CN101914261B - Polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material and synthesizing process thereof - Google Patents
Polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material and synthesizing process thereof Download PDFInfo
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Abstract
The invention discloses a new polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material and a synthesizing process thereof. The average particle diameter of the emulsion colloidal particles is less than 200nm, the topography characteristic of the particles is a multi-layer colloidal particle structure, the core is a polyurethane oil polyacrylate graft copolymer, and the outer layer is a hydrophilic polymer of the polyurethane oil. The synthesizing process comprises the following steps: preparing an alcoholysate from drying oil or semi-drying oil and low-molecular-weight polyalcohol; synthesizing a polyurethane oil solution and ionizing; preparing polyurethane oil-water dispersion; and preparing the polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material LIPN PUO/PA. Compared with the general water dispersion, the emulsion of the invention has higher luster and can effectively solve the problem of surface finish of a general water-base metal coating, a wooden ware coating, a leather coating and a paper coating, thus further improving the over-all properties of the material.
Description
Technical field
The present invention relates to can be used as and be coated with in hide finishes and oil polish, wood lacquer brightening agent, the automobile and latex interpenetrating net polymer and the synthesis technique thereof of top coat, metal finishing coating, specifically a kind of polyurethane oil/polyacrylate latex interpenetrating network emulsion material and synthesis technique thereof.
Background technology
Latex interpenetrating net polymer (LIPN) L.H.Sperling﹠amp; D.A.Thomas has just applied for United States Patent (USP) (U.S.Pat.3,833,404 (1974)) in 1974, be mainly used to make damping paint.Also carry out the research work of LIPN the domestic eighties, but still do not solved up to now the common drawback of all aqueous dispersion materials---the problem of " coating gloss is low ".It is reported European Main Auto manufacturing company exterior decoration from primary coat, be coated onto face and be coated with all Water-borne modification, but owing to the gloss reason has still kept the solvent based coating Lacquer finish; It is representational coating that leather, particularly leatheroid are covered with paint, lacquer, colour wash, etc. as soft coating, same because the gloss problem is still keeping the coatings volatile organic compounds Lacquer finish in many concrete application; The performance of aqueous wooden ware house ornamentation lacquer reaches a standard substantially, even has entered the streamline application, but also is only limited to the decoration of dumb light door and window.Obviously, development high gloss waterborne film-forming thing is an important component part popularizing the water-based coating material in an all-round way.
Summary of the invention
Purpose of the present invention is exactly aqueous dispersion material---the polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material that a kind of high gloss is provided in order to solve the low problem of aqueous dispersion materials glossiness, this material is with respect to general water dispersion, has higher gloss, can effectively solve the face cap optical issue of general water-based metal coating, woodenware coating, leather coating, paper coating, the material over-all properties is further improved.
Further aim of the present invention provides the synthesis technique of described polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material.
The present invention is achieved in that a kind of polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material, the median size of this emulsion colloidal is less than 200nm, the topography of this particle is characterized as multiple layer micellar structure, examines as the polyurethane oil graft copolymers of polyacrylates, outerly is the hydrophilic polymer of polyurethane oil.
The synthesis technique of described polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material may further comprise the steps:
1. prepare alcoholysate (a): make alcoholysate (a) with siccative oil or semi-drying oil and low molecular polylol generation alcoholysis reaction in the presence of catalyzer; Described catalyzer is lithium hydroxide or calcium oxide;
2. with following raw materials according synthesis of polyurethane oil solution:
Alcoholysate (a), polyvalent alcohol, diisocyanate monomer, chainextender and thinner; Wherein, described polyvalent alcohol is polyether glycol or polyester polyol, described diisocyanate monomer is a kind of in aromatic diisocyanate, aliphatic diisocyanate or the alicyclic diisocyanate or any two or more mixture, and described thinner comprises reactive thinner;
3. carry out ionization with neutralizing agent to 2. going on foot made polyurethane oil solution, make Ionized polyurethane oil solution; Under high-speed stirring, described polyurethane oil Solution Dispersion in deionized water, is made polyurethane oil water dispersion (b);
4. in polyurethane oil water dispersion (b), add vinylformic acid hard monomer, vinylformic acid soft monomer and function monomer, initiator and emulsifying agent, carry out free-radical emulsion polymerization in 70～90 ℃, reacted 2-4 hour, system is cooled to 40 ℃ of dischargings, makes the polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material.
