CN101033360A - Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion - Google Patents
Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion Download PDFInfo
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Abstract
The invention discloses a new method for manufacturing Interpenetrating Polymer Network of organic or inorganic reaction latex, which belongs to macromolecule manufacturing polymer synthesis. The emulsion has excellent storage stability. Its coating with a high pencil hardness, excellent scratch resistance, water-resistance, stain resistance, chemical resistance and aging resistance, can be used for wood, metal and surface decoration and construction exterior paint, The water emulsion polymer can be made through the following steps: (a) At least two unsaturated compounds, allyl monomer and inorganic nano particle are polymerized to the cross-linked structure seed emulsion. (b) The unsaturated compounds with reaction and allyl monomer are polymerized to core / shell structure emulsion on the basis of the seed emulsion. (c) In the core / shell structure emulsion, organic / inorganic hybrid with cross-linked structure semi-IPN emulsion can be got for adding cross-linker.
Description
[technical field]:
The present invention relates to a kind of preparation method of inorganic nano particle modified latex semi-intercrossing network; more specifically; relate to a kind of reactive half interpenetrating network structure acrylic ester emulsion composition; said composition can be used for the decoration of woodenware, metal, stone implement, plastics, glass, leather surface and anticorrosion; building inside and outside wall coating; fabric treating, the protection of cultural artifact surface etc. especially can be as the matrix resin of making water-borne wood coating.
[technical background]:
Traditional woodwork coating is generally solvent-borne type, from early stage phenolic paint, alkyd paint, the pyroxylin(e)finish polyurethane paint of consumption maximum up till now, all contain a large amount of volatile organic matters, in the production of coating and use, discharge a large amount of deleterious organic compound (VOC), not only poison operator, atmosphere pollution, slowly discharge but also can be penetrated in the porous timber, threaten human beings'health.As the improvement of solvent-borne type wood lacquer, aqueous woodware paint as main thinner, has significantly reduced the pollution of solvent based coating with water.Aqueous woodware paint can be divided into aqueous alkide resin, water-based Nitrocellulose, water-borne acrylic resin and waterborne polyurethane resin coating according to the resin composition.The exploitation of aqueous alkide resin type wood lacquer early, main application fields is to decorate, be to piece together with other base-material (as ACRYLIC EMULSION) to use as a rule, it is strong that it is coated with membrane permeability, do not need to use film coalescence aid, but its polymer chain is than facile hydrolysis, the weathering resistance of filming is relatively poor, have reaction between siccative and auxiliary agent, siccative is easily adsorbed by color stuffing, has reduced the rate of drying of filming.Water-based Nitrocellulose type has advantages such as dried soon, that the transparency is good, but its tack of filming is relatively poor, and decorative effect is bad, and weathering resistance is relatively poor, can not be used for the application of industrial woodenware.And water-and acrylate resin and waterborne polyurethane resin are two the most promising class water-base resins.Aqueous polyurethane lacquer film formation at low temp is good, good leveling property, fullness ratio height, anti-wear-resisting, good hand touch, chemical resistance and anti-after tackiness are excellent, but price is higher, has limited its application.And acrylate resin have fast dried, fast light, have excellent weather resistance and characteristics such as price is lower, and have respiratory, especially be fit to woodwork coating, so be widely used in the decoration priming paint and the finish paint of woodenware.But after traditional ACRYLIC EMULSION film forming, it is filmed is thermoplastic, shortcoming such as have water tolerance, anti-after tackiness and snappiness is relatively poor, hardness is lower.
