CN101481443A - Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof - Google Patents
Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof Download PDFInfo
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Abstract
The invention relates to a polyurethane-polyacrylic ester interpenetrating network polymer and a preparation method and the application thereof. The following steps are comprised: self-emulsifying anionic polyurethane water dispersoid containing carbon-carbon double bonds are synthesized through a step addition polymerization method; the synthesized polyurethane water dispersoid is used as seeding emulsion and polymer surface active agent; in-situ emulsion polymerization is carried out on acrylic ester monomer in an emulsification system by using dropwise adding evocating agents, so that the pre-emulsifying acrylic monomers in the system can be polymerized and (or) cross-linked on the inner part and the surface of seeding emulsion particles, and then the polyurethane-polyacrylic ester interpenetrating network polymer emulsion can be obtained; after dried, emulsion powder which has good water resisting property and cohesiveness when re-dispersed in water is obtained; the polyurethane-polyacrylic ester interpenetrating network polymer not only can be used with inorganic cementing materials such as cement, white lime or plaster for manufacturing overcoating mortar, pointing-joint agents, plastering agents and building bonding agents, but also can be independently used as film forming binder for preparing dry powder emulsion coating.
Description
Technical field
The present invention relates to redispersible polymer and preparation method thereof, more particularly, relate to a kind of redispersible polyurethane-polyacrylate interpenetrating net polymer and its production and application.
Background technology
The redispersible polymer latex powder has been widely used in multiple fields such as powder coating, tackiness agent, material of construction.At building materials field, as extraordinary fields such as external insulating mortar, ceramic tile tackiness agent, putty, gravity flowing levelling mortar, concrete repair, thin layer bonding/mending mortar, plastering mortars, all use the redispersible polymer latex powder, to improve the performance of above-mentioned material of construction, as can improve the multiple performance of mortar by interpolation redispersible polymer emulsion powder in cement based or gypsum base dry-mixed mortar, as the cohesive force that improves material, the water-absorbent that reduces material, folding strength, impact-resistance, wear resistance and the weather resistance of strongthener.It is worth noting especially, adopt the redispersible polymer latex powder, be expected to make novel wall surface material real zero VOC, that performance is suitable with traditional latex coating performance.The production of this novel wall surface material will bring revolutionary variation to Architectural Paint in China, fundamentally changes the unfavorable situation of VOC harmful to human and environment in the latex coating, and economic benefit and social benefit will be very remarkable, have broad application prospects.
About the research of redispersable latex powder, mainly concentrate on Germany, France,, the major company of advanced technology country such as U.S., Japan.Nineteen fifty-seven, Germany's watt gram (Wacker) chemical company takes the lead in developing first-generation vinyl acetate between to for plastic type homopolymer latex powder, has released the vinyl acetate-ethylene copolymer latex powder subsequently again, thereby has begun the research and the production of redispersible polymer latex powder.At that time, redispersable latex powder also was mainly the polyvinyl acetate (PVA) type, and being mainly used in wood glue, metope priming paint and cement is wall material etc.But because the limitation of the performances such as redispersible, minimum film-forming temperature, water tolerance and alkali resistance of redispersable latex powder, its use has been subjected to bigger restriction.Up to the sixties in 20th century, minimum film-forming temperature is 0 ℃, have better water tolerance and alkali-proof redispersable latex powder to be developed after, its use is just extensively got up, and the scope of use also expands to various structures and non-structural construction tackiness agent, dry-mixed mortar modification, wall thermal insulating and facing system, body of wall levelling glue and fields such as sealing emplaster, powder coating and building putties.At present, the bigger redispersable latex powder manufacturer in the world mainly contains Hoechst company, Wacker chemical company, the Rhodia company of France, the National Starch company of the U.S. and the Shanxi three-dimensional chemical industry group company of Air Products company and China of Germany.The product of these companies mainly is the redispersable latex powder of polyethylene vinyl acetate ester class.
Prior art generally believes that the preparation principle of redispersable latex powder is: add protective colloid after the polymeric matrix emulsification, become free flowable power-product through spraying drying.Take a broad view of patent documentation; the preparation principle of the redispersable latex powder of people's proposition at present can not be expressed the preparation process of redispersable latex powder fully; be Special attention will be given in the redispersable latex powder preparation process; the back adds the importance of protective colloid, has ignored the importance of emulsion self performance.For example, what polyethylene vinyl acetate ester latex powder, the US4859751 that patent CN1903894A, CN101125946A, CN101121768A, US6716941, US5118751 relate to related to is polyethylene-vinyl chloride-base polymer latex powder, or the like.People study the more good acrylic polymer redispersion latex powder of over-all properties gradually subsequently.For example patent US 6706805 has invented polyethylene vinyl acetate ester-acrylate copolymer latex powder, patent US 5403894, CN 101173021A etc. have related to the technology of preparing of the polyacrylic ester latex powder with nucleocapsid structure, patent CN 1903898A, US 7183358 adopt siloxanes that acrylic polymer has been carried out modification matter, have further improved the performance of emulsion polymer.Above-mentioned research has greatly improved the performance of emulsion polymer self.But; because these redispersible polymer latex powder have adopted a large amount of tensio-active agents when emulsion is synthetic; and when drying, all adopt water miscible polyvinyl alcohol as protective colloid; thereby the gained rubber powder contains polyvinyl alcohol and at least a tensio-active agent; thereby poor water resistance, cohesive strength has much room for improvement.
In a word, from at present domestic and international reality, redispersible polymer latex powder product is more single, the product of homogeneity is many, aspects such as bond performance behind water remain in the improved place of many needs product in water tolerance and redispersion, can't be used for the good dry powder latex paint of processability as the film forming binding substances separately.The preparation synthetic and latex powder that can be used for the high performance polyurethane-polyacrylate interpenetrating network polymer emulsion of dry powder latex paint does not at home and abroad appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of redispersible polyurethane-polyacrylate interpenetrating net polymer is provided, the excellent flexibility, sticking power and the adhesive property that had both had urethane on its performance, have the good weathering resistance and the water tolerance of acrylic ester polymer again, thereby can be used as the film forming binding substances of dry powder latex paint.
The present invention also aims to provide the preparation method of polyurethane-polyacrylate interpenetrating net polymer.
The present invention also aims to provide the application of described polyurethane-polyacrylate interpenetrating net polymer in preparation coating.