The present invention the is at first synthetic alcoholysate (a) of step 1., is about to siccative oil or semi-drying oil, low molecular polylol and catalyzer; by the consumption adding agitator, pumped vacuum systems are installed; in the reactor of reflux exchanger and heating installation, be heated to 120 ℃ under stirring, be evacuated to the 760mmHg dehydration 1-2 hour; then lay down vacuum; pass into nitrogen protection, be heated to 210-250 ℃, reacted 2-5 hour; tolerance is qualified to surveying, and namely gets " alcoholysate " (a).This alcoholysate (a) is for comprising dibasic alcohol monoleate, monohydroxy-alcohol dioleate, a small amount of oil and the mixture of polyvalent alcohol.Should " alcoholysate " (a) both can cooling discharge, for subsequent use as intermediate after packing, also can proceed next step reaction.
2. the step is with traditional method synthesis of polyurethane oil solution in the present invention the: will " alcoholysate " (a), polyether glycol or polyester polyol press in the container of consumption adding with agitator, condenser, vacuum system and heating system, be evacuated to 750～760mmHg under stirring, in 100～120 ℃ of insulations 1-2 hour, it was clean to make it dehydration.System temperature is down to 50-60 ℃, adds diisocyanate monomer again, then react in 70～90 ℃ of scopes, reaction was carried out 3～4 hours.Question response is down to 50-60 ℃ with system temperature after finishing, and adds the chainextender of specified amount and an amount of thinner, and lower reaction 3～8 hours refluxes.
3. the present invention goes on foot the previous reaction liquid temp is down to 40 ℃, add that neutralizing agent neutralizes and stir with higher speed and make its ionization, make Ionized polyurethane oil solution, again under high-speed stirring, be distributed in the deionized water, make the polyurethane oil water dispersion that contains a certain amount of thinner or reactive thinner.
4. the step is on the basis of polyurethane oil water dispersion in the present invention the, do not add or add the emulsifying agent of a small amount of (micelle-forming concentration is following), temperature is risen to 60-75 ℃, add again part initiator, buffer reagent, begin to drip the monomer mixture that is formed by vinylformic acid hard monomer, vinylformic acid soft monomer and function monomer in 70-85 ℃, in 2～2.5 hours, dropwise, continue reaction 1～2 hour at 70～90 ℃ subsequently; Be cooled to 45-50 ℃, add initiator and reductive agent, continue reaction 0.5～1.0 hour, in 40 ℃ of dischargings, filter and package, namely get the polyurethane oil/polyacrylate latex interpenetrating network high gloss polymer emulsion material with multilayer structure.
The present invention be directed to and utilize general letex polymerization and traditional synthetic low this drawback of the ubiquitous surface luster of water dispersion institute of latex interpenetrating(polymer)networks synthetic technology, invented a kind of synthesis technique of polyurethane oil/polyacrylate latex interpenetrating network high gloss polymer emulsion material, and utilize this technique successfully to synthesize the polyurethane oil/polyacrylate latex interpenetrating network high gloss polymer emulsion material of nano-scale, gloss generally can meet or exceed 80%, can satisfy the needs of general coating surface Lacquer finish.
Among the present invention, described siccative oil and semi-drying oil are tung oil, Chinese catalpa oil, synourin oil, Semen Lini oil, perilla oil, cannabis oil, soya-bean oil, Yatall MA or sunflower seed oil; Described low molecular polylol is glycerine, tetramethylolmethane or TriMethylolPropane(TMP).
Among the present invention; the 1. the technique in step be: with siccative oil or semi-drying oil; low molecular polylol and catalyzer are heated to 110-130 ℃ under stirring, and are evacuated to the 760mmHg dehydration 1-2 hour; then lay down vacuum; pass into nitrogen protection, be heated to 210-250 ℃, reacted 2-5 hour; tolerance is qualified to surveying, and namely gets " alcoholysate " (a).
Among the present invention, described polyether glycol is polyethers 1000, polyethers 2000 or polyethers 3000; Described polyester polyol is polyethylene glycol adipate glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol-glycol ether esterdiol, poly-hexanodioic acid-1,4 butanediol ester glycol, poly-adipate glycol-1,4 butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol or the poly-carbonic acid 1 of poly-epsilon-caprolactone glycol, 6-hexylene glycol esterdiol.
