CN100345879C - New type polyurethane/polyacrylic ester latex interpenetrating network polymer emulsion material and its synthesis technology - Google Patents
New type polyurethane/polyacrylic ester latex interpenetrating network polymer emulsion material and its synthesis technology Download PDFInfo
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- CN100345879C CN100345879C CNB2004100124585A CN200410012458A CN100345879C CN 100345879 C CN100345879 C CN 100345879C CN B2004100124585 A CNB2004100124585 A CN B2004100124585A CN 200410012458 A CN200410012458 A CN 200410012458A CN 100345879 C CN100345879 C CN 100345879C
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Abstract
The present invention discloses novel interpenetrating polymer network polymer emulsion materials of polyaminoester / polyacrylate rubber latex. The particle diameter of the emulsion rubber particle is from 30 to 100 nm, the core is polyurethane polyacrylic ester graft copolymers, the secondary outer layer of the core is polyacrylic ester interpenetrating polymer network polymers, and the outermost layer is polyaminoester hydrophilic polymers. In the synthesis technology, interpenetrating polymer network polymer prepolymers with polyacrylic ester [1]/ polyacrylic ester [2] rubber latex are synthesized with the fractional step method; polyurethane carboxyl solutions are synthesized with the traditional method and ionized; the prepolymers are added to the ionized polyurethane solutions under high-speed agitation, diluting agents are further distilled out and recovered, and subsequently, the prepolymers react for 2 hours at 70 to 90 DEG C right along, and are cooled to obtain LIPNPU/PA[1]/PA[2]/PU emulsion materials with multilayer structures. The emulsion is suitable for being used as base materials of leather finishing agents, woodenware lacquer, automobile damping paint, automobile intermediate coating and metal anti-corrosion lacquer.
Description
Technical field
The present invention relates to can be used as the latex interpenetrating net polymer and the synthetic method thereof of hide finishes, wood lacquer, automobile damping paint, automobile inter coat, metal anti-corrosion paint, specifically a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material and synthetic method thereof.
Background technology
About 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 carried out research work (Yao CN85104741 that rears people of LIPN the domestic eighties; CN85104749), mainly concentrate on LIPN PMAA/PBA polystyrene/butyl polyacrylate latex interpenetrating(polymer)networks (LIPNPS/PBA), polymethylmethacrylate/butyl polyacrylate latex interpenetrating(polymer)networks systems such as (LIPNPS/PBA), but majority is in theoretical research stage.Simultaneously we have also carried out the work (1993 the 1st phases of Hebei University of Science and Technology's journal) of this respect in this, and 0 make damping paint and pushed suitability for industrialized production to, are extensive use of in automobile industry, thereby have obtained Hebei province's progress prize in science and technology.In the leading in early days research of having carried out polyurethane/polyacrylate latex interpenetrating net polymer (LIPNPU/PA) the emulsion material nineties, a series of paper (1999 the 2nd phases of Hebei University of Science and Technology's journal have been delivered; 2002 the 1st phases; 2000 the 2nd phases of Hebei academy of sciences journal and the 4th phase; Modern coating and 2002 the 1st phases of application) etc., pushed suitability for industrialized production to as hide finishes.After this research report that many LIPNPU/PA occurred, even my two students have also used our early stage Request For Work patent (CN1355267A).Such as above-mentioned, all belong to the general latex interpenetrating(polymer)networks emulsion of utilizing the two-layer nucleocapsid structure of method of fractional steps preparation, although this interpenetrating net polymer macromolecular chain has separately also reached the blend on the molecular dimension, blend than general macromole state of aggregation improves, but because limited consistency between the different macromole, tightly by the winding of macromolecular chain in the finite depth between two-layer with run through the compatibility problem that can't fundamentally solve between the macromole, particularly for the more special like this interpenetrating(polymer)networks system of polyurethane/polyacrylate (PU/PA), because polyurethane aqueous dispersion body is to utilize the typical solutions polycondensation, form the urethane acetone soln of high-hydrophilic by the dihydroxyl compound chain extension, make its ionization through the tertiary amine neutralization again, last water is forced to disperse and is obtained.Because the high-hydrophilic of this polyurethane aqueous dispersion body, thereby to carry out the polyacrylic acid polyisocyanate polyaddition with it as seed be to synthesize the LIPN PU/PA with anti-phase " nuclear-shell " structure, this just " CN1355267A " proposed, also be we a long time ago research conclusion (1999 the 2nd phases of Hebei University of Science and Technology's journal; 2002 the 1st phases; 2000 the 2nd phases of Hebei academy of sciences journal and the 4th phase and monarch's Xiao Ji Ph D dissertation in 1999).
