CN102153712B - Water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from same - Google Patents
Water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from same Download PDFInfo
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Abstract
The invention relates to water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from the same, in particular to water-based polyurethane-acrylate emulsion and re-dispersible latex powder prepared from the same and a preparation method of the latex powder. The water-based polyurethane-acrylate emulsion has good stability in the polymerization process, and the re-dispersible latex powder prepared from the emulsion has the advantages of low film forming temperature and good mechanical property.
Description
Technical field
The present invention relates to a kind of water-based polyurethane-acrylate emulsion, and redispersible latex powder prepared therefrom, more specifically, the present invention relates to a kind of water-based polyurethane-acrylate emulsion, and relate to the preparation method of redispersable latex powder prepared therefrom and this rubber powder, described water-based polyurethane-acrylate emulsion has satisfactory stability in polymerization process, and it is low that redispersion latex powder prepared therefrom has film-forming temperature, the advantage of good mechanical property.
Background technology
Redispersable latex powder is the free flowable polymer powder of one obtaining after the efflorescence of polymer emulsion drying, after adding water therein, latex powder can be re-dispersed in water and generate stable dispersion liquid, forms and the original regeneration emulsion that polymer emulsion performance is identical, purposes is similar.Compared with polymer emulsion, redispersable latex powder has outstanding advantage: stability in storage is good, and the shelf lives is long, can be because not freezing or moisture evaporation goes bad; Packing is simple, volume is little, lightweight and transportation cost is low; Can arbitrarily allocate easily with other raw materials such as cement, gypsum, easy to use.
At present for the production of the polymkeric substance of latex powder or take Vinyl Acetate Copolymer as main, but other class redispersable latex powder is also developed in succession, as vinyl acetate and ethylene copolymer rubber powder, vinyl acetate and ethene and higher fatty acid vinyl acetate terpolymer rubber powder, vinyl acetate and higher fatty acid vinyl acetate copolymerization rubber powder, pure acrylate latex powder, acrylate and styrene copolymerized rubber powder, vinyl acetate and acrylate and higher fatty acid vinyl acetate terpolymer rubber powder, vinylbenzene and butadiene copolymer rubber powder etc.Wherein acrylate is relatively outstanding in aspect performances such as weather-proof, water-fast, resistance to solvent, gloss retentions, such latex powder is on the basis of original redispersible latex powder technology, and stability in storage, redispersible, water tolerance, alkali resistance have all obtained raising in various degree.But esters of acrylic acid latex powder film-forming temperature is high, the feature of bad mechanical property, limit the multi-field marketization application of latex powder.
Urethane because its mechanical property adjustable extent is wide, with the superiority of the aspect such as the cohesiveness of base material is good, be used widely in a lot of fields.Aqueous polyurethane is in polyurethane backbone, to introduce ionic group, by the ionization in water of ionic group, urethane is scattered in WATER AS FLOW MEDIUM and the polyurethane aqueous dispersions that forms.In the preparation process of aqueous polyurethane, do not need additional emulsifying agent and its stability in use is greatly improved; And each bound pair environmental issue more and more payes attention to, the use of aqueous polyurethane is widelyd popularize.But aqueous polyurethane be yet there are no and mentioned for the production of the technique of redispersible latex powder.
Based on the different characteristics of aqueous polyurethane and acrylate, if the advantages of the two is used, can prepare excellent property, polymer polyurethane-acrylate (PUA) emulsion with low cost.In addition this polymer emulsion does not need additional emulsifying agent, the negative impact bringing can avoid using emulsifying agent time; And urethane can be connected by chemical bond with acrylate, reduce unstable the brought poor shortcoming of the mechanical property of materials of two-phase interface, to obtaining the preparation of the good emulsion polymer of physical strength for redispersable latex powder.
Summary of the invention
[technical problem]
The present invention is designed to address the above problem.The object of this invention is to provide a kind of water-based polyurethane-acrylate emulsion, redispersable latex powder prepared therefrom, this water-borne polyurethane-acrylate redispersable latex powder has lower film-forming temperature, excellent mechanical property and cheap cost.
[technical scheme]
To achieve these goals, one aspect of the present invention provides a kind of water-based polyurethane-acrylate emulsion, and this water-based polyurethane-acrylate emulsion is prepared as follows:
The preparation of A, aqueous polyurethane prepolymer: polycaprolactone glycol is joined in reactor, be warming up to 70～85 ℃ and also drip wherein isocyanate reaction, then add hydrophilic chain extender, continue reaction;
The preparation of the aqueous polyurethane prepolymer of B, two key end-blockings: the prepolymer mixed solution of preparing in A step is cooled to 50～60 ℃, dilute this prepolymer by acetone or acrylate part, and in backward described aqueous polyurethane prepolymer, add the end-blocking monomer that comprises hydroxyl and two keys, being warming up to 60～75 ℃ reacts;
C, ionomeric preparation: at 40～55 ℃, use in neutralizing agent and the aqueous polyurethane prepolymer of described pair of key end-blocking;
D, in the time using acetone diluted in step B: under normal temperature, in described ionomer, add distilled water rapid dispersion, then acrylate part, initiator, buffer reagent joined in emulsion together, be dispersed into uniform emulsion; In the time diluting by acrylate part in step B: add distilled water rapid dispersion under normal temperature in described ionomer, then initiator, buffer reagent are joined in emulsion together, be dispersed into uniform emulsion;
E, containing the polymerization of the polyaminoester emulsion of acrylate part: join reactor by 1/3 of the polyaminoester emulsion of preparing in step D in, at 75～85 ℃, react after 1 hour, then drip remaining 2/3 emulsion and react;
85～90 ℃ of F, rising temperature of reaction, continue reaction 1 hour.