Among the present invention, described aromatic isocyanate is: tolylene diisocyanate (TDI), diphenylmethane diisocyanate component (MDI), poly methylene poly phenyl poly isocyanate (PAPI) or xylylene diisocyanate (XDI); Described aliphatic diisocyanate is: hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), trimethylammonium hexamethylene diisocyanate (TMDI); Described alicyclic diisocyanate is: isophorone diisocyanate (IPDI) or hexahydrotoluene vulcabond (HTDI); Described chainextender is: dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA) or 2,3 dyhydrobutanedioic acids (tartrate); Described thinner is: butanone, acetone, methylethylketone, dioxane or toluene; Described reactive thinner is one or more the mixture in the following Acrylic Acid Monomer: vinylbenzene, methyl methacrylate, vinyl cyanide, alpha-methyl styrene, butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl or butyl methacrylate; Described neutralizing agent is ammoniacal liquor or triethylamine;
Among the present invention, described vinylformic acid hard monomer is: vinylbenzene, methyl methacrylate, vinyl cyanide, alpha-methyl styrene; Described vinylformic acid soft monomer is: butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl or butyl methacrylate; Described function monomer comprises carboxylic monomer and cross-linking monomer: vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, n-methylolacrylamide or glycidyl acrylate, divinylbenzene, ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate triglycol ester and three triallyl isocyanurates.
Among the present invention, described initiator is ammonium persulphate, Potassium Persulphate, Diisopropyl azodicarboxylate, tertbutyl peroxide, benzoyl peroxide or lauroyl peroxide; Described emulsifying agent is nonionic emulsifying agent or anion surfactant; Wherein nonionic emulsifying agent is alkyl (C
8-C
9) polyoxyethylenated alcohol or alkyl (C
8-C
9) phenol polyethenoxy ether; Anion surfactant is Sodium dodecylbenzene sulfonate, MS-1 or sodium lauryl sulphate.
Among the present invention, described each raw materials by weight portion is:
Siccative oil or semi-drying oil 2.0～4.0
Low molecular polylol 0.4～1.2
Catalyzer 0.003～0.007
Polyether glycol or polyester polyol 3.0～5.5
Diisocyanate monomer 4.0～6.0
Chainextender 0.5～3.0
Thinner 0～2.0
Neutralizing agent 0.3～0.7
Initiator 0.04～0.6
Buffer reagent 0.04～0.6
Vinylformic acid soft monomer 4.0～8.0
Vinylformic acid hard monomer 4.0～8.0
Function monomer 0.15～0.3
Deionized water 65.0～80.0
Description of drawings:
Fig. 1 is the embodiment of the invention 1 particle diameter test result.
Fig. 2 is the embodiment of the invention 2 particle diameter test results.
Fig. 3 is the particle diameter test result of Comparative Examples of the present invention.
Fig. 4 is the embodiment of the invention 1 transmissioning electric mirror test result.
Fig. 5 is the embodiment of the invention 1 DMA test result.
Fig. 6 is the embodiment of the invention 2 DMA test results.
Embodiment
The alkali of 110 grams was floated in cannabis oil and 500 milliliters the four-hole bottle of 23.5 gram glycerine addings with heating installation and pumped vacuum systems, start stirring, heat temperature raising, begin to vacuumize when treating near 100 ℃, vacuum keep is at 750-760mmHg, to 120 ℃ of insulations 2 hours, dewater.Then lay down vacuum; pass into nitrogen protection, load onto reflux exchanger, add 0.2 gram hydroxide Lithium; be warming up to 200-240 ℃ of reaction 2-3 hour; until the tolerance of methyl alcohol is 1: during 2-3, add 0.2 gram phosphoric acid, after stirring; be cooled to rapidly 40-50 ℃; discharging, filtration, packing namely get alcoholysate, and be stand-by.