Acid is the shortcoming of emulsion at aforesaid propylene, and people have developed inorganic nano particle modified acrylate resin on the one hand, inorganic particulate is introduced improved the performance of filming in the polymkeric substance, for example, picture CN1632015, CN1632011, CN1488684, CN1465633, as described in the CN1431234, at first prepare conventional emulsions, add inorganic nano-particle then, disperse to obtain inorganic nano particle modified emulsion by mechanical stirring, can be used for coating for internal and external wall.Because nanoparticle is reunited easily, and nanoparticle can not keep stable by electrostatic repulsion and hydration as latex particle.Therefore, by the nano modification emulsion that blend obtains, its stability is generally all not so good, and sedimentation and coacervation take place nanoparticle easily, the emulsion property variation, and the transparency of filming is also poor.People have developed latex interpenetrating net polymer resin and have improved the emulsion film energy on the other hand.Patent CA 1252241 has described a kind of method of the thermoplastic latex's of preparation interpenetrating net polymer.At first on the basis of seed emulsion, by semi-continuous emulsion polymerizing, obtain hydrophilic and have cancellated nuclear polymer with monomers such as vinylbenzene, butyl acrylate, vinylformic acid, allyl methyl acrylate; Be that polymerization single polymerization monomer carries out semi-continuous emulsion polymerizing and obtains hydrophobic and have cancellated shell polymeric with vinylbenzene, divinyl then, thereby obtain thermoplastic latex's interpenetrating(polymer)networks, have good light and heat stability and mechanical property.Patent U.S.P.5183859 has described a kind of preparation method of thermoplastic latex's interpenetrating net polymer, utilize the nuclear of the polymkeric substance of rubbery state as the latex interpenetrating(polymer)networks, polymkeric substance by the swelling rubbery state, carry out the shell of emulsion polymerization prepared vitreous state then, obtain the latex interpenetrating(polymer)networks, this latex interpenetrating net polymer has good processing flowability, can improve the erosion-resisting characteristics of resin with the resin melt blending.Patent U.S.P.6031045, CN1597739 are respectively seed with the polyether polyols with reduced unsaturation, and unsaturated monomers such as vinyl are obtained the latex interpenetrating(polymer)networks of polyurethane/acrylate hydridization by letex polymerization, have favorable mechanical performance and adhesive property.Patent CN1453304, CN1083504, CN1355267, CN1548462 etc. obtain the latex interpenetrating net polymer by preparing crosslinked nuclear polymer and crosslinked shell polymeric respectively, are used for fields such as coating and binding agent.Yet, above-mentioned latex interpenetrating net polymer resin, its cross-linked network only is confined in each latex particle scope, promptly tens in the hundreds of nanometer range, behind the emulsion film forming, it is filmed and is still thermoplasticly, and limited to the raising of interpenetrating(polymer)networks film performance, the hardness of coating, water tolerance, anti-after tackiness, chemical proof etc. are not ideal.In order to overcome the deficiency of prior art, the present invention has carried out a large amount of tests to acrylic ester emulsion, study in each side such as stability in storage, coating pencil hardness, water tolerance, print resistance, chemical resistance, resistance to deterioration and mechanical propertys, the present invention arises at the historic moment in this case.
[summary of the invention]:
The purpose of this invention is to provide a kind of inorganic nano particle modified reactive latex semi-interpenetrating network polymer resin, can form the full interpenetrating(polymer)networks coating of thermoset of hybrid behind its dried coating film.Described coating also has good anti-scratch performance, chemical-resistant, contamination resistance, ageing resistance and stability in storage etc. except possessing in demand performances such as high pencil hardness, excellent in water resistance and sticking power.
To achieve these goals, the invention provides a kind of acrylic acid series aqueous emulsion polymkeric substance, wherein contain: (one) a kind of inorganic nano particle modified reactive semi-intercrossing network emulsion polymer that obtains by following steps: will comprise the olefinic compounds that has two unsaturated groups in (a) molecule at least, (b) in a molecule, has the olefinic compounds of a unsaturated group, (c) inorganic nano-particle, (d) co-stabilizer and emulsifying agent obtain the nanometer particle-modified emulsion polymer I with crosslinking structure by the mini-emulsion polymerization method after utilizing the ultrasonic dispersing inorganic nano-particle; With emulsion polymer I as seed, on the basis of this emulsion with have (e) that unsaturated compound, (f) that crosslinking reaction at room temperature can take place at least aly have the unsaturated compound of carboxyl or anhydride group, (b) has a unsaturated group in a molecule olefinic compounds and emulsifying agent obtains crosslinkable semi-interpenetrating network structure emulsion polymkeric substance II under the inorganic nano particle modified room temperature by conventional emulsion polymerization; (2) a kind of water-soluble and the compound (g) of chemically crosslinked can at room temperature can take place with (e); (3) contain the mixture of a kind of additive or additive at least.