Wherein, the number-average molecular weight of described polycaprolactone glycol is 500～2500, and the mol ratio R of the hydroxyl sum in isocyanate groups and described polycaprolactone glycol and end-blocking monomer is 1.2～1.8, and described acrylate part comprises hard monomer and soft monomer.
Wherein, described isocyanic ester is aliphatic isocyanates; Described hydrophilic chain extender is carboxylic acid type chainextender; The described end-blocking monomer that comprises hydroxyl and two keys is hydroxy alkyl ester; Described neutralizing agent is triethylamine; Degree of neutralization in described step C is 80～100%; Described initiator is selected from ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Described buffer reagent is selected from sodium-acetate, sodium bicarbonate, Sodium phosphate dibasic and sodium sulfate; Described hard monomer is to be selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate and vinylbenzene; And soft monomer is for being selected from ethyl propenoate, n-butyl acrylate, vinylformic acid pentyl ester and propylene be one or more in ester just; Soft, hard monomer weight ratio is 5: 5～6: 4.
Wherein, described isocyanic ester is hexamethylene-diisocyanate, hydrogenation 4,4 '-diphenylmethanediisocyanate or isophorone diisocyanate; Described hydroxy alkyl ester is selected from methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester and vinylformic acid-5-hydroxyl pentyl ester; Described carboxylic acid type chainextender is selected from dimethylol propionic acid, amino acid or diaminobenzoic acid; Described initiator amount is 0.5～1.0% of acrylate part gross weight; Described buffer reagent consumption is acrylate part gross weight 0.2～0.5%.
Another aspect of the present invention provides the acrylate of being prepared by above-mentioned water-based polyurethane-acrylate emulsion redispersable latex powder.
[beneficial effect]
According to the present invention, the urethane composition of contained mechanical property excellence in emulsion, uses it for and prepares redispersible latex powder, film-forming properties, physical strength, water tolerance that the latex powder of gained has had.Polyurethane-acrylic ester emulsion polymerization process in the present invention simultaneously does not need to use additional emulsifying agent, the poor negative impact of polymerization stability of avoiding additional emulsifying agent to bring.
Embodiment
One aspect of the present invention provides a kind of water-based polyurethane-acrylate emulsion, and this water-based polyurethane-acrylate emulsion is prepared as follows:
The preparation of A, aqueous polyurethane prepolymer: polycaprolactone glycol is joined in reactor, be warming up to 70～85 ℃ and also drip wherein isocyanate reaction, then add hydrophilic chain extender, continue reaction;
The preparation of the aqueous polyurethane prepolymer of B, two key end-blockings: the prepolymer mixed solution of preparing in A step is cooled to 50～60 ℃, with this prepolymer of dilution of acetone or acrylate part, then in described aqueous polyurethane prepolymer, add the end-blocking monomer that comprises hydroxyl and two keys, be warming up to 60～75 ℃ and react;
C, ionomeric preparation: at 40～55 ℃, use in neutralizing agent and the aqueous polyurethane prepolymer of described pair of key end-blocking;
D, in the time using acetone diluted in step B: under normal temperature, in described ionomer, add distilled water rapid dispersion, then acrylate part, initiator, buffer reagent joined in emulsion together, be dispersed into uniform emulsion; In the time diluting by acrylate part in step B: add distilled water rapid dispersion under normal temperature in described ionomer, then initiator, buffer reagent are joined in emulsion together, be dispersed into uniform emulsion;
E, containing the polymerization of the polyaminoester emulsion of acrylate part: join reactor by 1/3 of the polyaminoester emulsion of preparing in step D in, at 75～85 ℃, react after 1 hour, then drip remaining 2/3 emulsion and react;
85～90 ℃ of F, rising temperature of reaction, continue reaction 1 hour.
Water-based polyurethane-acrylate emulsion of the present invention is characterised in that this emulsion is that aqueous polyurethane oligopolymer take two key end-blockings is as self-emulsifier, this oligopolymer and acrylate part are scattered in WATER AS FLOW MEDIUM under stirring action, obtain polyurethane-acrylate (PUA) emulsion by letex polymerization.
For realizing the present invention's object, the aqueous polyurethane oligopolymer of described two key end-blockings is being prepared on aqueous polyurethane prepolymer basis, the chemical reaction of pass through-NCO and hydroxyl (OH), the end that unsaturated double-bond is incorporated into polyurethane molecular chain obtains.Now both can play the effect of letex polymerization emulsifying agent with the polyurethane prepolymer of two key end-blockings, can participate in again follow-up Raolical polymerizable.Hydrated ion base assurance letex polymerization contained in aqueous polyurethane can more stably be carried out, the negative impact having brought while having reduced by additional emulsifying agent; Reduce in addition urethane, uncompatibility that polyacrylic ester two is alternate, make the PUA polymkeric substance of gained there is excellent mechanical property.
Described in the present invention is a kind of ionomer forming through step-reaction polymerization and salt-forming reaction with isocyanic ester, oligomer polyol, hydrophilic chain extender, the end-blocking monomer, the neutralizing agent etc. that comprise hydroxyl and two keys containing the urethane oligomer of hydration radical ion.
Described isocyanic ester generally includes aromatic 2,4-tolylene diisocyanate (TDI), 4,4 '-diphenylmethanediisocyanate (MDI) and aliphatic hexamethylene-diisocyanate (HDI), hydrogenation MDI (HMDI), isophorone diisocyanate (IPDI).In polyurethane chain, the carbamate groups that isocyanic ester and polyol reaction form is the integral part that forms poly-amino hard section, is the important support structure of mechanical strength in polyurethane material.The prepared urethane of common aromatic isocyanic ester has good physical strength, but weather resisteant, photostabilization etc. are poor.The urethane of preparing when this kind isocyanate is during for building structural materials, especially outdoor building materials, and its work-ing life is shorter.And aliphatic isocyanic ester can overcome these shortcomings, specifically, application aliphatic isocyanates can also make, after the urethane life-time service of gained, base material still to be had to very strong sticking power.In the present invention, preferably prepare Waterborne Polyurethane Prepolymer with aliphatic isocyanates, for example, hexamethylene-diisocyanate (HDI), hydrogenation MDI (HMDI), isophorone diisocyanate (IPDI).
Described oligomer polyol comprises polyether glycol, polyester polyol, polydimethylsiloxanediols diols (PDMS).Wherein common polyether glycol includes polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran diol (PTHF) etc., and polyester polyol comprises polyethylene glycol adipate glycol, polycaprolactone glycol (PCL), polycarbonate diol etc.These oligomer polyol are incorporated in polyurethane molecular chain as soft section, make the polyurethane prepolymer of gained have good snappiness and film-forming properties, even if also can form at low temperatures regular film.
In polyether type aqueous urethane, owing to there being the existence of ehter bond, under acid-base condition, there is higher stability to hydrolysis resistance than polyester polyol; In addition, the second-order transition temperature of polyether(poly)urethane is low, and resistance to low temperature is good, has good toughness and extensibility.But poor as soft section of prepared urethane mechanical strength by polyether glycol.PAUR intensity is high, bonding force good, but because the anti-hydrolytic performance of polyester itself is poorer than polyethers, therefore the polyester type aqueous polyurethane that adopts general raw material to make, its shelf stable for periods is shorter.But by adopting hydrolytic resistance polyester polyol, as polycarbonate diol, polycaprolactone glycol (PCL), for the preparation of aqueous polyurethane, can improve the stability to hydrolysis resistance of aqueous polyurethane, extend the work-ing life of aqueous polyurethane.And polydimethylsiloxanediols diols is incorporated in polyurethane backbone, can strengthen the water tolerance after polyurethane film-forming, give aqueous polyurethane with good film formation at low temp simultaneously.
Oligomer polyol, according to the difference of molecular weight, also can obtain different performance polyurethane prepolymer.In general, suppose that polyurethane molecular amount is identical, if its soft section of polyester, the increase of the intensity polyester glycol molecular weight of urethane and improving; If soft section is polyethers, the increase of the intensity polyether glycol molecular weight of urethane and declining.Soft section of polarity of polyester type own is just stronger, and molecular weight is large and structural regularity is high, favourable to improving intensity; Polyester soft segment polarity a little less than, if molecular weight increases, in WPU, the relative content of hard section just reduces, strength degradation.
Based on above consideration, for obtaining the urethane of good combination property, the present invention preferably adopts polycaprolactone glycol (PCL) to prepare urethane as soft section; According to actual needs, regulate snappiness, film formation at low temp and the water tolerance etc. of urethane with polyether-type, polysiloxane type dibasic alcohol.The PCL using is for number-average molecular weight is at 500～2500 oligopolymer.
In the process of preparing aqueous polyurethane, to add small molecules hydrophilic chain extender, introduce hydrophilic radical.In this class chainextender, usually contain the hydrophilic radicals such as carboxyl, sulfonic group or secondary amine, in the time that it is keyed in polyurethane molecular chain, can make on urethane segment, with can ionizable group, to obtain polyaminoester emulsion by the mode of self-emulsifying.Application is at present more, effect is preferably carboxylic acid type negatively charged ion chainextender.Carboxylic acid type chainextender has dimethylol propionic acid (DMPA), amino acid, diaminobenzoic acid etc.Wherein DMPA can produce best emulsifying effectiveness, is to prepare a kind of wetting ability chainextender that aqueous polyurethane is conventional.Its molecular weight is little, less consumption just can provide abundant carboxyl amount, and in DMPA-COOH is connected with tertiary carbon atom, sterically hindered large, in chain extension process-COOH with-chance that NCO reacts is few, the polyurethane chain intermediate ion concentration obtaining is high, self-emulsifying ability is strong, the emulsion particle diameter forming is little, and stability is high.In urethane, DMPA consumption will be controlled at suitable scope, when consumption is large, makes to contain more hydrophilic radical in polyurethane chain, and the water resistance of material does not reach requirement; Consumption is too low, can cause emulsification insufficient.In the present invention, urethane will play the effect of emulsifying agent, if emulsification is insufficient, can cause follow-up acrylate free-radical emulsion polymerization stability decreases, and its consumption control is 5～10% of two key end-blocking aqueous polyurethane total amounts.
The mol ratio R (being R=-NCO/-OH) of the hydroxyl sum in isocyanate groups and described oligomer polyol and end-blocking monomer need to be controlled in suitable scope.When R value is less, generate the base polyurethane prepolymer for use as that molecular weight is larger, make follow-up hydration emulsification become difficulty; And R value is too large, gained base polyurethane prepolymer for use as molecular weight, can make urethane snappiness variation, and hydro-combination process is also wayward, and for the film-forming properties variation of whole latex system.In the present invention, the span of control of R value is 1.2～1.8.
Prepared aqueous polyurethane prepolymer has larger viscosity, carry out next step reaction before, sometimes also need to use solvent to dilute it.Conventional solvent has acetone, butanone, N,N-dimethylacetamide etc., these solvents add the reduced viscosity that can make polyurethane prepolymer.For reducing the discharge of inert organic solvents in the two key end-blocking aqueous polyurethane processes of preparation, also can dilute base polyurethane prepolymer for use as by acrylate part of the present invention.
The present invention intends utilizing the hydroxyl in described end-blocking monomer to react the end two keys are incorporated into polyurethane prepolymer with the residue-NCO in polyurethane prepolymer.Described end-blocking monomer comprises hydroxy alkyl ester, for example methacrylic acid-2-hydroxy methacrylate (HEMA), methacrylic acid-3-hydroxy propyl ester (HPMA), vinylformic acid-4-hydroxyl butyl ester (HBA) and vinylformic acid-5-hydroxyl pentyl ester.
The consumption of described end-blocking monomer is according to after isocyanic ester and polyol reaction, remaining-NCO is definite in theory.
By small molecules hydrophilic chain extender be incorporated in polyurethane chain hydrophilic radical need to be under the effect of neutralizing agent salify, the ionomer obtaining like this could form stable water dispersion in WATER AS FLOW MEDIUM.For anionic polyurethane, can be used as neutralizing agent with the alkaloids of anionic group generation neutralization reaction, conventional have alkaline matters such as sodium hydroxide, ammoniacal liquor, triethylamine (TEA).From stability of emulsion aspect, with in sodium hydroxide and after aqueous polyurethane particle diameter large, poor stability; There is the problem of xanthochromia in ammoniacal liquor; With tertiary amine or coordinate other alkaloids, its stability, dispersed far better comparatively speaking, the neutralizing agent using in the present invention preferably uses TEA.
The consumption of neutralizing agent also has larger impact to the performance of emulsion, and triethylamine consumption is too little does not reach desired emulsification degree; Along with triethylamine consumption increases, latex particle size reduces, and viscosity increases, and is conducive to latex stable, and general degree of neutralization should be controlled at 80%～100%.
Preparing in urethane process, preferably use catalyzer.The catalyzer that is usually used in preparing urethane comprises triethylenediamine, trolamine, dibutyl tin dilaurate (DBTL), stannous octoate, these catalyzer contribute to fast reaction speed, and the consumption control of catalyzer is 0.1～0.2% of urethane part gross weight.
The PUA emulsion that the polyurethane copolymerization of the acrylate part described in the present invention and two key end-blockings forms, within urethane part and propionic ester part will be controlled at certain proportional range, the two advantage of competence exertion like this, finally prepares the PUA latex powder of excellent performance.In the present invention, the gross weight of acrylate part gross weight and urethane part (PA: PU) control is at 3: 7～5: 5.Unless statement in addition, acrylate part gross weight described here refers to the gross weight of soft monomer and hard monomer, end-blocking monomer, hydrophilic chain extender and neutralizing agent gross weight that urethane part gross weight refers to isocyanic ester, oligomer polyol, comprises hydroxyl and two keys.
Described acrylate part is made up of hard monomer and soft monomer, and hard monomer is used for guaranteeing the intensity that PUA system has had, and soft monomer is used for regulating snappiness and the film-forming properties of PUA.Soft or hard monomer will be controlled at suitable scope, and soft, hard monomer weight ratio control of the present invention is 5: 5～6: 4.
Soft monomer of the present invention comprises ethyl propenoate (EA), at least one in n-butyl acrylate (n-BA), vinylformic acid penta polyester (n-PA), the just own ester of propylene (n-HA).
Hard monomer described in the present invention comprises at least one in methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA), Tert-butyl Methacrylate (t-BMA), vinylbenzene (St).
In emulsion polymerization process of the present invention, needed initiator mainly uses water miscible inorganic initiation machine, comprise the wherein one in ammonium persulphate (APS), Sodium Persulfate (SPS), Potassium Persulphate (KPS), initiator amount is controlled at 0.5～1.0% of acrylate part gross weight.
Letex polymerization need to be used buffer reagent that pH value is controlled in desired scope.Described buffer reagent can be selected from the wherein one of sodium-acetate, sodium bicarbonate, Sodium phosphate dibasic, sodium sulfate, and consumption is about acrylate part gross weight 0.2～0.5%.
Another aspect of the present invention is on the basis of preparation PUA emulsion, prepares redispersible, water tolerance, film-forming properties, all good PUA redispersable latex powders of mechanical property.
Redispersible latex powder of the present invention is on the basis of gained PUA emulsion; coordinate other auxiliary agent; as anti-caking agent, protective colloid, defoamer, sterilant etc., form the technique of powder fluidized polymer material by the atomization drying efflorescence of dewatering, said composition body proportioning is as follows
Table 1
Protective colloid of the present invention be alcoholysis degree more than 90%, the polyvinyl alcohol (PVA) that the polymerization degree is 300～1200.The polymerization degree, lower than 300 PVA, can not play a very good protection, and the polymerization degree is excessive to colloid, can make emulsion viscosity increase, and affects the carrying out of atomization process.PVA consumption is controlled at 10～25% of PUA weight.
Inorganic anti-caking agent is adsorbed on latex particle and forms inorganic dispersion protective layer around; when dry, Castor Oil tower wall and pipeline improve the dry yield of latex powder; can avoid the latex particle reunion that sticks together; extend its stability in storage: it has certain wetting ability simultaneously, when redispersion, can make latex powder better disperse.Inorganic anti-agglomerating agent of the present invention comprises calcium carbonate, silicon-dioxide, and pure aluminium silicate, talcum powder, at least one in kaolin, consumption is between PUA polymer weight 10%～20%.
According to the needs of dry pulverizing process or latex powder performance, need to add some functional aids, mainly comprise defoamer, sterilant etc.
This latex powder is that the spray method by adopting rotary atomizer obtains, and the method comprises the steps:
The composition of the dry gained of spraying;
After latex powder forms, separate through rotary gas separator, collect powder in tower exit with stainless steel storage tank;
Filter and obtain latex powder with 200 mesh filter screens.
For obtaining even, the stay-in-grade latex powder of outward appearance, spray art condition of the present invention is defined as: atomizing wheel rotating speed 200～600r/min, and 100～120 ℃ of drying tower inlet temperature, drying tower temperature out is 60～80 ℃, input speed is 80～100gmin
-1.Spray-drying tower is furnished with suction pressure device, after latex powder forms, separates through cyclonic separator, collects powder in tower exit with stainless steel storage tank, after 200 mesh filter screens filter, is placed in loft drier preserves with bag sealing.
Specific implementation method: the process that the present invention prepares PUA redispersible latex powder comprises the process of preparation and the dry efflorescence of PUA emulsion of PUA emulsion.
embodiment
Hereinafter, will describe in further detail preferred embodiment of the present invention.Before being described, should be appreciated that the term using in specification sheets and appending claims should not be construed to only limits to general or literal connotation, but makes an explanation based on correspondence technical elements of the present invention allowing contriver suitably to limit for best interpretations ground on the basis of principle of term.Therefore, the description proposing in specification sheets is only for explaining the object of the invention preferred embodiment, but not be intended to limit the scope of the invention, thereby be appreciated that in the situation that not departing from the spirit and scope of the invention, can make being equal to it substituting and revising.
Starting material and processing thereof:
Polyisocyanates described in the present invention, polycaprolactone dibasic alcohol (PCL) and other oligopolymer dibasic alcohol: industrial goods, Guang Zhouhui adopts coatings chemistry product company limited; Dimethylol propionic acid (DMPA), triethylamine (TEA), N, N-dimethyl pyrrolidone (NMP): analytical pure, Ke Miou chemical reagent development centre, Tianjin; Acetone, acrylate, methacrylic ester, (methyl) acrylic acid hydroxy alkyl ester, persulphate: analytical pure, the north, Tianjin day medical chemistry chemical reagent work; Sodium bicarbonate (NaHCO
3) analytical pure, Tianjin Kai Tong chemical reagent company limited.
The auxiliary agent using in spray process is all industrial goods, and wherein defoamer is BYK-088, originates from German Bi Ke chemistry.
Under the condition that before PCL uses, 90 ℃, vacuum tightness are 0.1MPa in vacuum drying oven, dewater 2 hours; DMPA uses initial vacuum dry; TEA, acetone, NMP soak with molecular sieve; Acrylate, methacrylic ester, (methyl) acrylic acid hydroxy alkyl ester remove stopper processing before using; IPDI directly uses, distilled water self-control.
Embodiment 1
1, the preparation of PUA emulsion: the ratio of each component is as shown in table 2, wherein, R is-NCO/-OH=1.4, degree of neutralization 100%.
Table 2
Polymerization procedure is as follows:
The preparation of A, aqueous polyurethane prepolymer: the weight described in table 2 is joined PCL with thermometer, whipping appts, condensing reflux pipe, constant pressure funnel, N
2in the reactor of breather, and the temperature of reactor is raised to 80 ℃; In IPDI being splashed into reactor at this temperature and react 1 hour; Then the DMPA solution (weight ratio of NMP and DMPA is 2: 1) being dissolved in NMP is joined in reactor, at this temperature, react 3 hours, finally obtain aqueous polyurethane prepolymer;
B, the temperature of reactor is dropped to 60 ℃, add acetone 10g with dilution prepolymer, obtain low viscous pre-polymer solution; Then will join in reactor according to the HEMA of weight shown in table 2, be warmed up to 70 ℃, react 3 hours, obtain the aqueous polyurethane prepolymer of two key end-blockings;
C, temperature of reaction kettle drop to 50 ℃, use in TEA and the aqueous polyurethane prepolymer of two key end-blockings, and neutralization reaction is carried out about half an hour, obtains ionomer;
Under D, room temperature, distilled water is joined to rapid dispersion in ionomer, obtain aqueous polyurethane emulsion; Then acrylate part, initiator, buffer reagent are joined in polyaminoester emulsion in the lump, be dispersed into the uniform polyaminoester emulsion containing acrylate part for subsequent use;
E, get 1/3 of the emulsion prepared in D step, put into thermometer, whipping appts, condensing reflux pipe, constant pressure funnel, N
2in the reactor of breather, be slowly warmed up to 80 ℃, react 1 hour; The emulsion that then drips residue 2/3, dropwised at 3～3.5 hours;
F, then temperature is raised to 90 ℃, continues emulsion polymerization 1 hour; After having reacted, reactor is dropped to room temperature, obtain PUA emulsion and store for future use;
2, the preparation of PUA redispersable latex powder
Table 3
Choosing the polymerization degree is 400, and the PVA that alcoholysis degree is 92% is mixed with weight concentration and is 20% the aqueous solution and join in the PUA emulsion of above-mentioned preparation, and adds calcium carbonate and the defoamer BYK-088 of weight shown in table 3, stirs and is uniformly dispersed.After each auxiliary agent is dispersed in PUA emulsion, the emulsion of gained passes into Centrafugal spray drying tower under peristaltic pump guiding, and setting atomizer rotating is 300rmin
-1, inlet temperature is 105 ℃, temperature out is 70 ℃, input speed 80gmin
-1, spray with this understanding dry.Spray-drying tower is furnished with suction pressure device, after latex powder forms, separates through cyclonic separator, collects powder in tower exit with stainless steel tubbiness storage tank, after 200 mesh filter screens filter, is placed in loft drier preserves with bag sealing.
Embodiment 2
1, the preparation of PUA emulsion
Replace SPS at embodiment 2 use KPS, in emulsion preparation process, will not re-use acetone polyurethane prepolymer is diluted.Owing to not using in this embodiment acetone, can reduce the use of organic volatile in production process, and step is relatively easier, enhances productivity.Embodiment is as follows:
A, first react by IPDI, PCL, DMPA the aqueous polyurethane prepolymer obtaining, the temperature of reactant is dropped to 50 ℃;
B, by formula in MMA, n-BA join in reactor, until reactant becomes the solution of homogeneous transparent;
C, add the required HEMA of formula, be warmed up to 70 ℃, react 3 hours, obtain pair urethane of key end-blocking and the mixture of Acrylic Acid Monomer;
D, this mixture at ambient temperature, add the distilled water in formula to be uniformly dispersed, and add initiator, buffer reagent joins in emulsion, becomes the aqueous polyurethane emulsion containing propylene monomer;
The letex polymerization of E, follow-up acrylate is with carrying out in mode similarly to Example 1.
Table 4
2, the preparation of PUA redispersable latex powder
Table 5
Selecting the polymerization degree is 600, and the aqueous solution that the PVA that alcoholysis degree is 95% is mixed with 20wt% uses; Inorganic anti-caking agent is selected kaolin and silicon-dioxide, the mixed solution according to the weight shown in table 5 for the preparation of preparation PUA redispersable latex powder; Then, to carry out dry nebulization with the identical mode in embodiment 2.
Embodiment 3
1, the preparation of PUA emulsion
Except using HMDI to replace IPDI, and vinylbenzene (St) is replaced outside MMA, feed intake and prepare PUA emulsion according to the weight shown in table 5 in the mode identical with embodiment 2.
Table 6
2, the preparation of PUA redispersable latex powder
Table 7
Selecting the polymerization degree is 800, and the PVA that alcoholysis degree is 97.5% is mixed with 20% the aqueous solution; Inorganic anti-caking agent is selected pure aluminium silicate and silicon-dioxide; Mixed solution according to the weight shown in table 7 for the preparation of preparation PUA redispersable latex powder; Then, to carry out dry nebulization with the identical mode in embodiment 2.
Embodiment 4
1, the preparation of PUA emulsion
Except replacing PCL so that siloxanes segment is incorporated in polyurethane chain by PDMS part, and HEMA is reacted at 60 ℃ with aqueous polyurethane prepolymer and add DBTL with this reaction of catalysis, the Tert-butyl Methacrylate (t-BMA) that working strength is higher replaces vinylbenzene to do outside hard monomer, prepares PUA emulsion in the mode that embodiment 3 is identical according to the weight shown in table 8.In acrylate, the ratio of soft or hard monomer is adjusted into 4: 6 in this embodiment.
Table 8
2, the preparation of PUA redispersable latex powder
Selecting the polymerization degree is 1000, and the PVA that alcoholysis degree is 98% is mixed with 20% aqueous solution use; Inorganic anti-caking agent is selected talcum powder and silicon-dioxide; Mixed solution according to the weight shown in table 9 for the preparation of preparation PUA redispersable latex powder; Then, carry out dry nebulization in the mode identical with embodiment 3.
Table 9
Comparative example 1
Table 10
A, in the ratio in table 10, each Acrylic Acid Monomer is mixed for subsequent use; Then, by water, emulsifying agent, the disposable reactor joining with thermometer, whipping appts, balance dropping funnel of buffer reagent, mix;
B, then in reactor, add the acrylate monomer of 20wt%, stir after 30 minutes, it is distributed in water equably; Then heat to 80 ℃ of insulations approximately 30 minutes, until reactant becomes the blue seed emulsion that forms;
C, keep this temperature, in stratum nucleare seed emulsion, drip remaining monomer, control rate of addition, in 3.5 hours, dropwise, continue insulation and within 1 hour, form emulsion;
D, cool to room temperature gradually, filter with 100 order steel meshes, and discharging obtains the acrylic ester emulsion that solid content is 40wt%.
E, except selecting this emulsion, in all the other components situation identical with embodiment 1 with technique, prepare latex powder.
Pure acrylate emulsion and the latex powder performance of gained are shown in Table 14.The film-forming properties of pure-acrylic emulsion and film strength are poor compared with PUA; And latex powder redispersion is in water time, it is dispersed not as good as PUA latex powder, then water-intake rate after lactiferous film forming is also larger.
Comparative example 2
Table 11
Except reacting according to the compound of the weight shown in table 11, prepare PUA emulsion in the mode identical with embodiment 1 according to the weight shown in table 11, wherein, in step B, still use 10g acetone with dilution water based polyurethane prepolymer.As shown in table 11, the weight ratio of PU and acrylate part is 4: 6.After letex polymerization completes, find that there is a large amount of aggregates, stability of emulsion is poor, can not carry out the dry efflorescence of emulsion.
Comparative example 3
Table 12
The PCL that is 3000 except number-average molecular weight replaces the PCL in embodiment 1, prepares PUA emulsion in the mode identical with embodiment 1 according to the weight of the compound shown in table 12, finds hydration emulsification difficulty, cannot carry out letex polymerization.
Comparative example 4
Table 13
Except soft or hard monomer ratio is adjusted into 3: 7, prepare PUA emulsion in the mode identical with embodiment 1 according to the weight of the compound shown in table 13, wherein, in step B, still use 10g acetone with dilution water based polyurethane prepolymer, discovery polymerization completes in gained emulsion a large amount of aggregates, and letex polymerization is unstable.
Analytical test:
(1) a certain amount of PUA emulsion is placed in the mould of tetrafluoroethylene, at room temperature dry 3 days; Then the film of moulding is dried to one day again under the vacuum condition of 50 ℃, obtains the film that thickness is 0.2mm;
According to GB/T1402-92 standard, film thick 0.2mm is made to the dumbbell shape sample of standard, then use RGT-5KN type electronic tensile machine (Shenzhen Rui Geer Instrument Ltd.) to measure the tensile strength of film, draw speed is 50mm/min.
(2) emulsion minimum film-forming temperature (MFT):
QMB minimum film-forming temperature determinator (Tianjin material-testing machine factory) test obtains.
(3) rubber powder film-forming properties:
10 parts by weight of deionized water, add 5 weight part emulsion powders to stir and obtain dispersion liquid, and the thickness curtain coating on sheet glass by this dispersion liquid with 200 microns of builds, then at 50 ℃ of dry films that obtain for 6 hours.
Rank 1: the film that forms evenly and have certain toughness;
Rank 2: can film forming but poor toughness;
Rank 3: can not film forming;
(4) mensuration of regeneration emulsion film water-intake rate
A certain amount of regeneration emulsion is placed in the mould of tetrafluoroethylene, at room temperature dry 3 days; Then the film of moulding is dried to one day again under the vacuum condition of 50 ℃, obtains the film that thickness is 0.2mm;
Prepared film is cut into the sample that size is 0.2 × 4 × 4mm, and the distilled water that is placed in certain temperature soaks, and timing is taken out, and weighs after blotting film coated surface washmarking with filter paper, is calculated as follows the water-intake rate of film:
Water-intake rate=(m
1-m
0)/m
0× 100%
In formula: m
0for the weight after film constant weight;
M
1for the weight after film water suction 24h.
Gained emulsion and latex powder performance comparison in each example:
Table 14
Claims (7)
1. a water-based polyurethane-acrylate emulsion, it is prepared as follows:
The preparation of A, aqueous polyurethane prepolymer: will join in reactor through the polycaprolactone glycol of dehydration, heat up and drip wherein isocyanate reaction, then add hydrophilic chain extender, continue reaction;
The preparation of the aqueous polyurethane prepolymer of B, two key end-blockings: by the prepolymer mixed solution cooling of preparing in A step, dilute this prepolymer by acetone or acrylate part, then in described aqueous polyurethane prepolymer, add the end-blocking monomer that comprises hydroxyl and two keys to react;
C, ionomeric preparation: use in neutralizing agent and the aqueous polyurethane prepolymer of described pair of key end-blocking;
D, when use acetone diluted in step B time: under normal temperature, in described ionomer, add distilled water rapid dispersion, then acrylate part, initiator, buffer reagent joined in emulsion together, be dispersed into uniform emulsion; In the time diluting by acrylate part in step B: add distilled water rapid dispersion under normal temperature in described ionomer, then initiator, buffer reagent are joined in emulsion together, be dispersed into uniform emulsion;
E, containing the polymerization of the polyaminoester emulsion of acrylate part: join reaction kettle for reaction after 1 hour by 1/3 of the polyaminoester emulsion of preparing in step D, then drip remaining 2/3 emulsion and react;
F, rising temperature of reaction, continue reaction 1 hour;
Wherein, the number-average molecular weight of described polycaprolactone glycol is 500～2500, and the mol ratio R of the hydroxyl sum in isocyanate groups and described polycaprolactone glycol and end-blocking monomer is 1.2～1.8, and described acrylate part comprises hard monomer and soft monomer;
Wherein, described isocyanic ester is aliphatic isocyanates; Described hydrophilic chain extender is carboxylic acid type chainextender; The described end-blocking monomer that comprises hydroxyl and two keys is hydroxy alkyl ester; Described neutralizing agent is triethylamine; Degree of neutralization in described step C is 80～100%; Described initiator is selected from ammonium persulphate, Sodium Persulfate and Potassium Persulphate; Described buffer reagent is selected from sodium-acetate, sodium bicarbonate, Sodium phosphate dibasic and sodium sulfate; Described hard monomer is to be selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Tert-butyl Methacrylate and vinylbenzene; And soft monomer is for being selected from ethyl propenoate, one or more in the just own ester of n-butyl acrylate, vinylformic acid pentyl ester and propylene; Soft, hard monomer weight ratio is 5:5～6:4;
Wherein, described isocyanic ester is hexamethylene-diisocyanate, hydrogenation 4,4 '-diphenylmethanediisocyanate or isophorone diisocyanate; Described hydroxy alkyl ester is selected from methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester and vinylformic acid-5-hydroxyl pentyl ester; Described carboxylic acid type chainextender is selected from dimethylol propionic acid, amino acid or diaminobenzoic acid; Described initiator amount is 0.5～1.0% of acrylate part gross weight; Described buffer reagent consumption is acrylate part gross weight 0.2～0.5%.
2. water-based polyurethane-acrylate emulsion according to claim 1, wherein, the consumption of described carboxylic acid type chainextender is 5～10% of two key end-blocking aqueous polyurethane gross weights.
3. water-based polyurethane-acrylate emulsion according to claim 1 wherein, further adds polyether glycol, polyester polyol or polydimethylsiloxanediols diols in steps A; In steps A, add catalysts, this catalyzer is triethylenediamine, trolamine, dibutyl tin dilaurate or stannous octoate, and the consumption of catalyzer is 0.1～0.2% of urethane part gross weight.
4. water-based polyurethane-acrylate emulsion according to claim 3, wherein, described polyether glycol is polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran diol.
5. a latex powder, it obtains by the composition spray that comprises following component is dry:
Water-based polyurethane-acrylate emulsion in the claim 1～4 of 100 weight parts described in any one, its solid content is 40wt%;
Based on the described water-based polyurethane-acrylate emulsion of 100 weight parts, the inorganic coagulation-prevention agent of 4～8 weight parts;
Based on the described water-based polyurethane-acrylate emulsion of 100 weight parts, the PVA aqueous solution of 10～50 weight parts, wherein, the content of the PVA of the PVA aqueous solution is 20wt%;
Based on the described water-based polyurethane-acrylate emulsion of 100 weight parts, other auxiliary agent of 0.05～0.1 weight part;
Described inorganic coagulation-prevention agent is to be selected from one or more in calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder and kaolin; Described other auxiliary agent is defoamer or sterilant.
6. latex powder according to claim 5, wherein, the alcoholysis degree of described PVA is more than 90%, and the polymerization degree is 300～1200.
7. latex powder according to claim 6, it is to obtain by the spray method of employing rotary atomizer, the method comprises the steps:
The dry composition claimed in claim 5 of spraying;
After latex powder forms, separate through cyclonic separator, collect powder in tower exit with stainless steel storage tank;
Filter and obtain latex powder with 200 mesh filter screens;
Wherein, spray art condition is: atomizing wheel rotating speed 200～600r/min, and 100～120 ℃ of drying tower inlet temperature, drying tower temperature out is 60～80 ℃, input speed is 80～100mL.min
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| CN105237688A (en) * | 2015-10-30 | 2016-01-13 | 江门市珍图新材料有限公司 | Water dilution type polyester modified acrylic polyol resin |
| CN105237685A (en) * | 2015-10-30 | 2016-01-13 | 江门市珍图新材料有限公司 | Novel modified resin for manufacturing digital ink |
| CN109251274B (en) * | 2017-07-13 | 2021-03-02 | 和友纺织股份有限公司 | Method for preparing super-soft aqueous polyacrylate-urethane shell-core copolymer by solvent-free process |
| CN107286306B (en) * | 2017-07-25 | 2019-09-10 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
| CN109970935A (en) * | 2019-04-04 | 2019-07-05 | 北京材华科技有限公司 | A kind of preparation method of stimuli responsive type enhanced water resistance aqueous polyurethane emulsion |
| CN110003398B (en) * | 2019-04-28 | 2021-07-23 | 安徽匠星联创新材料科技有限公司 | Polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion |
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| CN101475679A (en) * | 2009-01-16 | 2009-07-08 | 中山大桥化工集团有限公司 | Aqueous polyurethane acrylate resin, and preparation and use thereof |
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