In the above-mentioned alcoholysate and 1000 milliliters of four-hole bottles of 30.6 gram polyethers, 1000 addings with heating and vacuum system with 26.7 grams, start to stir and be heated to 100 ℃ and begin to vacuumize, it is 750-760mmHg dehydration 1-1.5 hour in vacuum tightness that temperature remains on 120 ℃, shed vacuum, be cooled to 60 ℃ and install back flow condenser, add 46.5 gram isophorone diisocyanates (IPDI), keep 70-90 ℃ of temperature, react and be cooled to 60 ℃ after 3-4 hour, add 7.8 gram dihydroxyl butyric acid (DMBA) and 20 milliliters of butanone, it is lower to 75-85 ℃ of reaction 5-6 hour to reflux.Be cooled to 40 ℃, add 3.1 gram triethylamines and fully stirred 5 minutes, improve stirring velocity, add 654 gram deionized waters, the water dispersion that obtains polyurethane oil is network I; Then be warming up to 75 ℃, add the mixing solutions with 10 ml waters dissolving, 0.5 gram Potassium Persulphate and 0.5 gram buffer reagent sodium bicarbonate, after stirring, slowly drip the mix monomer that is consisted of by 58 gram methyl methacrylates, 45 gram butyl acrylates and 2 gram vinylformic acid in 75-85 ℃, be controlled in 2-2.5 hour and dropwise, then keep constant temperature to continue reaction after 1.5 hours.Be reduced to 45 ℃, slowly add by 5 ml waters dissolving, 0.5 gram tertbutyl peroxide solution, slowly drip again the aqueous solution by 5 ml waters dissolving, 0.5 gram reductive agent rongalite after stirring, continue reaction 30 minutes, filter and package in 40 ℃ of dischargings, namely get the compound polyurethane oil polyacrylate latex interpenetrating network of network I and network II and be designated as LIPN PUO/PA.
The coating of the made emulsion material of present embodiment is utilized the test of the intelligent gloss degree of KGZ-1C instrument, and glossiness is 89%.Figure 1 shows that embodiment 1 particle diameter test result, illustrate that the made emulsion particle diameter of present embodiment distributes near 150 nanometers, wherein, most of emulsion particle diameter is less than 150 nanometers.Transmissioning electric mirror test result shown in Figure 4 shows that the particle of made latex interpenetrating network polymer emulsion material still is approximate concentric " nuclear-shell " multiple layer micellar structure in the topography feature.DMA test shown in Figure 5 shows that the made emulsion material of present embodiment belongs to typical inierpeneirating network structure.
Embodiment 2
20.0 grams are restrained hydroxide Lithium through cannabis oil and 4.7 glycerine that restrain and 0.052 that alkali floats, be heated to 120 ℃ under stirring, then under the 750-760mmHg vacuum, dewatered 1 hour, then shedding vacuum is warming up to 220-250 ℃ to carry out the alcoholysis 2-3 hour tolerance to methyl alcohol is 1: during 2-3, the catalyzer that adds an amount of phosphorolytic cleavage remnants, be cooled to rapidly 150 ℃, add 30.6 gram polyethers 1000 and temperature is remained on 120 ℃ to reactor, vacuum tightness is 750-760mmHg dehydration 1.5 hours.Shed vacuum, be cooled to 60 ℃ and install back flow condenser, add 50.5 gram isophorone diisocyanates (IPDI), keep 70-80 ℃ of temperature, react and be cooled to 60 ℃ after 3-4 hour, add 6.7 gram dimethylolpropionic acid (DMBA) and 15 milliliters of butanone, it is lower to 75-85 ℃ of reaction 6 hours to reflux.Be cooled to 40 ℃, add 3.1 gram triethylamines and fully stirred 5 minutes, improve stirring velocity, the water dispersion that adding 765 gram deionized waters obtain Polyurethane oil is network I; Then be warming up to 75 ℃, after adding the mixing solutions stirring all with 10 ml waters dissolving, 0.5 gram Potassium Persulphate and 0.5 gram sodium bicarbonate, in the 75-85 ℃ of dropping that blows slowly 52 gram butyl methacrylate are arranged, the mix monomer that 51 gram vinylbenzene and 2 gram vinylformic acid consist of, be controlled in 2-2.5 hour and dropwise, and under constant temperature, continue polyreaction after 1 hour, be reduced to 45 ℃, slowly add by 5 ml waters dissolving, 0.5 gram tertbutyl peroxide solution, slowly drip again after stirring by 5 milliliters of water-soluble 0.5 gram rongalite aqueous solution, add an amount of rear reaction 45 minutes that continues, discharging filters and packages, namely get the compound polyurethane oil polyacrylate latex interpenetrating network material of network I and network II, be designated as LIPN PUO/PA.