When preparation latex interpenetrating network polymer emulsion, normally adopt the multi-step emulsion polymerization method.At first add multi-functional compound and acrylate monomer by the crosslinked seed emulsion of emulsion polymerization prepared, promptly crosslinked nuclear polymer I; On the basis of this seed emulsion, add multi-functional compound and acrylate monomer again by the crosslinked shell polymeric of emulsion polymerization prepared, thereby obtain latex interpenetrating network polymer emulsion II.In the process of preparation shell polymeric, owing to the swelling of monomer to nuclear polymer, IPN can take place in nuclear polymer and shell polymeric on certain degree, forms inierpeneirating network structure.Yet on the one hand, because crosslinking structure only is confined in each latex particle scope, promptly tens in the hundreds of nanometer range; On the other hand, in the film process of latex particle, because latex particle is crosslinked reticulated structure, in when, between particle and the particle coalescence taking place, the diffusion hindered of molecular chain causes the degree of IPN limited, thereby it is thermoplastic that last coating is still, and the raising of coating performance is undesirable.
In brief, the outstanding feature of acrylic acid series aqueous emulsion polymkeric substance of the present invention is, when the preparation nuclear polymer is not to adopt conventional letex polymerization, but take inorganic nano-particle to have mini-emulsion polymerization down, utilize miniemulsion droplet nucleation principle to make the inorganic nano-particle outside be crosslinked netted polymer molecule coating; Do not add multi-functional cross-linking monomer copolymerization in preparation during shell polymeric, but monomer that can self-crosslinking when being added in film forming.Therefore be half interpenetrating network structure through the core/shell structure latex particle that obtains hybrid after the two step letex polymerizations, promptly nuclear polymer is the network molecule of crosslinking structure, and shell is the linear molecule of non-crosslinking structure.The latex particle biggest advantage of this structure is: because the inorganic nano-particle outside is coated by high molecular polymer and emulsifying agent molecule, can keep stable by electrostatic repulsion and hydration on the one hand, emulsion has excellent stability in storage; On the other hand in the process of emulsion film forming, the linear molecule of the network molecule of the crosslinking structure of nuclear polymer and shell non-crosslinked structure, and sufficient diffusion can take place between the molecular chain between particle and the particle, at first form a big semi-intercrossing network; Along with the volatilization of moisture and ammonia, crosslinking reaction takes place in the active group on the shell polymeric under the katalysis of carboxyl then, forms heat cured full interpenetrating(polymer)networks.These heat cured interpenetrating(polymer)networks have synergistic effect through whole coating in certain scope, make the pencil hardness of coating, and performances such as mechanical property are greatly improved; The most important thing is that inorganic nano-particle in the nuclear polymer fills phase as hard in filler, performances such as the pencil hardness of filming, anti-scratch property are greatly improved, filming simultaneously has the excellent transparency.The acrylic ester emulsion of this method preparation has that stability in storage is good, coating pencil hardness height, has water tolerance, advantages such as print resistance, chemical resistance, resistance to deterioration and good mechanical property.Practical application of the present invention is the acrylic acid series aqueous emulsion polymkeric substance to obtain, add therein and can be made into the coating that the thermoset latex interpenetrating(polymer)networks that can form hybrid under the room temperature are filmed after coatings additive(s) mixes, be applied in all respects such as woodwork coating building inside and outside wall coating.