So-called inverted structure is meant: prepare the synthesising law of latex interpenetrating net polymer by the general method of fractional steps, urethane should be nuclear as network I, and polyacrylic ester should be a shell as network II, and this belongs to positive phase structure; Why the urethane of solution polymerization can be dispersed in the water is by extremely strong wetting ability is arranged self, this wetting ability is much larger than the wetting ability of polyacrylic ester network II, thereby in the forming process of LIPNPU/PA, urethane network I water diffusion to the outside is inevitable, thereby the structure of formation phase reversion never is a fresh problem.But give the original intention of carrying out LIPN PU/PA research originally just because of " inverted structure " problem, particularly " particle design " on the molecular designing basis brought inconvenience, and the desired performance of its research LIPN PU/PA is also had a greatly reduced quality.At first, because polyacrylic ester is enclosed in the centre of micelle as nuclear, thereby this LIPN PU/PA more is that embodiment urethane is wear-resisting, flexible characteristic, ageing-resistant to polyacrylic ester, anti-weather can not effectively be brought into play, not such urethane aromatic urethane not ageing-resistant particularly just, easily xanthochromia can not be controlled effectively, promptly as the such special system of LIPN PU/PA, utilize traditional LIPN synthetic method can not bring into play the specific function of LIPN technology effectively, can not reach more effectively that " CN1355267A " mentioned ... " the PU/PA composite emulsion can overcome their shortcomings separately, makes the most of the advantage " ...Secondly, because the LIPN PU/PA of antiphase nuclei-shell structure only is the winding of certain depth between nuclear/shell, can not well bring into play mutual appearance effect of forcing of traditional LIPN and synergistic effect, thereby consistency can not obtain more effective raising, causes polyurethane/polyacrylate advantage separately not bring into play more fully.The dynamic viscoelasticity spectrum of accompanying drawing-4 (L-7) has illustrated this point.
Summary of the invention
Purpose of the present invention is exactly that a polyurethane/polyacrylate latex interpenetrating network polymer emulsion material and the synthetic method thereof that kind is novel will be provided, to improve the consistency of different polymeric constituents, bring into play the advantage of urethane and each component of polyacrylic ester in the interpenetrating net polymer more fully, material property is further improved.
The present invention is achieved in that a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material, the particle diameter of this emulsion colloidal is 30～100nm, this particle is characterized as approximate concentric multilayer spheric micellar structure in topography, centronucleus is that polyurethane polyureas acrylate graft copolymers, nuclear time skin are that polyacrylate interpenetrating network polymer, outermost layer are the urethane hydrophilic polymer, specifically is expressed as LIPNPU/PA[1]/PA[2]/PU.
The synthetic method of described new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material may further comprise the steps:
(a), utilize hard monomer, soft monomer, function monomer, tensio-active agent, initiator, buffer reagent etc., give aggressiveness (LIPN PA[1]/PA[2]) by synthetic polyacrylic ester [1]/polyacrylic ester [2] the latex interpenetrating net polymer that has of the method for fractional steps;
(b), by polyether glycol, polyester polyol, vulcabond, chainextender, thinner, neutralizing agent be with traditional method synthesis of polyurethane carboxyl solution, and with organic amine it is carried out ionization, makes Ionized polyurethane solution;
(c), under high-speed stirring, with (a) step synthetic LIPN PA[1]/PA[2] give aggressiveness and join in the Ionized polyurethane solution of (b) step gained, carry out high speed dispersion and make it reach the fineness of regulation; And further thinner is steamed and reclaims, continue subsequently system to be cooled to 40 ℃ of dischargings, filtrations, to pack, makes the LIPN PU/PA[1 with multilayered structure 70～90 ℃ of reactions 2 hours]/PA[2]/PU material emulsion material.