The coating of the made emulsion material of present embodiment is utilized the test of the intelligent gloss degree of KGZ-1C instrument, and glossiness is 85%.Figure 2 shows that embodiment 2 particle diameter test results, illustrate that the made emulsion particle diameter of present embodiment distributes near 200 nanometers.DMA test chart shown in Figure 6 is spoken frankly the made emulsion material of bright present embodiment and is belonged to typical inierpeneirating network structure.
Embodiment 3
20.1 grams are restrained calcium oxide through tung oil and 12 TriMethylolPropane(TMP)s that restrain and 0.03 that alkali floats, be heated to 120 ℃ under stirring, then under the 760mmHg vacuum, dewatered 2 hours, then shedding vacuum is warming up to 240-250 ℃ to carry out 3 hours tolerances to methyl alcohol of alcoholysis is 1: during 2-3, add the catalyzer of an amount of phosphorolytic cleavage remnants and be cooled to rapidly 150 ℃, and backward reactor adds 51.6 gram polyethers 2000, temperature is remained on 110 ℃, be 750-760mmHg dehydration 1 hour in vacuum tightness, shed vacuum, be cooled to 60 ℃ and install back flow condenser, add 54.86 gram isophorone diisocyanates (IPDI), keep 70-80 ℃ of temperature, react and be cooled to 50 ℃ after 4 hours and add 10.54 gram dihydroxypropionic acid (DMBA) and 20 milliliters of butanone, reflux and reacted 5 hours in 75-85 ℃ down.Be cooled to 40 ℃, add 6.9 gram triethylamines and fully stirred 5 minutes, improve stirring velocity, add 550 gram deionized waters, the water dispersion that obtains polyurethane oil is network I; Then be warming up to 75 ℃, after adding stirs with 20 ml waters dissolving, 0.5 gram Potassium Persulphate and 0.5 mixing solutions that restrains sodium bicarbonate, in the 75-85 ℃ of dropping that blows slowly 50 gram butyl acrylates are arranged, the mix monomer that 50 gram methylpropanoic acid methyl esters and 2 gram vinylformic acid consist of, be controlled at dropwise in 2-2.5 hour after, continue polyreaction under the constant temperature after 1 hour, be reduced to 45 ℃, slowly add by 10 ml waters dissolving, 0.5 gram tertbutyl peroxide solution, slowly drip again the aqueous solution by 10 ml waters dissolving, 0.5 gram rongalite after stirring, add an amount of rear reaction 40 minutes that continues, discharging filters and packages, and namely gets the compound polyurethane oil polyacrylate latex interpenetrating network of network I and network II and is designated as LIPN PUO/PA.
The coating of the made emulsion material of present embodiment is utilized the test of the intelligent gloss degree of KGZ-1C instrument, and glossiness is 90%.
Embodiment 4
40 grams are restrained hydroxide Lithium through perilla oil and 4.2 tetramethylolmethanes that restrain and 0.069 that alkali floats, be heated to 120 ℃ under stirring, then under the 750-760mmHg vacuum, dewatered 1 hour, then shedding vacuum is warming up to 220-250 ℃ to carry out the alcoholysis 2-3 hour tolerance to methyl alcohol is 1: during 2-3, the catalyzer that adds an amount of phosphorolytic cleavage remnants, be cooled to rapidly 150 ℃, add 54.5 gram polyethylene glycol adipate glycol to reactor, and temperature remained on 120 ℃, vacuum tightness is 750-760mmHg dehydration 1.5 hours.Shed vacuum, be cooled to 60 ℃ and install back flow condenser, add 58.9 gram tolylene diisocyanates (TDI), keep 70-80 ℃ of temperature, react and be cooled to 60 ℃ after 3-4 hour, add 28.5 gram dimethylol propionic acid (DMPA) and 15 milliliters of acetone, it is lower to 75-85 ℃ of reaction 6 hours to reflux.Be cooled to 40 ℃, add 6.8 gram ammoniacal liquor and fully stirred 5 minutes, improve stirring velocity, the water dispersion that adding 780 gram deionized waters obtain polyurethane oil is network I; Then be warming up to 75 ℃, after adding stirs with 10 ml waters dissolving, 0.5 gram Potassium Persulphate and 0.5 mixing solutions that restrains sodium bicarbonate, in the 75-85 ℃ of dropping that blows slowly 79.2 gram ethyl propenoates are arranged, 78.6 the mix monomer that gram vinyl cyanide and 2.8 gram Propylene glycol monoacrylates consist of, be controlled in 2-2.5 hour and dropwise, and under constant temperature, continue polyreaction after 1 hour, be reduced to 45 ℃, slowly add by 5 ml waters dissolving, 0.5 gram azo isobutyronitrile solution, slowly drip again after stirring by 5 milliliters of water-soluble 0.5 gram rongalite aqueous solution, add an amount of rear reaction 45 minutes that continues, discharging filters and packages, namely get the compound polyurethane oil polyacrylate latex interpenetrating network material of network I and network II, be designated as LIPN PUO/PA.