To further introduce various components, reaction process and the reaction principle of acrylic acid series aqueous emulsion polymkeric substance of the present invention below.(1) raw material:
At least the olefinic compounds (a) that has two unsaturated groups in the above-mentioned molecule can be two (methyl) acrylate or three (methyl) acrylate and the alkene that contains two unsaturated double-bonds at least, and object lesson comprises: (alkoxide) cyclohexane dimethanol diacrylate, (alkoxide) hexanediyl ester, (alkoxide) bisphenol a diacrylate, diethylene glycol diacrylate, butylene glycol diacrylate, (alkoxide) neopentylglycol diacrylate, polyethyleneglycol diacrylate, the tetraethylene-glycol diacrylate, the Triethylene glycol diacrylate, (alkoxide) Viscoat 295, three (2-hydroxyethyl) isocyanuric acid triacrylate, pentaerythritol triacrylate, (alkoxide) glycerol triacrylate and fourth (penta) diene.It is monomeric 0.01%～20.0% that above-mentioned two (methyl) acrylate or three (methyl) acrylate or the amount of alkene that contains two unsaturated double-bonds at least preferably account for whole nuclear polymer, and more preferably 0.1%～10%.This be because, when two (methyl) acrylate or three (methyl) acrylate or the amount of alkene that contains two unsaturated double-bonds at least were lower than 0.01%, nuclear polymer network structure cross-linking density was little, coating performance is poor; When two (methyl) acrylate or three (methyl) acrylate amount were higher than 20%, nuclear polymer network structure cross-linking density was too big, and when emulsion film forming, molecular chain diffusion motion difficulty can not form inierpeneirating network structure, the film performance variation.
The olefinic compounds (b) that has a unsaturated group in the above-mentioned molecule can be (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) ethyl propenoate, (methyl) Hydroxyethyl acrylate, (methyl) glycidyl acrylate, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, (methyl) acrylamide, propenal, vinylchlorid, vinylidene chloride, vinyl pyridine, vinylbenzenesulfonic acid sodium, preferred at least two kinds of monomeric mixtures wherein.
The inorganic nano-particle of above-mentioned employing (c) can be wherein a kind of, two or more a composition of silicon-dioxide, aluminium sesquioxide, ferric oxide, Z 250, titanium oxide, polynite, lime carbonate, carbon pipe and mineral dye;
The co-stabilizer of above-mentioned employing (d) comprises long chain aliphatic alcohol, and its molecular structural formula is C
nH
2n+1OH (n=8～20), as cetyl alcohol, long chain alkane, its molecular structural formula is C
nH
2n+2(n=8～20), as n-Hexadecane, long-chain fat mercaptan, its molecular structural formula is C
nH
2n+1SH (n=8～20) is as Dodecyl Mercaptan, poly-(methyl) methyl acrylate, polystyrene and polyvinyl alcohol is wherein a kind of, two or more composition;
The above-mentioned unsaturated compound (e) that crosslinked group at room temperature can take place that has is characterized in that unsaturated compound (e) object lesson can be diacetone-acryloamide(DAA), (methyl) propenal, methyl vinyl ketone, (methyl) vinylformic acid acetoacetoxy groups ethyl ester, (methyl) vinylformic acid acetoacetyl amido ethyl ester.The above-mentioned amount that has the unsaturated compound (e) that crosslinked group at room temperature can take place preferably accounts for 0.5%～80.0% of whole amount of monomer, and more preferably 1.0%～40.0%.Be lower than 0.5%, the network structure cross-linking density of formation is low, poor performance such as the pencil hardness of coating and mechanical property; When being higher than 80.0%, emulsion polymerization systems possibility less stable has more gel and occurs; Because cross-linking set is too many, and it is more crisp to cause filming, coating performance does not reach service requirements simultaneously.
The above-mentioned unsaturated compound (f) that has carboxyl or anhydride group can be (methyl) vinylformic acid, MALEIC ANHYDRIDE, (methyl) tetrahydrophthalic anhydride.The above-mentioned unsaturated compound that has carboxyl or anhydride group preferably accounts for 0.1%～20.0% of whole amount of monomer.More preferably 0.2%～10%.Carboxyl can play the katalysis of crosslinking reaction in the process of emulsion film forming.Be lower than at 0.1% o'clock, katalysis is not obvious, and crosslinking reaction is slow; Be higher than at 20% o'clock, wetting ability strengthens the water tolerance deficiency because the introducing of too much carboxyl will cause filming.