The present invention be directed to and utilize traditional latex interpenetrating(polymer)networks synthetic technology, in this special system of LIPN PU/PA, use some drawbacks that occurred, invented a kind of synthetic method of new latex interpenetrating net polymer, latex interpenetrating(polymer)networks synthesis method step by step/synchronously, and utilize this method successfully synthesized " polyurethane/polyacrylate [1] of the multilayer micellar structure of nano-scale/polyacrylic ester [2]/polyurethane rubber latex interpenetrating net polymer (LIPN PU/PA[1]/PA[2]/PU) emulsion material ".PA[1] with PA[2] be respectively polyacrylic acid ester large molecule with different second-order transition temperatures, according to requirement to material property, when carrying out particle design, PA[1] and PA[2] can be respectively hard component polymer and soft component polymkeric substance, also can be respectively soft component polymkeric substance and hard component polymer.Like this, not only the design to latex interpenetrating net polymer material provides more possibility, to the also expansion accordingly of range of application of material.In addition, because having formed the LIPN PU/PA of original two-layer anti-phase mechanism, the proposition of this method has approximate concentric multilayer globosity, the LIPN PU/PA[1 of positive and anti-phase mutual existence]/PA[2]/PU, the centronucleus that is spheroid is the graft copolymer of urethane and polyacrylic ester, inferior skin is the hard component polymer or the soft component polymkeric substance of polyacrylic ester, skin is the soft component polymkeric substance or the hard component polymer of polyacrylic ester once more, outermost layer then is the anti-phase hydrophilic polyurethane that comes out, and sees accompanying drawing-5.Obviously, the polymer billet of such multilayered structure, simultaneously be again that (accompanying drawing-1 and accompanying drawing-2) compared with the micelle with two-layer inverted structure in the nano-scale range, the phase farmland presents significantly reduction, thereby the consistency of polyacrylic ester and urethane is significantly improved.Nature, use properties have also obtained significantly to improve (shown in embodiment and Comparative Examples comparison sheet).
This LIPN PU/PA[1]/PA[2]/particle diameter of PU is 30～100 nanometers, specific embodiment 1 and example 2 samples to the back produce BI-90Plus type laser particle analyzer mensuration with U.S. Bu Luhaiwen company, particle diameter is respectively 61.4 nanometers and 78.1 nanometers, sees accompanying drawing-1 and accompanying drawing-2; From the topography of particle, this micelle has tangible three-decker, sees accompanying drawing-5 (embodiment 1 photo).Figure-5 utilizes the H-600 of Hitachi type transmission electron microscope observing, the particle shape of dyed sample, the photo that the amplification of taking pictures on the basis of observing is 60000 times.
This photo as mentioned above, penetralia mainly is by the formed nuclear of the graft copolymer of polyacrylic ester and urethane; The middle layer is to be hard monomer component and with the excessive layer of the latex interpenetrating net polymer of butyl acrylate soft component with polymethylmethacrylate and Hydroxyethyl acrylate, this one deck is by different glass temperature (being soft monomer/hard monomer) and has different hydrophilic polyacrylic ester and form in the substep interpenetrating(polymer)networks are synthetic, come down to double-layer structure, but because the shooting of this electromicroscopic photograph is to dye by phospho-wolframic acid, obtain with the transmission electron microscope photograph, according to phospho-wolframic acid dyeing transmission electron microscope observing technology, urethane belongs to the material that is colored, thereby be colored and be dark-coloured, and belonging to saturated material, polyacrylic ester is not colored, thereby present transparence, and because P[MMA-HEA]/P[BA] (promptly poly-(methyl methacrylate-ethyl propenoate)/butyl polyacrylate latex interpenetrating(polymer)networks) be not colored simultaneously, be transparence equally, thereby the hard formation in electromicroscopic photograph and soft formation are failed separately.Skin is to cause the formed layer of polyurethane that overturns mutually owing to contain the strongly hydrophilic of a large amount of carboxyls on the polyurethane macromolecular chain naturally.4 layers of structure so in fact, and look it is 3-tier architecture.
The LIPN PU/PA[1 that the present invention makes]/PA[2]/the PU emulsion, natural levelling film forming on flat glass plate then utilizes daily output DDV-II-Ea dynamic viscoelasticity spectrum determinator to measure its dynamic viscoelasticity spectrum figure at normal temperatures, measures frequency: 3.5HZ; Range of measuring temp :-80 to 150 ℃; Heat-up rate: 2 ℃/min.Concrete collection of illustrative plates is seen figure-4.Figure the-4th, the dynamic viscoelasticity spectrum figure of the embodiment 1 of back, embodiment 2 and Comparative Examples 1, i.e. L-8, L-9 and L-7 dynamic viscoelasticity spectrum curve.This sets of curves shows that embodiment 1 and embodiment 2 have higher IPN degree, and the IPN degree of Comparative Examples 1 is lower, and the vitrifying zone of transition is tangible trench.LIPN PU/PA[1]/PA[2]/the PU emulsion, belong to typical latex inierpeneirating network structure, the second-order transition temperature that expression urethane divides about-35 ℃, the second-order transition temperature of expression polyacrylic ester component about 40 ℃, the intermediary trench is is almost filled and led up, and this belongs to latex interpenetrating net polymer characteristic spectrum.