The coating of the made emulsion material of present embodiment is utilized the test of the intelligent gloss degree of KGZ-1C instrument, and glossiness is 91%.
Comparative Examples one
66.87 gram polyethers 2000 and 22.27 gram polyethers 3050 are added in 2000 milliliters of reactors with two reinforced drop bottles, stirring, heating and pumped vacuum systems, be heated to 120 ℃ under stirring, keep dewatering in 1.0-1.5 hour at vacuum tightness 750-760mmHg.System temperature is down to 50 ℃, add 39.40 gram isophorone diisocyanates, be heated to 80 ℃ under stirring, keep under the constant temperature making it carry out sufficient condensation reaction in 2 hours, then cool the temperature to 40 ℃, dimethylol propionic acid and 80 milliliters of acetone of adding 21.59 grams, reaction is 3 hours under the reflux temperature, adds 20 milliliters of acetone and continues reaction after 1 hour, viewing system viscosity situation, can add 10～20 milliliters of acetone, stir, stir the lower triethylamines that add 10.41 grams, stir with rotating speed faster, lower deionized water with 458.4 grams adds system at a high speed, carries out high speed dispersion and makes polyurethane aqueous dispersion body as network I.
Weighing 12.8 gram vinylbenzene, 31.6 gram butyl acrylates, 1.05 gram Hydroxyethyl acrylates and 2.0 gram diacrylate binaryglycol esters mix, it is stand-by to add reinforced drop bottle-1, and weighing 0.52 gram sodium bicarbonate and 0.46 gram Potassium Persulphate add reinforced drop bottle-2 after restraining water dissolution with 10.The reactive system of polyurethane aqueous dispersion body network I with above-mentioned 1/3 is heated to 75 ℃, stir lower material with two reinforced drop bottles, add equably reactive system, in 4～6 hours, add, then be incubated again 1 hour, be cooled to 40 ℃, discharging, filtration, packing, namely obtain the LIPN PU/PA emulsion that our early stage research work is prepared, this emulsion is used as hide finishes, in industrialization of calendar year 2001.
The coating of the made emulsion material of present embodiment is utilized the test of the intelligent gloss degree of KGZ-1C instrument, and glossiness is 55%.This sample micelle belongs to nanometer particle, and the median size of practical measurement is 125nm.
Claims (5)
1. polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material, it is characterized in that the median size of this emulsion colloidal is less than 200nm, the topography of this particle is characterized as multiple layer micellar structure, examines as the polyurethane polyureas acrylate graft copolymers, outerly is the hydrophilic polymer of polyurethane oil; Described polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material is made by following steps:
1. prepare alcoholysate (a): with siccative oil or semi-drying oil, low molecular polylol and catalyzer, be heated to 110-130 ℃ under stirring, be evacuated to the 760mmHg dehydration 1-2 hour, and then laid down vacuum, pass into nitrogen protection, be heated to 210-250 ℃, reacted 2-5 hour, tolerance is qualified to surveying, and namely gets " alcoholysate " (a); Described catalyzer is lithium hydroxide or calcium oxide; Described low molecular polylol is glycerine, tetramethylolmethane or TriMethylolPropane(TMP);
2. with following raw materials according synthesis of polyurethane oil solution:
Alcoholysate (a), polyvalent alcohol, diisocyanate monomer, chainextender and thinner; Wherein, described polyvalent alcohol is polyethers
ManyUnit's alcohol or polyester polyol, described polyethers
ManyUnit's alcohol is polyethers 1000, polyethers 2000 or polyethers 3000; Described polyester polyol is polyethylene glycol adipate glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol-glycol ether esterdiol, poly-hexanodioic acid-1,4 butanediol ester glycol, poly-adipate glycol-1,4 butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C ester polyol or the poly-carbonic acid 1 of poly-epsilon-caprolactone glycol, 6-hexylene glycol esterdiol; Described diisocyanate monomer is a kind of in aromatic diisocyanate, aliphatic diisocyanate or the alicyclic diisocyanate or any two or more mixture, and described thinner comprises reactive thinner;
3. carry out ionization with neutralizing agent to 2. going on foot made polyurethane oil solution, make Ionized polyurethane oil solution; Under high-speed stirring, described polyurethane oil Solution Dispersion in deionized water, is made polyurethane oil water dispersion (b);
4. in polyurethane oil water dispersion (b), add hard monomer, vinylformic acid soft monomer and function monomer, initiator and emulsifying agent, carry out free-radical emulsion polymerization in 70～90 ℃, reacted 2-4 hour, system is cooled to 40 ℃ of dischargings, makes the polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material; Described hard monomer is vinylbenzene, methyl methacrylate or vinyl cyanide; Described vinylformic acid soft monomer is butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl or butyl methacrylate; Described function monomer is vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, n-methylolacrylamide, glycidyl acrylate, divinylbenzene, ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate triglycol ester or three triallyl isocyanurates.
2. polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material according to claim 1 is characterized in that described siccative oil and semi-drying oil are tung oil, Chinese catalpa oil, synourin oil, Semen Lini oil, perilla oil, cannabis oil, soya-bean oil, Yatall MA or sunflower seed oil.
3. polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material according to claim 1 is characterized in that described aromatic isocyanate is: tolylene diisocyanate, diphenylmethane diisocyanate component, poly methylene poly phenyl poly isocyanate or xylylene diisocyanate; Described aliphatic diisocyanate is: hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, trimethylammonium hexamethylene diisocyanate; Described alicyclic diisocyanate is: isophorone diisocyanate (IPDI) or hexahydrotoluene vulcabond; Described chainextender is: dimethylol propionic acid, dimethylolpropionic acid or 2,3 dyhydrobutanedioic acids; Described inert diluent is: butanone, acetone, methylethylketone, dioxane or toluene; Described reactive thinner is one or more the mixture in the following monomer: vinylbenzene, methyl methacrylate, vinyl cyanide, alpha-methyl styrene, butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl or butyl methacrylate; Described neutralizing agent is ammoniacal liquor or triethylamine.
4. polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material according to claim 1 is characterized in that described initiator is ammonium persulphate, Potassium Persulphate, Diisopropyl azodicarboxylate, tertbutyl peroxide, benzoyl peroxide or lauroyl peroxide; Described emulsifying agent is nonionic emulsifying agent or anion surfactant; Wherein nonionic emulsifying agent is C
8-C
9Alkyl alcohol Soxylat A 25-7 or C
8-C
9Alkylphenol polyoxyethylene; Anion surfactant is Sodium dodecylbenzene sulfonate, MS-1 or sodium lauryl sulphate.
5. the synthesis technique of polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material according to claim 1 is characterized in that described each raw materials by weight portion is:
Siccative oil or semi-drying oil 2.0～4.0
Low molecular polylol 0.4～1.2
Catalyzer 0.003～0.007
Polyether glycol or polyester polyol 3.0～5.5
Diisocyanate monomer 4.0～6.0
Chainextender 0.5～3.0
Thinner 0～2.0
Neutralizing agent 0.3～0.7
Initiator 0.04～0.6
Buffer reagent 0.04～0.6
Vinylformic acid soft monomer 4.0～8.0
Hard monomer 4.0～8.0
Function monomer 0.15～0.3
Deionized water 65.0～80.0
Emulsifying agent 0～1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010251314 CN101914261B (en) | 2010-08-12 | 2010-08-12 | Polyurethane oil/polyacrylate latex interpenetrating network polymer emulsion material and synthesizing process thereof |
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| CN103483535A (en) * | 2013-08-27 | 2014-01-01 | 苏州博纳化学科技有限公司 | Preparation method of special type self-crosslinking interpenetrating polymer network polyurethane aqueous dispersion |
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