Above-mentioned water-soluble and compound (g) that can chemically crosslinked at room temperature can take place with (e) is the binary soluble in water and the hydrazides of polycarboxylic acid, as carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, a few diacid two hydrazides, N (CH
2CH
2CONHNH
2)
3, H
2NHNCOCH
2CH
2)
2NCH
2CH
2N (CHCHCONHNH
2), the polynary hydrazides of polymkeric substance; Wherein said compound (g) also comprises water-soluble binary and polyamine, as quadrol, butanediamine, hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polymkeric substance polyamine.
Above-mentioned water-soluble and can that the compound (g) of chemically crosslinked and (e) monomeric equivalence ratio at room temperature can take place is preferred 0.3～2.0 with (e), more preferably 0.6～1.5.Equivalence ratio is lower than at 0.6 o'clock, and a large amount of (e) can not get crosslinked, and the cross-linking density of filming is low, and film performance is poor; Equivalence ratio is higher than at 1.5 o'clock, and the introducing of a large amount of hydrophilic compounds (g) in the coating descends the water tolerance of coating.
The polymerization technique that is used for preparing the aqueous emulsion polymkeric substance is well known in the art.In emulsion polymer preparation process of the present invention, wherein mini-emulsion polymerization and conventional emulsion polymerization can use common tensio-active agent, for example negatively charged ion or nonionic emulsifying agent, for example, alkyl, aryl, or alkaryl vitriolic alkali metal salts or ammonium salt, the alkali metal salts or ammonium salt of sulfonic acid or phosphoric acid; Alkylsulphonic acid; Sulfosuccinate; Lipid acid; The alcohol or the phenols of unsaturated tensio-active agent of olefinic and ethoxylation.In monomer weight, employed tensio-active agent is usually from 0.1～10%.
Can use conventional radical initiator, superoxide for example is as hydrogen peroxide, sodium peroxide, Potassium peroxide, tert-butyl peroxide, ammonium persulphate, persulfuric acid an alkali metal salt, Sodium peroxoborate, peroxophosphoric acid and salt thereof, potassium permanganate; An alkali metal salt of ammonium peroxydisulfate and peroxy-disulfuric acid thereof and azo-compound such as Diisopropyl azodicarboxylate.Can also use oxidation-reduction initiator, as using outside the above-mentioned oxygenant, described reductive agent is for example: sodium sulfoxylate formaldehyde, xitix, saccharosonic acid, vitriolated an alkali metal salt and ammonium salt are as S-WAT, sodium bisulfite, Sulfothiorine or sodium hyposulfate.Can use the redox reaction catalytic metal salt of iron, copper, manganese, silver, platinum, vanadium, nickel, cadmium, chromium or palladium.In total monomer weight, its common consumption is from 0.01～3.0%.
Can effectively use conventional buffer reagent when carrying out letex polymerization among the present invention, as yellow soda ash, sodium bicarbonate, sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic or their mixture.
Say that for example emulsion polymer I is preparation like this:
Inorganic nano-particle and polyfunctional monomer and simple function group monomer are mixed the back inorganic nano-particle of reuniting is dispersed into elementary nanoparticle with ultrasonic wave, ultrasonic dispersing again after the pre-then emulsification, obtain pre-emulsification nuclear polymer monomer, in the reactor that agitator, prolong and dropping funnel are housed, add above-mentioned pre-emulsification nuclear polymer monomer, stirring also is warmed up to 76 ℃, add initiator and carry out polyreaction, obtaining with the inorganic nano-particle is the emulsion polymer I with crosslinking structure of nuclear.
Say that for example emulsion polymer II is preparation like this:
To contain the shell mix monomer emulsification in advance that the crosslinking reaction compound can take place.In the reactor that agitator, prolong and dropping funnel are housed, add a certain amount of above-mentioned emulsion polymkeric substance I, be warmed up to 76 ℃, add the initiator initiated polymerization.Drip pre-emulsification shell polymeric monomer with certain speed and carry out letex polymerization, obtain emulsion polymer II, cooling is with ammoniacal liquor pH=7～9 that neutralize, add a certain amount of linking agent, obtain to form under the room temperature hybrid thermoset latex interpenetrating network polymer emulsion.
When preparation emulsion polymer II, can on the basis of above-mentioned emulsion polymkeric substance I, directly carry out letex polymerization, also can carry out letex polymerization in other reactor again being moved into behind the emulsion polymer I.
In order to obtain needed performance, pigment dyestuff, mineral dye and mill base that acrylic acid series aqueous emulsion polymkeric substance of the present invention can also add that people know and widely use are as titanium dioxide, zinc oxide, stibium trioxide, zinc sulfide white, lead-chrome yellow, iron oxide yellow, lead silicate, strontium calcium yellow, transparent yellow, diarylide yellow, Chinese sand yellow, lemon yellow, iron oxide red, red, chrome red, transparent red, phthalocyanine blue, ultramarine, carbon black, iron oxide black, graphite and versicolor mill base etc.
In order to obtain better practical effect, acrylic acid series aqueous emulsion polymkeric substance of the present invention at least also contains a kind of in the following additive, comprises metal inhibitor, mill base, wax slurry (powder), thickening material, defoamer, flow agent, sterilant, anti-settling agent, wetting agent and film coalescence aid.
Acrylic acid series aqueous emulsion fluoropolymer resin of the present invention can adopt modes such as roller coating, spraying, showering, dip-coating, brushing and scraper coating to be coated on substrate surfaces such as timber and obtain heat cured coating.
(2) chemical equation and reaction principle:
(1) crosslinking reaction
Above-mentioned reaction is to contain the acrylic ester emulsion of ketone carbonyl and the situation that has the compound generation crosslinking reaction of hydrazide group, this is reflected in the emulsion and can take place, at room temperature reach in the film forming process of acrylic ester emulsion, volatilization along with moisture and ammonia, under the katalysis of carboxyl, crosslinking reaction generation gradually forms heat cured emulsion coating.
(2) the hybrid thermoset latex interpenetrating(polymer)networks formation principle of filming:
By the mini-emulsion polymerization preparation is the nuclear emulsion polymer I with crosslinking structure of nuclear with the inorganic nano-particle, has cancellated molecule and is confined to belong to the micronetwork structure in each latex particle; On nuclear emulsion polymer basis, carry out conventional shell letex polymerization then, obtain the composite emulsion particle that shell has the core/shell structure of reactive group; In the process of emulsion film forming, along with the volatilization of moisture, latex particle is assembled and ordered arrangement, and latex particle is in contact with one another and is deformed into regular hexagon, along with the further volatilization of moisture, and under capillary force, latex particle generation coalescence.Because it is crosslinking structure that the composite emulsion particle of core/shell structure only has only the stratum nucleare polymkeric substance, the shell polymkeric substance is linear non-crosslinked structure, so latex particle inner nuclear layer crosslinking structure polymer molecular chain and shell polymer molecular chain, and between the particle polymer molecular chain be easy to spread, whole coating forms a big semi-intercrossing network; Meanwhile, along with the further volatilization of moisture and ammonia, coating system becomes acidity by alkalescence, and under the katalysis of carboxyl, ketone carbonyl and hydrazide group generation crosslinking reaction form the full interpenetrating(polymer)networks of huge thermoset and film.
(3) preparation of coating and performance test thereof:
Table 1 is to adopt the acrylic ester emulsion of the present invention's preparation as main component---resin, adds the example of resin additive and the prescription of Comparative Examples and forms table;
Table 2 is the The performance test results contrast tables that adopt coatings formulated of the present invention and several comparisons.
Table 1 example and comparative example prescription
| Form | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Emulsion | By 88 parts of embodiment 1 emulsions | By 88 parts of |
By 88 parts of embodiment 3 emulsions | By 88 parts of Comparative Examples 1 emulsions | By 88 parts of Comparative Examples 2 emulsions | By 88 parts of Comparative Examples 3 emulsions |
| Defoamer | 0.5 part | 0.5 part | 0.5 part | 0.5 part | 0.5 part | 0.5 part |
| Film coalescence aid | 1.2 part | 1.2 part | 1.2 part | 1.2 part | 1.2 part | 1.2 part |
| Wetting agent | 0.5 part | 0.5 part | 0.5 part | 0.5 part | 0.5 part | 0.5 part |
| Thickening material | 1.0 part | 1.0 part | 1.0 part | 1.0 part | 1.0 part | 1.0 part |
| Flow agent | 0.8 part | 0.8 part | 0.8 part | 0.8 part | 0.8 part | 0.8 part |
| Mould inhibitor | 0.3 part | 0.3 part | 0.3 part | 0.3 part | 0.3 part | 0.3 part |
| H 2O | 7.7 part | 7.7 part | 7.7 part | 7.7 part | 7.7 part | 7.7 part |
| Add up to | 100 parts | 100 parts | 100 parts | 100 parts | 100 parts | 100 parts |
In emulsion, add defoamer, film coalescence aid, ammoniacal liquor, thickening material, wetting agent, mould inhibitor, flow agent and defoamer under the high-speed stirring successively, high speed dispersion 30min, filter with 400 eye mesh screens, obtain inorganic nano particle modified thermoset latex interpenetrating(polymer)networks emulsion polymer.Get the tinplate of 120mm * 50mm * 0.2mm, earlier with 0
#The tin coating on tinplate surface is removed in sand papering, uses the acetone scrub again.Adopt dip-coating or brushing method to be uniformly coated on the tinplate dry at least one week under room temperature, about 25 microns of build the emulsion that obtains in the foregoing description and the comparative example.Coating hardness is according to national standard " coating hardness pencil assay method " GB/T 6739-1996 test, and scratching to film is standard; Sticking power is tested according to national standard " cross cut test of paint and varnish paint film " GB 9286-88; Water tolerance is tested according to national standard " paint film water tolerance assay method " GB/T 1733-93; Tensile strength is tested according to national standard " plastic tensile performance small sample experimental technique " GB/T16421-1996; Stability in storage is tested according to national standard " the new test method of coating storage-stable " GB 6753.3-86.The film performance test result is shown in Table 2.
Table 2 example and comparative example The performance test results
| Test item | Detected result | ||||||
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| Solid content (%) | 40 | 40 | 40 | 40 | 40 | 40 | |
| Sticking power/level | 0 | 0 | 0 | 1 | 1 | 1 | |
| Pencil hardness (galling) | 3H | 3H | 3H | 2B | B | HB | |
| Resistance to marring (100g) | Do not scratch | Do not scratch | Do not scratch | Serious damage | Scratch | Scratch | |
| Tensile strength (Pa) | 17.1 | 16.8 | 18.3 | 5.1 | 6.5 | 6.9 | |
| Water tolerance | Water tolerance (24h) | No abnormal | No abnormal | No abnormal | Bubble | The slight foaming | The slight foaming |
| Resistance to boiling water (15min) | No abnormal | No abnormal | No abnormal | Bubble | Bubble | Bubble | |
| Stain resistance | Vinegar (1h) | No abnormal | No abnormal | No abnormal | Bubble | The slight foaming | The slight foaming |
| Green tea (1h) | No abnormal | No abnormal | No abnormal | Bubble | The slight foaming | The slight foaming | |
| Coffee (1h) | No abnormal | No abnormal | No abnormal | Bubble | The slight foaming | The slight foaming | |
| Alkali resistance (50g/L NaHCO 3，1h) | No abnormal | No abnormal | No abnormal | Bubble | Bubble | Bubble | |
| Alcohol resistance (50%, 1h) | No abnormal | No abnormal | No abnormal | Be partly dissolved | