amine 54g, methacryloxy trimethoxy organosilicon 24g, the pre-emulsification Acrylic Acid Monomer, standby.Perhaps water 100g, sodium lauryl sulphate 2g, OP-10 3.1g; Vinylbenzene 125g, butyl acrylate 95g, isobornyl acrylate 11g, the pre-emulsification Acrylic Acid Monomer, standby.
Get above-mentioned polyester-polyurethane ester aqueous dispersion 67g, add entry 312g, sodium lauryl sulphate 3.9 g, Potassium Persulphate 0.35g, sodium bicarbonate 0.7g, stir evenly and be warming up to 70 ℃, then drip 20% standby pre-emulsification Acrylic Acid Monomer emulsion, divide to add in 2-3 hour, continued reaction approximately 3-5 hour; Drip again remaining pre-emulsification Acrylic Acid Monomer emulsion, divide to add in 4-5 hour, be incubated again 2-3 hour under 80 ℃ of left and right conditions.Add Potassium Persulphate 0.03g, continue reaction, with the triethylamine neutralization, transfer pH to 7 left and right, cooling, discharging.
Embodiment 2
Succinic acid during synthesizing polyester in embodiment 1 is changed into the hexanodioic acid of equivalent, ethylene glycol changes 1,3 propylene glycol of equivalent into, changes the dimethylol propionic acid of urethane part into dimethylolpropionic acid, and other is constant.
Embodiment 3
Succinic acid in polyester in embodiment 1 is changed into the pentanedioic acid of equivalent, methacryloxy trimethoxy organosilicon equivalent changes Isooctyl acrylate monomer in acrylic acid modified middle pre-emulsion, and temperature of reaction is promoted to 90 ℃, and other is constant.
Embodiment 4
Polyester-OH in embodiment 1 is transferred to 3.5%, and in the urethane preparation, the IPDI equivalent replaces with TDI, and other is constant.
Polyester-polyurethane-polyacrylate aqueous dispersion that above-mentioned 4 embodiment are obtained transfers to 25% with its solid part respectively, making respectively thickness 18 ± 3 μ m(glass surface thickness on glass and tinplate compares with tinplate, estimate thickness), its test-results is as follows:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Hardness (glass film plates) | 2H | 1H | 2H | 3H |
| Drip boiling water (glass film plates) | Non-whitening | Non-whitening | Turn white | Non-whitening |
| Snappiness (tinplate) | 1mm | 1mm | 1mm | 1mm |
| Fast light (QUV), loss of gloss are less than 10%, and aberration is less than 3.0, h | 360 | 312 | 336 | 408 |
Claims (6)
1. the preparation method of water-fast, a weather-proof polyester-polyurethane-polyacrylate aqueous dispersion, is characterized in that comprising the steps:
(1) be that dibasic alcohol and the diprotic acid of 1:1.5～3 adds in reactor with weight ratio, add again the butyl stannonic acid catalyzer, pass into nitrogen, be warming up to 80-150 ℃ of reaction, then dewater under 200-240 ℃ of condition, until acid value≤3mgKOH/g, the hydroxyl of synthetic polyester account for 3.0 ~ 4.0%, effectively solid part be 100%, till weight-average molecular weight≤2000;
(2) the polyester bottoming to synthesize in reactor, adding acetone solution to become weight solid part is the solution of 45-55%, pass into nitrogen, add successively isocyanic ester, dihydroxylated acid, branched polyvalent alcohol, organotin catalysts and chainextender dimethylethanolamine, control isocyanate index between 1.5-2.5; Reacted 3-4 hour under 60 ~ 90 ℃ of conditions, be cooled to 40-60 ℃ after the hydroxyl completely dissolve, then add the organic amine neutralization to be scattered in water, decompression at last steams acetone, obtains the polyester-polyurethane ester aqueous dispersion;
(3) with small-molecular emulsifier pre-emulsification Acrylic Acid Monomer, pre-emulsification Acrylic Acid Monomer total amount be described polyester-polyurethane solid part 3-10 doubly, in reactor with the bottoming of described polyester-polyurethane ester aqueous dispersion, adding weight is polyester-polyurethane ester aqueous dispersion weight 3-10 water doubly, add again small-molecular emulsifier, sodium bicarbonate and the persulphate that accounts for persulphate total amount 90-95%, then drip 10 ~ 30% the pre-emulsification Acrylic Acid Monomer 2 ~ 3 hours that consumption is equivalent to the Acrylic Acid Monomer total amount under 70 ~ 90 ℃ of conditions, react and use again 3 ~ 5 hours after 3-6 hour and drip remaining Acrylic Acid Monomer, be incubated 2 ~ 4 hours, add at last into remaining persulphate and continue reaction, get final product to 6-8 until the amount of residual Acrylic Acid Monomer when being less than or equal to 0.5%, is regulated the pH value.
2. the preparation method of a kind of water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion according to claim 1, it is characterized in that: in step (1), neopentyl glycol in dibasic alcohol accounts for 30%, all the other are one or more in ethylene glycol, 1,3 propylene glycol, diethylene glycol, cyclohexanediol; Phthalic anhydride in diprotic acid accounts for 30%, and all the other are one or more in succinic acid, pentanedioic acid, hexanodioic acid.
3. the preparation method of a kind of water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion according to claim 1, it is characterized in that: described in step (2), isocyanic ester is hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate or tolylene diisocyanate; Described dihydroxylated acid is dimethylol propionic acid, dihydroxypropionic acid or dihydroxyl butyric acid; Described branched polyvalent alcohol is tetramethylolmethane; Described organotin catalysts is dibutyl tin laurate.
4. the preparation method of a kind of water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion according to claim 1, it is characterized in that: in step (3), describedly add the small-molecular emulsifier in small-molecular emulsifier to account for 1.2 ~ 2% of Acrylic Acid Monomer total amount, described persulphate total amount accounts for 0.1 ~ 0.5% of Acrylic Acid Monomer total amount, and described sodium bicarbonate accounts for 0.2 ~ 1.0% of Acrylic Acid Monomer total amount.
5. the preparation method of a kind of water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion according to claim 1, it is characterized in that: in step (3), the described 2-3.5% that accounts for the Acrylic Acid Monomer total amount with the small-molecular emulsifier consumption in small-molecular emulsifier pre-emulsification Acrylic Acid Monomer.
6. the preparation method of a kind of water-fast, weather-proof polyester-polyurethane-polyacrylate aqueous dispersion according to claim 1, it is characterized in that: in step (3), described small-molecular emulsifier is one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP series emulsifying agent; Described Acrylic Acid Monomer is one or more in ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, butyl methacrylate, (methyl) cyclohexyl acrylate, vinylbenzene, isobornyl acrylate, acrylamide, methacryloxy trimethoxy organosilicon.
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| CN101735721A (en) * | 2008-11-05 | 2010-06-16 | 北京高盟化工有限公司 | Pinhole-proof aqueous coating agent for powder-free PVC gloves and preparation method thereof |
| CN102133802A (en) * | 2010-01-21 | 2011-07-27 | 中国科学院化学研究所 | Flaky material with front and back surfaces having different properties and preparation method thereof |
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| CN101735721A (en) * | 2008-11-05 | 2010-06-16 | 北京高盟化工有限公司 | Pinhole-proof aqueous coating agent for powder-free PVC gloves and preparation method thereof |
| CN102133802A (en) * | 2010-01-21 | 2011-07-27 | 中国科学院化学研究所 | Flaky material with front and back surfaces having different properties and preparation method thereof |
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