(a) step in synthetic method of the present invention is with the synthetic LIPN PA[1 of the method for fractional steps]/PA[2], promptly in having 2000 milliliters reactor of agitator, reflux exchanger and heating installation, add an amount of water, add the emulsifying agent of specified amount or do not add emulsifying agent, temperature is risen to 60 ℃ add part initiator, buffer reagent, and begin to drip the mix monomer that constitutes by hard monomer, hydroxy component monomer and partial cross-linked monomer, add in 3 hours, be incubated 1 hour again at 60 ℃～85 ℃, finish PA[1] synthetic; Then begin mix monomer and part initiator that parallel dropping is made of soft monomer, a small amount of vinylformic acid and partial cross-linked monomer, dripped in 3 hours, then LIPN PA[1 is promptly finished in 65～85 ℃ of insulations 1 hour again]/PA[2] synthetic, be cooled to 40 ℃, stand-by.
(b) of synthetic method of the present invention step is that the polyvalent alcohol with specified amount adds have agitator, condenser, vacuum system and heating system 2000 milliliters in four-hole bottle, be evacuated to 500～760mmHg under stirring, in 100～110 ℃ of heating 1 hour, it was clean to make it dehydration.System temperature is reduced to 50 ℃ add the certain specification of specified amount and the vulcabond of kind, so react in 70～90 ℃ of scopes, reaction was carried out 1～3 hour.After condensation reaction finishes system temperature is reduced to 50 ℃ of chainextender and proper amount of diluting that add specified amounts, the reaction down 2～3 hours that refluxes is reduced to 40 ℃ with temperature of reaction, adds organic bases and neutralizes to stir with higher speed and make its ionization.
(C) of synthetic method of the present invention step is on the basis of urethane ionized water dispersion, system's rotating speed is transferred to higher speed, with above-mentioned synthetic LIPN PA[1]/PA[2] the aggressiveness that gives join reactor, it is qualified to fineness to carry out high speed dispersion; Further thinner is steamed and reclaims, continue subsequently to make the hydroxy component among its PA fully carry out graft reaction and relevant esterification,, promptly improve its lipophilicity to reduce the wetting ability of polyurethane macromolecular with polyurethane chain 70～90 ℃ of reactions 2 hours.Because improving, its lipophilicity is retained in stratum nucleare to impel; Fail to be able to do in time in this time part of grafting and esterification still is inverted to the skin of PA, thereby forms tangible three-decker or four-layer structure, as accompanying drawing-5.Like this, because in nano level particulate, the phase farmland is very little relatively, consistency increases greatly, and the trend that is separated reduces greatly, can bring into play the effect of interpenetrating(polymer)networks to a greater extent, makes its relevant performance obtain obviously to improve.
The hard monomer of (a) step indication of the inventive method comprises vinylbenzene, methyl methacrylate, vinyl cyanide or alpha-methyl styrene etc.; The soft monomer of indication comprises butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl, butyl methacrylate or tertiary ethylene carbonate etc.; The carboxylic monomer of indication comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, n-methylolacrylamide or glycidyl acrylate etc.; The cross-linking monomer of indication comprises divinylbenzene, ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate triglycol ester or three tricarbimide allyl esters etc.; The emulsifying agent of indication comprises nonionogenic tenside such as alkyl (C
8-C
9) polyoxyethylenated alcohol (10-20 repeating unit) or alkyl (C
8-C
9) phenol polyethenoxy ether (10-20 repeating unit); Anion surfactant such as Sodium dodecylbenzene sulfonate, MS-1 or sodium lauryl sulphate etc.Said initiator is ammonium persulphate, Potassium Persulphate, azo isobutyronitrile, benzoyl peroxide or laurylperoxide acyl etc.; Said buffer reagent is sodium bicarbonate or Sodium phosphate dibasic etc.
The said polyvalent alcohol of (b) step of synthetic method of the present invention comprises polyether glycol, polyester polyol, and polyether glycol comprises polyethers 1000, polyethers 2000 or polyethers 3050 etc.; Polyester polyol comprises 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, the poly-carbonic acid 1 of poly-epsilon-caprolactone glycol, 6-hexylene glycol esterdiol etc.; Said vulcabond comprises aromatic diisocyanate and aliphatic diisocyanate.Aromatic diisocyanate comprises tolylene diisocyanate and two mixture of isomers, ditane-4,4 ' vulcabond, naphthalene-1,5 vulcabond, xylylene diisocyanate etc.; Aliphatic diisocyanate comprises hexamethylene diisocyanate, isophorone diisocyanate etc., Methylcyclohexyl diisocyanate, dicyclohexyl vulcabond or dicyclohexyl methane diisocyanate etc.; Said chainextender comprises dimethylol propionic acid, tartrate, 1,4-butyleneglycol, glycol ether or hexylene glycol etc.; Said thinner comprises hydrophilic organic solvents such as acetone, methylethylketone, dioxane or toluene etc.
Each is former in the synthetic method of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material
Material is by weight:
(1) the polyvalent alcohol monomer 2.5～18 of urethane
(2) diisocyanate monomer 2.5～18 of urethane
(3) chainextender 0.5～2
(4) trimethylamine 0.5～2
(5) acrylic monomer 6～40
(6) function monomer 2～16
(7) tensio-active agent 0.6～2
(8) initiator 0.05～0.5
(9) buffer reagent 0.05～0.5
(10) deionized water 50～80.
Description of drawings:
The particle diameter test result of figure-1 embodiment of the invention 1 sample
The particle diameter test result of figure-2 embodiment of the invention 2 samples
The particle diameter test result of figure-3 Comparative Examples 1 samples of the present invention
The dynamic viscoelasticity spectrum test result of figure-4 embodiment of the invention and comparative example
The transmissioning electric mirror test result of figure-5 embodiment of the invention 1, the micelle that shows sample is a three-decker
Embodiment
The invention will be further described below in conjunction with specific embodiment.Subject area involved in the present invention is not limited only to this two embodiment.
Embodiment 1 (L-8):
It is stand-by that weighing 59.8 gram methyl methacrylates, 6 gram Hydroxyethyl acrylates and 2 gram divinylbenzenes and 0.75 gram Diisopropyl azodicarboxylate mix the reinforced drop bottle-1 of adding; Weighing 0.5 gram sodium bicarbonate is stand-by with the reinforced drop bottle-2 of 95 gram water dissolution addings; The deionized water of 967.5 grams and the OP-10 and 5 MS-1 that restrain of 1 gram are added system in the reactor that has stirring, two reinforced drop bottle (1,2), heating system, stir and be warming up to 65 ℃ of beginnings, begin parallel dropping mix monomer, initiator and damping fluid, dripped off in 3～4 hours 70 ℃ of controls, be incubated half an hour again; 59.8 gram butyl acrylates, 0.5 gram vinylformic acid and the 0.75 gram Diisopropyl azodicarboxylate dissolving that weighs up mixed and and the sodium bicarbonate aqueous solution (0.5 gram sodium bicarbonate restrains water dissolution with 95) of 95 grams 0.5%, add reinforced drop bottle (1,2) respectively and be controlled in 3～4 hours and drip, be incubated half an hour again, then be cooled to 40 ℃, discharging, filtration, packing, promptly to obtain LIPNP (MMA-HEA)/P (BA) water dispersion stand-by.
101.6 gram polyethers 2000 and 67.7 gram polyethers 3050 are added in 2000 milliliters of reactors that have agitator, well heater and a pumped vacuum systems, stir down and be heated to 105 ℃, dewatered in one hour in vacuum tightness 690mmHg maintenance.System temperature is reduced to 50 ℃, add 42.8 gram tolylene diisocyanates, be heated to 80 ℃ under stirring, constant temperature keeps making it carry out sufficient condensation reaction in 2 hours down, then cool the temperature to 40 ℃, add the tartrate and the 120 gram acetone of 13.2 grams, reflux temperature reacted 4 hours down, viewing system viscosity situation, can add 20～40 milliliters of acetone, stir, stir the trolamines that add 10 grams down, stir with rotating speed faster; Then at a high speed down with above-mentioned LIPN P (MMA-HEA)/P (BA) water dispersion, the Ionized polyurethane solution of high speed dispersion; And post-heating steams acetone, and further be heated to 75 ℃ the insulation 2 hours, carry out grafting, esterification and anti-phase, system is cooled to 40 ℃ of dischargings, filtration, packing, thereby make the water dispersion that LIPN PU/P (MMA-HEA)/P (BA)/PU has three layers or four-layer structure.
This emulsion appearance little blue fluorescence that is translucent belongs to nanometer particle, and the practical measurement particle diameter is 64.1nm.(seeing accompanying drawing-1); This sample micelle has three layers or four-layer structure (seeing accompanying drawing-5), this sample belongs to typical latex interpenetrating(polymer)networks dynamic viscoelasticity spectrum collection of illustrative plates, has bigger IPN degree (seeing the L-8 of accompanying drawing-4), this sample can be used as the resin dedicated use of high-grade clothing leather hide finishes, (its specific performance for details see attached table).
Embodiment 2 (L-9):
It is stand-by that weighing 23.22 gram vinylbenzene and 6 gram Hydroxyethyl acrylates and 1.02 gram diacrylate binaryglycol esters mix the reinforced drop bottle-1 of adding; Weighing 0.4 gram Potassium Persulphate and 0.5 gram sodium bicarbonate are stand-by with the reinforced drop bottle-2 of 50 gram water dissolution addings; The deionized water and the 0.5 gram vinylformic acid adding of 1200 grams are had in the reactor of stirring, two reinforced drop bottle (1,2), heating system, stir and be warming up to 65 ℃ of beginnings, begin parallel dropping mix monomer, initiator-buffer agent solution, dripped off in 3～4 hours in 70 ℃ of controls, be incubated half an hour again; With the 60.68 gram butyl acrylates that weigh up, the 50.9 gram aqueous solution that 1.02 gram diacrylate binaryglycol esters mixed also and be dissolved with 0.5 gram sodium bicarbonate, 0.4 gram Potassium Persulphate, add reinforced drop bottle (1,2) respectively and be controlled in 3～4 hours and drip, be incubated half an hour again, then be cooled to 40 ℃, discharging, filtration, packing, promptly to obtain agalasisa LIPN P (St-HEA)/PBA water dispersion stand-by.
125.8 gram polyethers 2000 and 42.84 gram polyethers 3050 are added in 2000 milliliters of reactors that have stirring, heating and a pumped vacuum systems, stir down and be heated to 120 ℃, dewatered in one hour in vacuum tightness 680mmHg maintenance.System temperature is reduced to 50 ℃, add 75.7 gram tolylene diisocyanates, be heated to 78 ℃ under stirring, constant temperature keeps making it carry out sufficient condensation reaction in 2 hours down, then cool the temperature to 40 ℃, tartrate and 140 milliliters of acetone of adding 41.48 grams, reflux temperature reacted 3 hours down, viewing system viscosity situation, can add 20～30 milliliters of acetone, stir, stir the trolamines that add 20 grams down, stir with rotating speed faster; Then at a high speed down with above-mentioned LIPN P (MMA-HEA)/PBA water dispersion, the Ionized polyurethane solution of high speed dispersion; And post-heating steams acetone, and further be heated to 75 ℃ of insulation reaction 2 hours, carry out grafting, esterification and anti-phase, make the water dispersion that LIPN PU/P (MMA-HEA)/PBA/PU has three layers or four-layer structure thereby system is cooled to 40 ℃ of dischargings, filtration, packings.
This emulsion appearance little blue fluorescence that is translucent belongs to nanometer particle, and the practical measurement particle diameter is 78.4nm.(seeing accompanying drawing-2), this sample belong to typical latex interpenetrating(polymer)networks dynamic viscoelasticity spectrum collection of illustrative plates, have bigger IPN degree (seeing the L-9 of accompanying drawing-4), and this sample can be used as the resin dedicated use (specific performance for details see attached table) of high-grade clothing leather hide finishes.
Comparative Examples 1 (L-7): the prescription of embodiment 2 is operated by the synthetic method of traditional latex interpenetrating net polymer.
128.5 gram polyethers 2000 and 42.84 gram polyethers 3050 are added in 2000 milliliters of reactors that have two reinforced drop bottles, stirring, heating and a pumped vacuum systems, stir down and be heated to 120 ℃, maintenance was dewatered in one hour more than vacuum tightness 740mmHg.System temperature is reduced to 50 ℃, add 75.7 gram tolylene diisocyanates, be heated to 80 ℃ under stirring, constant temperature keeps down making it carry out sufficient condensation reaction in 2 hours, then cool the temperature to 40 ℃, dimethylol propionic acid and 140 milliliters of acetone of adding 41.48 grams, reflux temperature reacted 3 hours down, added 20 milliliters of acetone and continued reaction after 1 hour, viewing system viscosity situation, can add 10～20 milliliters of acetone, stir, stir the trolamines that add 20 grams down, stir with rotating speed faster, down with the deionized water adding system of 1200 grams, carry out high speed dispersion and make polyurethane aqueous dispersion body at a high speed as network I.
Weighing 23.22 gram vinylbenzene, 60.68 gram butyl acrylates, 6 gram Hydroxyethyl acrylates mix with, 2.02 gram diacrylate binaryglycol esters that to add reinforced drop bottle-1 stand-by, and weighing 1 gram sodium bicarbonate and 0.8 gram Potassium Persulphate add the drop bottle-2 that feeds in raw material with 100 gram water dissolution.The reactive system of polyurethane aqueous dispersion body network I is added to 75 ℃, stir following material with two reinforced drop bottles, add reactive system equably, in 4～6 hours, add, be incubated 1 hour again, be cooled to 40 ℃, discharging, filtration, packing, promptly obtain the LIPN PU/PA emulsion that we prepare in early days, this emulsion is used as hide finishes, in calendar year 2001 industrialization.But all properties is far less than the performance of embodiment of the invention sample, for details see attached table.
This sample micelle belongs to micro-size particles, and the particle diameter of practical measurement is 157.3nm, and (as figure-3) far exceeded nanoparticle (10～100nm) category.Its IPN degree also can not show a candle to the collection of illustrative plates (seeing the L-7 of accompanying drawing-4) of embodiment 1,2.
Embodiment and Comparative Examples performance index contrast table look-up
Claims (9)
1, a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material, the particle diameter that it is characterized in that this emulsion colloidal is 30～100nm, the topography of this particle is characterized as multilayer micellar structure, nuclear is inferior outer for polyacrylate interpenetrating network polymer, outermost layer are the urethane hydrophilic polymer for polyurethane polyureas acrylate graft copolymers, nuclear, specifically is expressed as LIPN PU/PA[1]/PA[2]/PU.
2, the synthetic method of the described new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material of a kind of claim 1 is characterized in that may further comprise the steps:
(a), utilize hard monomer, soft monomer, function monomer, tensio-active agent, initiator, buffer reagent to give aggressiveness with the synthetic polyacrylic ester [1] of the method for fractional steps/polyacrylic ester [2] latex interpenetrating net polymer;
(b), by polyether glycol, polyester polyol, vulcabond, chainextender, thinner, neutralizing agent be with traditional method synthesis of polyurethane solution, and with organic amine it is carried out ionization, makes Ionized polyurethane solution;
(c), under high-speed stirring, (a) step synthetic polyacrylic ester [1]/polyacrylic ester [2] latex interpenetrating net polymer performed polymer is joined in (b) step gained Ionized polyurethane solution, carry out high speed dispersion; And further thinner is steamed and reclaims, continue subsequently system to be cooled to 40 ℃ of dischargings, filtrations, to pack, makes the latex interpenetrating network polymer emulsion material with multilayered structure 70～90 ℃ of reactions 2 hours.
3, the synthetic method of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material according to claim 2 is characterized in that described hard monomer comprises vinylbenzene, methyl methacrylate, vinyl cyanide or alpha-methyl styrene; Described soft monomer comprises butyl acrylate, ethyl propenoate, vinylformic acid ethylhexyl, butyl methacrylate or tertiary ethylene carbonate; Described function monomer is carboxylic monomer and cross-linking monomer, and wherein carboxylic monomer comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, n-methylolacrylamide or glycidyl acrylate; Cross-linking monomer comprises divinylbenzene, ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate triglycol ester or three triallyl isocyanurates.
4, the synthetic method of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material according to claim 2 is characterized in that described tensio-active agent comprises nonionogenic tenside and anion surfactant.
5, the synthetic method of new polyurethane according to claim 4 and polyacrylate latex interpenetrating network polymer emulsion material is characterized in that described ionic surfactant pack draws together the alkyl (C that repeating unit is 10-20
8-C
9) polyoxyethylenated alcohol) or repeating unit be the alkyl (C of 10-20
8-C
9) phenol polyethenoxy ether.
6, the synthetic method of new polyurethane according to claim 4 and polyacrylate latex interpenetrating network polymer emulsion material is characterized in that described anion surfactant comprises Sodium dodecylbenzene sulfonate, MS-1 or sodium lauryl sulphate.
7, the synthetic method of a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material according to claim 2 is characterized in that described initiator comprises ammonium persulphate, Potassium Persulphate, azo isobutyronitrile, benzoyl peroxide or laurylperoxide acyl.
8, the synthetic method of a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material according to claim 2 is characterized in that described polyether glycol comprises polyethers 1000, polyethers 2000 or polyethers 3050; Described polyester polyol comprises 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 vulcabond comprises tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditane-4,4 ' vulcabond, xylylene diisocyanate, naphthalene-1,5 vulcabond, Methylcyclohexyl diisocyanate, dicyclohexyl vulcabond or dicyclohexyl methane diisocyanate; Described chainextender comprises dimethylol propionic acid, tartrate, 1,4-butyleneglycol, glycol ether or hexylene glycol; Said thinner comprises acetone, methylethylketone, dioxane or toluene.
9, the synthetic method of a kind of new polyurethane/polyacrylate latex interpenetrating network polymer emulsion material according to claim 2 is characterized in that each raw materials by weight portion is:
(1) the polyvalent alcohol monomer 2.5～18 of urethane
(2) diisocyanate monomer 2.5～18 of urethane
(3) chainextender 0.5～2
(4) trimethylamine 0.5～2
(5) acrylic monomer 6～40
(6) function monomer 2～16
(7) tensio-active agent 0.6～2
(8) initiator 0.05～0.5
(9) buffer reagent 0.05～0.5
(10) deionized water 50～80.
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|---|---|---|---|---|
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| CN109734846B (en) * | 2019-01-23 | 2020-07-17 | 长春工业大学 | Core-shell type waterborne polyurethane/acrylate composite emulsion, preparation method thereof and damping coating |
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| CN113956824B (en) * | 2021-10-19 | 2022-10-25 | 安徽匠星联创新材料科技有限公司 | Reactive full-solid-content cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302553A (en) * | 1970-10-30 | 1981-11-24 | Harry L. Frisch | Interpenetrating polymeric networks |
| CN1065468A (en) * | 1991-02-28 | 1992-10-21 | 纳幕尔杜邦公司 | Can be scattered in the interpenetrating polymer networks of solvent |
| CN1277625A (en) * | 1997-10-24 | 2000-12-20 | 美国3M公司 | Enhanced dye durability through controlled dye environment |
| WO2002000429A1 (en) * | 2000-06-21 | 2002-01-03 | Agrolinz Melamin Gmbh | Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties |
| CN1355267A (en) * | 2001-12-24 | 2002-06-26 | 王申 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
| CN1400270A (en) * | 2002-07-22 | 2003-03-05 | 浙江大学 | Interpenetrating polymer networks wide temperature band damping adhesive and its preparation method |
-
2004
- 2004-08-03 CN CNB2004100124585A patent/CN100345879C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302553A (en) * | 1970-10-30 | 1981-11-24 | Harry L. Frisch | Interpenetrating polymeric networks |
| CN1065468A (en) * | 1991-02-28 | 1992-10-21 | 纳幕尔杜邦公司 | Can be scattered in the interpenetrating polymer networks of solvent |
| CN1277625A (en) * | 1997-10-24 | 2000-12-20 | 美国3M公司 | Enhanced dye durability through controlled dye environment |
| WO2002000429A1 (en) * | 2000-06-21 | 2002-01-03 | Agrolinz Melamin Gmbh | Fibre composites with excellent dimensional stability, weather resistance and flameproofing properties |
| CN1355267A (en) * | 2001-12-24 | 2002-06-26 | 王申 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
| CN1400270A (en) * | 2002-07-22 | 2003-03-05 | 浙江大学 | Interpenetrating polymer networks wide temperature band damping adhesive and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 离子型聚氨酯聚丙烯酸酯胶乳互穿聚合物网络 陈家华等，中国皮革，第28卷第5期 1999 * |
| 聚氨酯/聚丙烯酸酯复合乳液的研制进展 侯青顺 等，化工进展，第21卷第11期 2002 * |
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