The preparation method of polyurethane-polyacrylate interpenetrating net polymer of the present invention comprises:
---with polyisocyanates, polyether glycol, small molecule chain extender, wetting ability chainextender, the functional monomer that contains active function groups and carbon-to-carbon double bond, neutralizing agent, acrylic ester monomer is main raw material, at first by the synthetic self-emulsifying anionic polyurethane water dispersion that contains carbon-to-carbon double bond of progressively addition polymerization method;
---with the synthetic polyurethane aqueous dispersion body as seed emulsion and polymer type surface promoting agent, acrylic ester monomer in the emulsification system, thereby under the condition of not adding any tensio-active agent, by adopting the method that initiator carries out in-situ emulsion polymerization that drips, make pre-emulsified Acrylic Acid Monomer in the system carry out on the inside of seed emulsion particle and surface polymerization and (or) crosslinked, thereby prepared aqueous polyurethane-poly acrylate composite emulsion with nucleocapsid structure and interpenetrating net polymer (IPN) structure.
Specifically may further comprise the steps:
(1) preparation of prepolymer: polyisocyanates (TDI) and polyether glycol are added in the reaction vessel, after reacting 1～2 hour under 60～65 ℃, add wetting ability chainextender and N-methyl-2-pyrrolidone, be warmed up to 75～85 ℃ of reactions 0.5～1.5 hour, add small molecule chain extender and carried out chain extending reaction 1～2 hour, further improve the molecular weight of prepolymer at 65～75 ℃;
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: add the functional monomer that contains active function groups and carbon-to-carbon double bond in step (1) the synthetic product, NCO group and the 0H base in the functional monomer structure residual in the polyurethane prepolymer carried out polyaddition reaction 1.5～2.5 hours, make the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond; Add acrylic ester monomer, solution system is mixed;
(3) neutralization of prepolymer and emulsification: the polyurethane prepolymer that step (2) is obtained cools to 30～50 ℃, adds neutralizing agent, mixes, and obtains intermediate; Then deionized water is joined in the intermediate fast, stir, make the solution system Phase inversion emulsification, thereby obtain containing the polyether polyols with reduced unsaturation water dispersion of acrylic ester monomer;
(4) in-situ emulsion polymerization: the temperature to 60 of the system that raises gradually～70 ℃, begin to drip the acetone soln 1～2 hour that is dissolved with initiator, insulation reaction is 2～4 hours then, transformation efficiency reaches 98% when above, stopped reaction and cooling, discharging, filters, obtains urethane-acrylate interpenetrating network polymer emulsion;
The weight percent of above-mentioned raw materials is composed as follows:
Polyisocyanates 5～15%
Polyether glycol 4～15%
Small molecule chain extender 1～5%
Wetting ability chainextender 0.77～2.25%
The functional monomer 0.1～1% that contains active function groups and carbon-to-carbon double bond
Acrylic ester monomer 10.1～50.3%
Neutralizing agent 0.56～1.7%
Initiator 0.13～0.5%
Acetone 1～10%
N-methyl-2-pyrrolidone 0.2～1.5%
Deionized water 40～50%.
Described polyisocyanates can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate aromatic diisocyanates such as (MDI), and isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (H
12MDI) aliphatics, cycloaliphatic diisocyanates such as.Tolylene diisocyanate (TDI) has two kinds of isomer: 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.Polyisocyanates is the basis of synthetic styrene-acrylic polymkeric substance composite emulsion, the NCO base that it provides can play progressively polyaddition reaction with the compound (as polyether glycol, small molecule chain extender, dimethylol propionic acid, glycidyl methacrylate etc.) of hydroxyl or amino, thereby generates needed polymkeric substance.The preferred TDI of the present invention (mass ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate is 80/20) is the raw material of synthesis of polyurethane-polyacrylate interpenetrating network polymer emulsion.
Described polyether glycol can be polyether glycol, polyether triol; Preferred polyoxypropyleneglycol (PPG), PTMG are with filming of obtaining that snappiness is good, have excellent water-resistance.The consumption of control polyether glycol can be controlled in the polyurethane molecular structure performance of ratio to obtain to expect of hard section and soft section to a certain extent.
Described small molecule chain extender can be 1,4-butyleneglycol (BDO), ethylene glycol ,-chainextender such as diglycol ethylene, TriMethylolPropane(TMP) (TMP), hexylene glycol, quadrol, diethylenetriamine.Behind these small-molecule substances and the isocyanate reaction, can improve the content of hard section in the polyurethane structural, thereby improve the hardness and the wear resisting property of filming.Preferred 1, the 4-butyleneglycol of the present invention (BDO) small molecule chain extender.
Described wetting ability chainextender is the chainextender that can introduce hydrophilic radical.This class chainextender can be carboxyl type chainextender or sulfonate type chainextender.The carboxylic acid type chainextender can be dimethylol propionic acid (TMPA), dihydroxyl half ester, diaminobenzoic acid etc.The sulfonic acid type chainextender can be quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof etc.Preferred dimethylol propionic acid (TMPA) is as the hydrophilic monomer of synthetic usefulness, contain TMPA segmental polyether polyols with reduced unsaturation and have the self-emulsifying characteristic, it can be used as the polymer type surface promoting agent, under the condition of not adding any tensio-active agent, emulsion acrylic class monomer can obtain good emulsion stability, the preferable polymkeric substance composite emulsion of water-resistance property of coating.
The described functional monomer that contains active function groups and carbon-to-carbon double bond comprises functionalized acrylate and functionalized allyl group and vinyl ether, the monomer that particularly contains epoxide group, as glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, propyl glycidyl ether, or contain the monomer of hydroxyalkyl, as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate etc.These functional monomers both contain can with isocyanic ester-hydroxyl or the epoxy group(ing) of NCO radical reaction, also contain the carbon-to-carbon double bond that can carry out free-radical emulsion polymerization with acrylic ester monomer, therefore, the adding of these functional monomers is the bases that form interpenetrating polymer networks in latex particle, the performance of emulsion polymer, as water tolerance, acid-proof alkaline etc., also therefore be improved.The present invention preferentially selects glycidyl methacrylate as functional monomer.
Described neutralizing agent can be the inorganic and organic bases that sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine etc. can play neutralization reaction with the carboxyl (COOH) in the polymer molecular structure.In theory, the salifiable organic or inorganic alkaline matter of every energy and COOH group can both be made neutralizing agent, but in fact, the neutralizing effect that different alkaline matters plays is discrepant.When making neutralizing agent with NaOH, emulsion particle should be minimum, obtains stable emulsion; Use NH
4When making neutralizing agent, emulsion particle diameter is bigger, and variable color is very serious when neutralization and storage; With all better, uniform and stable in the tertiary amine with outward appearance.It is bigger that yet the product film forming water tolerance that NaOH, KOH neutralization obtains descends, and this may be the Na that exists in the glued membrane
+And K
+Ion, this helps entering of water; And organic cation has exhausted in the drying varniss process.So the preferred triethylamine of the present invention (TEA) is as neutralizing agent, and degree of neutralization is advisable 90～100%.
Described acrylic ester monomer comprises one or more the combination in nearly all acrylate monomer that can carry out radical addition polymerization reaction such as methyl methacrylate, vinylbenzene, butyl acrylate.Can be ethyl propenoate (EA), butyl acrylate (BA), Isooctyl acrylate monomer soft monomers such as (EHA); Can be methyl methacrylate (MMA), vinylbenzene (St), vinyl cyanide (AN), vinyl acetate hard monomers such as (VAC); Can be vinylformic acid (AA), methacrylic acid hydrophilic monomers such as (MAA); Can be Hydroxyethyl acrylate (HEA), Propylene glycol monoacrylate (HPA) etc. contains the function monomer of hydroxyl.The preferred St of the present invention is as hard monomer, the force of cohesion and the hardness of filming with raising; Preferred BA is as soft monomer, giving the glued membrane snappiness, and improves sticking power; Preferred AA is as hydrophilic monomer, to improve the stability of composite emulsion system.By the relative consumption of control BA and St, can adjust the glass transition temperature Tg of polymkeric substance, to obtain to have filming of different hardness and mechanical property.The hardness of latex film and tensile strength all increase along with the increase of BA/St ratio, and elongation at break reduces along with the increase of BA/St ratio.The comonomer BA and the St that introduce are hydrophobic monomer, and therefore along with the increasing of amount of monomer, the glued membrane water tolerance can strengthen.Wherein St is a hard monomer, and its consumption increase can cause the tensile strength of film to increase, and the increase of BA consumption, can improve the snappiness and the elongation of glued membrane.The monomeric main effect of vinylformic acid (AA) is the stability that improves emulsion system, can increase the water sensitivity of filming but its consumption is too high.Take all factors into consideration various factors, the present invention preferentially selects acrylic ester monomer and consumption thereof as follows
Vinylbenzene (St) 5～30%
Butyl acrylate (BA) 5～20%
Vinylformic acid (AA) 0.1～0.3%.
Described initiator can be azo-initiator such as Diisopropyl azodicarboxylate (AIBN), organic peroxy class initiator such as dibenzoyl peroxide (BPO), inorganic peroxy class initiator such as Potassium Persulphate K
2S
2O
8And ammonium persulphate (NH
4)
2S
2O
8, oxidation-reduction initiator such as hydrogen peroxide and S-WAT etc.The preferred AIBN of the present invention is the initiator that acrylic ester monomer carries out seeded emulsion polymerization, can obtain stable better, the good polymer emulsion system of film performance.
In building-up process, need to add certain amount of organic solvent to reduce the viscosity of system.Organic solvent can be acetone, methylethylketone, vinyl acetic monomer, N-BUTYL ACETATE, N, N-dimethyl formamide, N-methyl-2-pyrrolidone etc.It is helpful to the stability and the film forming homogeneity that improve product to add a spot of high boiling solvent such as butyl glycol ether, isooctyl acetate, N-methyl-2-pyrrolidone etc.So mixed solvent of the preferred lower boiling acetone of the present invention and high boiling solvent such as N-methyl-2-pyrrolidone etc.
For the ease of using, can select suitable protective colloid and inorganic mineral separant, the synthetic composite emulsion is carried out drying, thereby make polymkeric substance fine-powder uniform particle diameter, that have excellent fluidity, the weight percent of raw material is composed as follows:
Polyurethane-polyacrylate interpenetrating network polymer emulsion 80～95%
Protective colloid 2～15%
Inorganic mineral separant 2～10%
Described protective colloid can be polyvinyl alcohol (PVA) and derivative, silicon sol etc., especially polyvinyl alcohol material.In order to improve the cohesive strength behind the latex powder redispersion and the wear resistance of film, the protective colloid when the present invention selects the amido functional group polyvinyl alcohol to be the polymer emulsion spraying drying.Be dissolvable in water the amido functional group polyvinyl alcohol in the cold water, its saponification value is 0～250, and solid content is 30～50%, and comprising formula is CH=CH-(CH
2) x-NH
2The amido functional group ethylene unit, wherein, x=0～4.It prepares (patent is not described its application in the preparation of redispersion latex powder) by the disclosed method of patent US5155167.Do not compare with adding the prepared latex powder of PVA with the latex powder that obtains after the pre-treatment of amido functional group polyvinyl alcohol, outward appearance is better, and particle diameter is less, distributes also relatively evenly.The preferred amido functional group polyvinyl alcohol of the present invention (calculating) with 40% solid content.
Described inorganic mineral separant can be lime carbonate, barium sulfate, talcum powder, kaolin, pure aluminium silicate, diatomite, silicon-dioxide etc.These separants can improve polymer powder during spraying drying and dried anti-caking performance.Its granularity can be in 10 nanometers to 5 micron, are preferably between 20 nanometers to 1 micron.The preferred light calcium carbonate of the present invention is as the inorganic mineral separant.
Drying may further comprise the steps:
(1) pre-treatment of emulsion before dry: protective colloid and inorganic mineral separant are joined in the synthetic polymer emulsion system, are to stir 40～60 minutes under 100～300 rev/mins the condition at rotating speed, make the emulsion system uniformity.The solid content of pre-treatment post polymerization thing emulsion system is 20～70%, and preferred 30～60% emulsion is carried out spraying drying.
(2) drying: pretreated polymer emulsion can make redispersable latex powder by fluidised bed drying, lyophilize or spraying drying.The present invention preferentially adopts spraying drying.The atomizing of emulsion can be carried out by means of single fluid, two-fluid or multithread body nozzle in the spray drying unit of routine during spraying drying, also can adopt rotating disk to atomize.The present invention adopts rotating disk to atomize.Second-order transition temperature (Tg) and desired rate of drying according to described spray drying unit, polymkeric substance are determined drying temperature.It often is 45 ℃～120 ℃ that the present invention selects the spraying drying temperature out, preferred 60 ℃～90 ℃.
The mechanism that the present invention prepares urethane～acrylate interpenetrating net polymer latex powder is: the NCO base that (1) polyisocyanates TDI provides can play progressively polyaddition reaction with the compound (as polyether glycol, small molecule chain extender, dimethylol propionic acid etc.) of hydroxyl or amino, thereby generates needed polyurethane prepolymer.(2) functional monomer that adopts of the present invention both contained can with isocyanic ester-hydroxyl or the epoxy group(ing) of NCO radical reaction, also contain the carbon-to-carbon double bond that can carry out free-radical emulsion polymerization with acrylic ester monomer, therefore, can in latex particle, form interpenetrating polymer networks, make the interpenetrating net polymer of polyurethane-acrylate.(3) be hydrophilic monomer with dimethylol propionic acid (TMPA), synthetic contains TMPA segmental polyurethane dispersions and has the self-emulsifying characteristic, it can be used as the polymer type surface promoting agent, under the condition of not adding any tensio-active agent, and emulsion acrylic class monomer.(4) under action of evocating, pre-emulsified acrylate monomer can be seed emulsion with the polyurethane dispersions that forms in the system in the system, carry out in-situ emulsion polymerization, thereby prepared aqueous polyurethane-acrylate latex particle with nucleocapsid structure or interpenetrating polymer networks (IPN) structure.(5) the present invention adopts aqueous polyurethane dispersion as acrylic ester polymerization and stable polymer type emulsifying agent; not only under the condition of not adding any tensio-active agent, realized the emulsification of acrylic ester monomer; improved the water tolerance of polymer powder effectively; and since in the polyurethane molecular hydrophilic group be arranged in the periphery of latex particle; and with amido functional group polyvinyl alcohol protective colloid of the present invention hydrogen bond association is arranged, thereby can promote atomizing and the dispersion of latex particle when spraying drying effectively.(6) the water-based polyurethane polymer type emulsifying agent and the amido functional group polyvinyl alcohol protective colloid of the present invention's employing not only can satisfy the purpose of polymer powder in being scattered in water, and have good water tolerance and cohesive strength.
Polyurethane-acrylate interpenetrating net polymer latex powder solid content of the present invention is greater than 99%, and size of particles is more even, and particle diameter is 0.2～20 μ m, and 500 μ m screeningss are no more than 2%, have good flowability.In the constructing operation process, polymer emulsion powder has the splendid performance of mixing and stirring, almost can be wetted immediately; Application property there is not any negative impact; During sclerosis and other additive matching effect good, water-intake rate is low.
In addition, in the product of the present invention, total volatile organic compound (VOC) can not detect, and is a kind of real zero VOC material; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Do not contain formaldehyde; Skin, respiratory tract to the people are non-stimulated, belong to environmentally friendly product.
The present invention compared with prior art has following advantage and effect:
(1) polymkeric substance of the present invention has the self-emulsifying characteristic, can be used as the polymer type surface promoting agent, emulsion acrylic class monomer.
(2) be seed emulsion with synthetic urethane-acrylate water dispersion, under the condition of not adding any tensio-active agent, by adopting emulsion polymerization in situ, synthesized aqueous polyurethane-acrylate composite emulsion particle with nucleocapsid structure or interpenetrating polymer networks (IPN) structure.
(3) the present invention adopts aqueous polyurethane dispersion as acrylic ester polymerization and stable polymer type emulsifying agent; because hydrophilic group is arranged in the periphery of latex particle in the polyurethane molecular; and with amido functional group polyvinyl alcohol protective colloid of the present invention hydrogen bond association is arranged, thereby can promote atomizing and the dispersion of latex particle when spraying drying effectively.
(4) polymer emulsion powder of the present invention has good water tolerance and the cohesiveness of redispersion behind water, not only can together make and be used for making facing mortar, jointing agent, plaster material and building adhesive, and can be used for the good dry powder latex paint of processability as the film forming binding substances separately with cement inorganic material such as cement, white lime, water glass or gypsum.
Embodiment
Embodiment 1
1. emulsion is synthetic
The weight of polyurethane-polyacrylate interpenetrating network polymer emulsion of the present invention (100 kilograms of total amounts) composed as follows:
10 kilograms of tolylene diisocyanates (TDI)
9 kilograms of polyoxypropyleneglycols (PPG)
3 kilograms of 1,4-butyleneglycols (BDO)
0.8 kilogram of dimethylol propionic acid (TMPA)
0.1 kilogram of glycidyl methacrylate
18.0 kilograms of vinylbenzene (St)
5.0 kilograms of butyl acrylates (BA)
0.1 kilogram in vinylformic acid (AA)
0.6 kilogram of triethylamine (TEA)
0.502 kilogram of Diisopropyl azodicarboxylate (AIBN)
10 kilograms in acetone
1.3 kilograms of N-methyl-2-pyrrolidones
41.6 kilograms in water
Synthesis step is:
(1) preparation of prepolymer: according to above-mentioned prescription, 9 kilograms of polyether Glycols PPG of 10 kilograms of TDI and dehydration are joined in the reactor of 200L, be to stir material and be warmed up to 65 ℃ gradually under 300 rev/mins the situation at rotating speed, keep reaction after 1.5 hours, add hydrophilic chain extender DMPA and the N-methyl-2-pyrrolidone that measures by the prescription that designs, be warmed up to 80 ℃ of reactions 1.2 hours, continue to add small molecule chain extender BDO, carry out chain extending reaction 1.5 hours at 70 ℃, improve the molecular weight of prepolymer.
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in the product of step (1), add 0.1 kilogram of functional monomer containing active function groups and carbon-to-carbon double bond, residual NCO group and the OH base in the functional monomer structure carry out polyaddition reaction in the polyurethane prepolymer.The viscosity that adds 8 kilograms of acetone (staying 4 kilograms of acetone) reduction system with the dissolving initiator.Reacted 1.5～2.5 hours, and made the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond.According to prescription, add 18 kilograms of vinylbenzene (St), 5.0 kilograms of butyl acrylates (BA) and 0.1 kilogram of vinylformic acid (AA), and solution system is mixed.Add other all acrylic ester monomers, and solution system is mixed.
(3) neutralization of prepolymer and emulsification: the prepolymer that step (2) generates is lowered the temperature, when temperature reaches 40 ℃, add 0.6 kilogram of neutralizing agent triethylamine (TEA), mix under 600 rev/mins the rotating speed simultaneously, join 41.6 kilograms of deionized waters in the prepolymer fast then, sheared 5 minutes with 1500 rev/mins rotating speed high-speed stirring simultaneously, make the solution system Phase inversion emulsification, thereby obtain containing the polyurethane aqueous dispersion body of acrylic ester monomer.
(4) in-situ emulsion polymerization: the temperature to 70 of the system that raises gradually ℃ begins to drip acetone (2 kilograms) solution that is dissolved with 0.502 kilogram of initiator A IBN; The control rate of addition makes the dropping time of initiator be about 1 hour.After initiator is added dropwise to complete, make architecture heat preservation reaction 4 hours.Measure transformation efficiency and reach 98% when above, stopped reaction also cools to 40 ℃, and discharging, filtration, packing promptly obtain aqueous polyurethane-acrylate interpenetrating net polymer composite emulsion.
Aqueous polyurethane-acrylate the interpenetrating network polymer emulsion that makes with above-mentioned prescription and technology was placed 7 days in the condition of 50 ℃ of constant temperature, do not have corruption, not stratified, do not lump, have good preservation stability.
2. dry
(1) pre-treatment of dry preceding emulsion: according to the formula rate that designs in advance; 15 kilograms of the amido functional group polyvinyl alcohol and the machine mineral separant light calcium carbonate of protective colloid 40% solid content are joined in 80 kilograms of synthetic polymer emulsion systems for 5 kilograms; be to stir 60 minutes under 100 rev/mins the condition at rotating speed, make the mixed system uniformity.
(2) drying: treated mixed emulsion system joined by the feed rate of 5 kg/minute carry out spraying drying in the equipment, dry temperature out often is 60 ℃.
The polyurethane-acrylate interpenetrating net polymer latex powder solid content that drying obtains is greater than 99%, and size of particles is more even, and median size is 10 μ m, and 300 μ m screeningss are no more than 2%, have good flowability.The total volatile organic compound of product (VOC) can not detect; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Skin, respiratory tract to the people are non-stimulated.Latex powder and cement and other inorganic color stuffing etc. of gained are prepared the tile pointing agent together, have good construction performance and cohesive strength.Check after 6 months that the ceramic tile bonding is good, jointing place is complete, does not have to come off and metachromatism.
Embodiment 2
1. emulsion is synthetic
The starting material and the consumption of synthetic water based polyurethane-polyacrylate interpenetrating network polymer emulsion following (100 kilograms of total amounts):
5.0 kilograms of tolylene diisocyanates (TDI)
4.0 kilograms of polyoxypropyleneglycols (PPG)
1.0 kilograms of 1,4-butyleneglycols (BDO)
0.77 kilogram of dimethylol propionic acid (TMPA)
0.3 kilogram of glycidyl methacrylate
30.0 kilograms of vinylbenzene (St)
10.0 kilograms of butyl acrylates (BA)
0.2 kilogram in vinylformic acid (AA)
0.555 kilogram of triethylamine (TEA)
0.322 kilogram of Diisopropyl azodicarboxylate (AIBN)
3.4 kilograms in acetone
0.6 kilogram of N-methyl-2-pyrrolidone
43.9 kilograms in water
Synthesis step is:
(1) preparation of prepolymer: according to above-mentioned prescription, 4 kilograms of polyether Glycols PPG of 5.0 kilograms of TDI and dehydration are joined in the reactor of 200L, be to stir material and be warmed up to 60 ℃ gradually under 30 rev/mins the situation at rotating speed, keep reaction after 1.5 hours, add hydrophilic chain extender DMPA and the N-methyl-2-pyrrolidone that measures by the prescription that designs, be warmed up to 80 ℃ of reactions 1 hour, continue to add small molecule chain extender BDO, carry out chain extending reaction 1.5 hours at 80 ℃, improve the molecular weight of prepolymer.
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in the product of step (1), add 0.3 kilogram of functional monomer containing active function groups and carbon-to-carbon double bond, residual NCO group and the OH base in the functional monomer structure carry out polyaddition reaction in the polyurethane prepolymer.The viscosity that adds 2 kilograms of acetone (staying 1.4 kilograms of acetone) reduction system with the dissolving initiator.Reacted 2.5 hours, and made the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond.According to prescription, add 30.0 kilograms of vinylbenzene (St), 10.0 kilograms of butyl acrylates (BA) and 0.2 kilogram of vinylformic acid (AA), and solution system is mixed.Add other all acrylic ester monomers, and solution system is mixed.
(3) neutralization of prepolymer and emulsification: the prepolymer that step (2) generates is lowered the temperature, when temperature reaches 35 ℃, add 0.555 kilogram of neutralizing agent triethylamine (TEA), mix under 600 rev/mins the rotating speed simultaneously, join 43.6 kilograms of deionized waters in the prepolymer fast then, sheared 5 minutes with 1500 rev/mins rotating speed high-speed stirring simultaneously, make the solution system Phase inversion emulsification, thereby obtain containing the polyurethane aqueous dispersion body of acrylic ester monomer.
(4) in-situ emulsion polymerization: the temperature to 70 of the system that raises gradually ℃ begins to drip acetone (1.4 kilograms) solution that is dissolved with 0.322 kilogram of initiator A IBN; The control rate of addition makes the dropping time of initiator be about 1.5 hours.After initiator is added dropwise to complete, make architecture heat preservation reaction 4 hours.Measure transformation efficiency and reach 98% when above, stopped reaction also cools to 40 ℃, and discharging, filtration, packing promptly obtain aqueous polyurethane-acrylate interpenetrating net polymer composite emulsion.
Aqueous polyurethane-acrylate the interpenetrating network polymer emulsion that makes with above-mentioned prescription and technology was placed 7 days in the condition of 50 ℃ of constant temperature, do not have corruption, not stratified, do not lump, have good preservation stability.
2. spraying drying
(1) pre-treatment of dry preceding emulsion: according to the formula rate that designs in advance; 10 kilograms of the amido functional group polyvinyl alcohol and the machine mineral separant light calcium carbonate of protective colloid 40% solid content are joined in 85 kilograms of synthetic polymer emulsion systems for 10 kilograms; be to stir 50 minutes under 200 rev/mins the condition at rotating speed, make the mixed system uniformity.
(2) spraying drying: treated mixed emulsion system joined by the feed rate of 4 kg/minute carry out spraying drying in the equipment, dry temperature out often is 70 ℃.
The polyurethane-acrylate interpenetrating net polymer latex powder solid content that drying obtains is greater than 99%, and size of particles is more even, and particle diameter is 12 μ m, and 300 μ m screeningss are no more than 2%, have good flowability.The total volatile organic compound of product (VOC) can not detect; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Skin, respiratory tract to the people are non-stimulated, belong to environmentally friendly product.
The latex powder that makes with above-mentioned prescription and technology is the polymer bonding material, adds inorganic powder such as cement, coarse whiting, quartz sand, talcum powder etc. and a spot of cellulase, makes exterior wall facing mortar, has good construction performance and cohesive strength.Metope after the construction is firm, solid.Check the construction metope after 1 year, except light contamination, do not have phenomenons such as ftractureing, come off, be mouldy.
Embodiment 3
1. emulsion is synthetic
The starting material and the consumption of synthetic water based polyurethane-polyacrylate interpenetrating network polymer emulsion following (100 kilograms of total amounts):
15 kilograms of tolylene diisocyanates (TDI)
15 kilograms of polyoxypropyleneglycols (PPG)
5 kilograms of 1,4-butyleneglycols (BDO)
1.9 kilograms of dimethylol propionic acids (TMPA)
0.5 kilogram of glycidyl methacrylate
5.0 kilograms of vinylbenzene (St)
8.0 kilograms of butyl acrylates (BA)
0.1 kilogram in vinylformic acid (AA)
1.3 kilograms of triethylamines (TEA)
0.131 kilogram of Diisopropyl azodicarboxylate (AIBN)
5.0 kilograms in acetone
0.2 kilogram of N-methyl-2-pyrrolidone
42.9 kilograms in water
Synthesis step is:
(1) preparation of prepolymer: according to above-mentioned prescription, 15 kilograms of polyether Glycols PPG of 15 kilograms of TDI and dehydration are joined in the reactor of 200L, be to stir material and be warmed up to 65 ℃ gradually under 150 rev/mins the situation at rotating speed, keep reaction after 2 hours, add hydrophilic chain extender DMPA and the N-methyl-2-pyrrolidone that measures by the prescription that designs, be warmed up to 75 ℃ of reactions 1.5 hours, continue to add small molecule chain extender BDO, carry out chain extending reaction 2 hours at 75 ℃, further improve the molecular weight of prepolymer.
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in the product of step (1), add 0.5 kilogram of functional monomer containing active function groups and carbon-to-carbon double bond, residual NCO group and the OH base in the functional monomer structure carry out polyaddition reaction in the polyurethane prepolymer.The viscosity that adds 3 kilograms of acetone (staying 2 kilograms of acetone) reduction system with the dissolving initiator.Reacted 1.5 hours, and made the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond.According to prescription, add 5.0 kilograms of vinylbenzene (St), 8.0 kilograms of butyl acrylates (BA) and 0.1 kilogram of vinylformic acid (AA), and solution system is mixed.Add other all acrylic ester monomers, and solution system is mixed.
(3) neutralization of prepolymer and emulsification: the prepolymer that step (2) generates is lowered the temperature, when temperature reaches 50 ℃, add 1.3 kilograms of neutralizing agent triethylamines (TEA), mix under 600 rev/mins the rotating speed simultaneously, join 42.9 kilograms of deionized waters in the prepolymer fast then, sheared 5 minutes with 1500 rev/mins rotating speed high-speed stirring simultaneously, make the solution system Phase inversion emulsification, thereby obtain containing the polyurethane aqueous dispersion body of acrylic ester monomer.
(4) in-situ emulsion polymerization: the temperature to 65 of the system that raises gradually ℃ begins to drip acetone (2 kilograms) solution that is dissolved with 0.131 kilogram of initiator A IBN; The control rate of addition makes the dropping time of initiator be about 2 hours.After initiator is added dropwise to complete, make architecture heat preservation reaction 4 hours.Measure transformation efficiency and reach 98% when above, stopped reaction also cools to 40 ℃, and discharging, filtration, packing promptly obtain aqueous polyurethane-acrylate interpenetrating net polymer composite emulsion.
Aqueous polyurethane-acrylate the interpenetrating network polymer emulsion that makes with above-mentioned prescription and technology was placed 7 days in the condition of 50 ℃ of constant temperature, do not have corruption, not stratified, do not lump, have good preservation stability.
2. dry
(1) pre-treatment of dry preceding emulsion: according to the formula rate that designs in advance; 5 kilograms of the amido functional group polyvinyl alcohol and the machine mineral separant light calcium carbonate of protective colloid 40% solid content are joined in 88 kilograms of synthetic polymer emulsion systems for 7 kilograms; be to stir 40 minutes under 300 rev/mins the condition at rotating speed, make the mixed system uniformity.
(2) spraying drying: treated mixed emulsion system joined by the feed rate of 5 kg/minute carry out spraying drying in the equipment, dry temperature out often is 60 ℃.
The polyurethane-acrylate interpenetrating net polymer latex powder solid content that drying obtains is greater than 99%, and size of particles is more even, and particle diameter is 12 μ m, and 400 μ m screeningss are no more than 2%, have good flowability.The total volatile organic compound of product (VOC) can not detect; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Skin, respiratory tract to the people are non-stimulated, belong to environmentally friendly product.
The latex powder that makes based on above-mentioned prescription and technology, add color stuffings such as an amount of titanium dioxide, kaolin, add auxiliary agents such as a spot of solid defoamer, but made the scumbling construction, performance and present widely used latex coating suitable dry powder latex paint, its stable storing, convenient transportation.During construction, add the water latting drown and stir, adopt the method construction of brushing, roller coat or spraying then, gained is filmed and can be satisfied the technical requirements of internal wall emulsion coating national standard (GB/T 9756-2001), has good alkali resistance, water tolerance and washable wiping performance.Because the dry powder latex paint of being prepared does not contain VOC, so odorlessness, nontoxic, not environmental pollution, therefore on the same day of construction, resident family just moves in rest.Check after 6 months, the phenomenon of fading and coming off does not appear in wall surface levelling, clean and tidy.Listen resident family to say that this coating does not have any smell, keeping a public place clean property is good; In plum rain season, the interior metope that scribbles coating is not seen the dewfall phenomenon.
Embodiment 4
1. emulsion is synthetic
The starting material and the consumption of synthetic water based polyurethane-polyacrylate interpenetrating network polymer emulsion following (100 kilograms of total amounts):
8 kilograms of tolylene diisocyanates (TDI)
6 kilograms of polyoxypropyleneglycols (PPG)
1.8 kilograms of 1,4-butyleneglycols (BDO)
1.2 kilograms of dimethylol propionic acids (TMPA)
1.0 kilograms of glycidyl methacrylate
9.0 kilograms of vinylbenzene (St)
20.0 kilograms of butyl acrylates (BA)
0.3 kilogram in vinylformic acid (AA)
0.9 kilogram of triethylamine (TEA)
0.293 kilogram of Diisopropyl azodicarboxylate (AIBN)
1.0 kilograms in acetone
0.6 kilogram of N-methyl-2-pyrrolidone
50.0 kilograms in water
Synthesis step is:
(1) preparation of prepolymer: according to above-mentioned prescription, 6 kilograms of polyether Glycols PPG of 8 kilograms of TDI and dehydration are joined in the reactor of 200L, be to stir material and be warmed up to 60 ℃ gradually under 100 rev/mins the situation at rotating speed, keep reaction after 2 hours, add hydrophilic chain extender DMPA and the N-methyl-2-pyrrolidone that measures by the prescription that designs, be warmed up to 85 ℃ of reactions 0.5 hour, continue to add small molecule chain extender BDO, carry out chain extending reaction 1 hour at 85 ℃, further improve the molecular weight of prepolymer.
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in the product of step (1), add 1 kilogram of functional monomer containing active function groups and carbon-to-carbon double bond, residual NCO group and the OH base in the functional monomer structure carry out polyaddition reaction in the polyurethane prepolymer.Reacted 2.5 hours, and made the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond.According to prescription, add 9.0 kilograms of vinylbenzene (St), 20.0 kilograms of butyl acrylates (BA) and 0.3 kilogram of vinylformic acid (AA), and solution system is mixed.Add other all acrylic ester monomers, and solution system is mixed.
(3) neutralization of prepolymer and emulsification: the prepolymer that step (2) generates is lowered the temperature, when temperature reaches 30 ℃, add 0.9 kilogram of neutralizing agent triethylamine (TEA), mix under 600 rev/mins the rotating speed simultaneously, join 50 kilograms of deionized waters in the prepolymer fast then, sheared 5 minutes with 1500 rev/mins rotating speed high-speed stirring simultaneously, make the solution system Phase inversion emulsification, thereby obtain containing the polyurethane aqueous dispersion body of acrylic ester monomer.
(4) in-situ emulsion polymerization: the temperature to 65 of the system that raises gradually ℃ begins to drip acetone (1 kilogram) solution that is dissolved with 0.293 kilogram of initiator A IBN; The control rate of addition makes the dropping time of initiator be about 2 hours.After initiator is added dropwise to complete, make architecture heat preservation reaction 2 hours.Measure transformation efficiency and reach 98% when above, stopped reaction also cools to 40 ℃, and discharging, filtration, packing promptly obtain aqueous polyurethane-acrylate interpenetrating net polymer composite emulsion.
Aqueous polyurethane-acrylate the interpenetrating network polymer emulsion that makes with above-mentioned prescription and technology was placed 7 days in the condition of 50 ℃ of constant temperature, do not have corruption, not stratified, do not lump, have good preservation stability.
2. dry
(1) pre-treatment of dry preceding emulsion: according to the formula rate that designs in advance; 2 kilograms of the amido functional group polyvinyl alcohol and the machine mineral separant light calcium carbonate of protective colloid 40% solid content are joined in 90 kilograms of synthetic polymer emulsion systems for 8 kilograms; be to stir 45 minutes under 250 rev/mins the condition at rotating speed, make the mixed system uniformity.
(2) spraying drying: treated mixed emulsion system joined by the feed rate of 3.5 kg/minute carry out spraying drying in the equipment, dry temperature out often is 90 ℃.
The polyurethane-acrylate interpenetrating net polymer latex powder solid content that drying obtains is greater than 99%, and size of particles is more even, and particle diameter is 11 μ m, and 400 μ m screeningss are no more than 2%, have good flowability.The total volatile organic compound of product (VOC) can not detect; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Skin, respiratory tract to the people are non-stimulated, belong to environmentally friendly product.
To prepare the buildings inner and external wall putty together according to latex powder and dry powder (a kind of calcium carbonate powders), silica powder and other inorganic color stuffing that above-mentioned prescription and technology make.Find that in the constructing operation process polymer emulsion powder has the splendid performance of mixing and stirring, almost can be wetted immediately; Application property there is not any negative impact; Have good construction performance and cohesive strength.
Embodiment 5
1. emulsion is synthetic
The weight of raw material (100 kilograms of total amounts) composed as follows:
12.0 kilograms of tolylene diisocyanates (TDI)
10.5 kilograms of polyoxypropyleneglycols (PPG)
2.6 kilograms of 1,4-butyleneglycols (BDO)
2.25 kilograms of dimethylol propionic acids (TMPA)
0.8 kilogram of glycidyl methacrylate
11 kilograms of vinylbenzene (St)
11 kilograms of butyl acrylates (BA)
0.2 kilogram in vinylformic acid (AA)
1.7 kilograms of triethylamines (TEA)
0.464 kilogram of Diisopropyl azodicarboxylate (AIBN)
6.0 kilograms in acetone
1.5 kilograms of N-methyl-2-pyrrolidones
40.0 kilograms in water
Synthesis step is:
(1) preparation of prepolymer: according to above-mentioned prescription, 10.5 kilograms of polyether Glycols PPG of 12 kilograms of TDI and dehydration are joined in the reactor of 200L, be to stir material and be warmed up to 65 ℃ gradually under 100 rev/mins the situation at rotating speed, keep reaction after 1 hour, add hydrophilic chain extender DMPA and the N-methyl-2-pyrrolidone that measures by the prescription that designs, be warmed up to 80 ℃ of reactions 1 hour, continue to add small molecule chain extender BDO, carry out chain extending reaction 1 hour at 80 ℃, improve the molecular weight of prepolymer.
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in the product of step (1), add 0.8 kilogram of functional monomer containing active function groups and carbon-to-carbon double bond, residual NCO group and the OH base in the functional monomer structure carry out polyaddition reaction in the polyurethane prepolymer.The viscosity that adds 4 kilograms of acetone (staying 2 kilograms of acetone) reduction system with the dissolving initiator.Reacted 1.5 hours, and made the OH radical reaction complete, thereby obtain containing the polyurethane prepolymer of carbon-to-carbon double bond.According to prescription, add 11.0 kilograms of vinylbenzene (St), 11.0 kilograms of butyl acrylates (BA) and 0.2 kilogram of vinylformic acid (AA), and solution system is mixed.Add other all acrylic ester monomers, and solution system is mixed.
(3) neutralization of prepolymer and emulsification: the prepolymer that step (2) generates is lowered the temperature, when temperature reaches 40 ℃, add 1.7 kilograms of neutralizing agent triethylamines (TEA), mix under 600 rev/mins the rotating speed simultaneously, join 40 kilograms of deionized waters in the prepolymer fast then, sheared 5 minutes with 1500 rev/mins rotating speed high-speed stirring simultaneously, make the solution system Phase inversion emulsification, thereby obtain containing the polyurethane aqueous dispersion body of acrylic ester monomer.
(4) in-situ emulsion polymerization: the temperature to 70 of the system that raises gradually ℃ begins to drip acetone (2 kilograms) solution that is dissolved with 0.464 kilogram of initiator A IBN; The control rate of addition makes the dropping time of initiator be about 1.5 hours.After initiator is added dropwise to complete, make architecture heat preservation reaction 3 hours.Measure transformation efficiency and reach 98% when above, stopped reaction, and cool to 40 ℃, discharging, filtration, packing promptly obtain aqueous polyurethane-acrylate interpenetrating network polymer emulsion.
Aqueous polyurethane-acrylate the interpenetrating network polymer emulsion that makes with above-mentioned prescription and technology was placed 7 days in the condition of 50 ℃ of constant temperature, do not have corruption, not stratified, do not lump, have good preservation stability.
2. spraying drying
(1) pre-treatment of dry preceding emulsion: according to the formula rate that designs in advance; 3 kilograms of the amido functional group polyvinyl alcohol and the machine mineral separant light calcium carbonate of protective colloid 40% solid content are joined in 95 kilograms of synthetic polymer emulsion systems for 2 kilograms; be to stir 40 minutes under 300 rev/mins the condition at rotating speed, make the mixed system uniformity.
(2) spraying drying: treated mixed emulsion system joined by the feed rate of 4 kg/minute carry out spraying drying in the equipment, dry temperature out often is 80 ℃.
The polyurethane-acrylate interpenetrating net polymer latex powder solid content that drying obtains is greater than 99%, and size of particles is more even, and particle diameter is 11 μ m, and 300 μ m screeningss are no more than 2%, have good flowability.The total volatile organic compound of product (VOC) can not detect; Heavy metal chromium, cadmium, lead, mercury and halohydrocarbon (in methylene dichloride) etc. all do not detect; Skin, respiratory tract to the people are non-stimulated.
To prepare together self-leveling cement according to latex powder and cement, quartzy sand and other inorganic color stuffing that above-mentioned composition and engineering makes Mortar has good construction performance and flow leveling. Product is easy to construction, and gained cement mortar ground is firm, solid, level and smooth; When mortar hardening, the matching effect of polymer and cement and other material is good, and the ground waterproof performance is good, and water absorption rate is low. Construct 6 Check after month, auto-flowing floor is smooth, clean and tidy, does not have any cracking, plays powder or damages phenomenon.
Claims (10)
1, a kind of preparation method of polyurethane-polyacrylate interpenetrating net polymer is characterized in that:
---with polyisocyanates, polyether glycol, small molecule chain extender, wetting ability chainextender, the functional monomer that contains active function groups and carbon-to-carbon double bond, neutralizing agent, acrylic ester monomer is main raw material, at first by the synthetic self-emulsifying anionic polyurethane water dispersion that contains carbon-to-carbon double bond of progressively addition polymerization method;
---with the synthetic polyurethane aqueous dispersion body as seed emulsion and polymer type surface promoting agent, acrylic ester monomer in the emulsification system, by adopting the method that initiator carries out in-situ emulsion polymerization that drips, make pre-emulsified Acrylic Acid Monomer in the system carry out on the inside of seed emulsion particle and surface polymerization and (or) crosslinked, obtain the polyurethane-polyacrylate interpenetrating network polymer emulsion.
2, method according to claim 1 is characterized in that may further comprise the steps:
(1) preparation of prepolymer: polyisocyanates and polyether glycol are added in the reaction vessel, after reacting 1～2 hour under 60～65 ℃, add wetting ability chainextender and N-methyl-2-pyrrolidone, be warmed up to 75～85 ℃ of reactions 0.5～1.5 hour, add small molecule chain extender and carried out chain extending reaction 1～2 hour at 65～75 ℃;
(2) contain the preparation of the polyurethane prepolymer of carbon-to-carbon double bond: in step (1) synthetic product, add the functional monomer that contains active function groups and carbon-to-carbon double bond, NCO group and the OH base in the functional monomer structure residual in the polyurethane prepolymer carried out polyaddition reaction 1.5～2.5 hours, obtain containing the polyurethane prepolymer of carbon-to-carbon double bond, add acrylic ester monomer, solution system is mixed;
(3) neutralization of prepolymer and emulsification: the polyurethane prepolymer that step (2) is obtained cools to 30～50 ℃, adds neutralizing agent, mixes, and obtains intermediate; Then deionized water is joined in the intermediate fast, stir, make the solution system Phase inversion emulsification, thereby obtain containing the polyether polyols with reduced unsaturation water dispersion of acrylic ester monomer;
(4) in-situ emulsion polymerization: the temperature to 60 of the system that raises gradually～70 ℃, begin to drip the acetone soln 1～2 hour that is dissolved with initiator, insulation reaction is 2～4 hours then, transformation efficiency reaches 98% when above, stopped reaction and cooling, discharging, filters, obtains urethane-acrylate interpenetrating network polymer emulsion;
The weight percent of above-mentioned raw materials is composed as follows:
Polyisocyanates 5～15%
Polyether glycol 4～15%
Small molecule chain extender 1～5%
Wetting ability chainextender 0.77～2.25%
The functional monomer 0.1～1% that contains active function groups and carbon-to-carbon double bond
Acrylic ester monomer 10.1～50.3%
Neutralizing agent 0.56～1.7%
Initiator 0.13～0.5%
Acetone 1～10%
N-methyl-2-pyrrolidone 0.2～1.5%
Deionized water 40～50%.
3, method according to claim 1 and 2 is characterized in that described polyisocyanates is one or more mixtures in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, the dicyclohexyl methane diisocyanate.
4, method according to claim 3 is characterized in that described polyether glycol is polyether glycol and/or polyether triol; Described small molecule chain extender is one or more in 1,4-butyleneglycol, ethylene glycol, glycol ether, TriMethylolPropane(TMP), hexylene glycol, quadrol, the diethylenetriamine; Described wetting ability chainextender is dimethylol propionic acid, dihydroxyl half ester, diaminobenzoic acid, quadrol base ethyl sulfonic acid sodium or 1,4-butyleneglycol-2-sodium sulfonate; The described functional monomer that contains active function groups and carbon-to-carbon double bond is glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, propyl glycidyl ether, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate; Described neutralizing agent is sodium hydroxide, potassium hydroxide, ammoniacal liquor or triethylamine; Described acrylic ester monomer comprises one or more mixtures in methyl methacrylate, vinylbenzene, the butyl acrylate; Described initiator is azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
5, method according to claim 4 is characterized in that it is 80/20 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate that described polyisocyanates is selected mass ratio for use; Polyether glycol is selected polyoxypropyleneglycol (PPG) and/or PTMG for use; Small molecule chain extender is selected 1,4-butyleneglycol (BDO) for use; The wetting ability chainextender is selected dimethylol propionic acid (TMPA) for use; Functional monomer is selected glycidyl methacrylate for use; Neutralizing agent is selected triethylamine (TEA) for use; Initiator is selected Diisopropyl azodicarboxylate (AIBN) for use.
6, method according to claim 5 is characterized in that described acrylic ester monomer and consumption thereof are as follows:
Vinylbenzene (St) 5～30%
Butyl acrylate (BA) 5～20%
Vinylformic acid (AA) 0.1～0.3%.
7, the polyurethane-polyacrylate interpenetrating network polymer emulsion for preparing of the described method of one of claim 1-6 is used to prepare the method for dry powder latex paint; it is characterized in that drying is carried out in polyurethane-polyacrylate interpenetrating network polymer emulsion, protective colloid, the mixing of inorganic mineral separant, the weight percent of described raw material is composed as follows:
Polyurethane-polyacrylate interpenetrating network polymer emulsion 80～95%
Protective colloid 2～15%
Inorganic mineral separant 2～10%.
8, method according to claim 7 is characterized in that described protective colloid is polyvinyl alcohol (PVA) and derivative or silicon sol; Described inorganic mineral separant is lime carbonate, barium sulfate, talcum powder, kaolin, pure aluminium silicate, diatomite or silicon-dioxide.
9, method according to claim 8 is characterized in that protective colloid selects the amido functional group polyvinyl alcohol for use; The inorganic mineral separant selects for use light calcium carbonate as the inorganic mineral separant.
10, method according to claim 9 is characterized in that drying may further comprise the steps:
(1) pre-treatment of dry preceding emulsion: protective colloid and inorganic mineral separant are joined in the polyurethane-polyacrylate interpenetrating network polymer emulsion, be to stir 40～60 minutes under 100～300 rev/mins the condition at rotating speed, the solid content of pre-treatment post polymerization thing emulsion system is 30～60%;
(2) drying: pretreated polymer emulsion carries out drying by fluidised bed drying, lyophilize or spraying drying, and dry temperature out is 60 ℃～90 ℃.
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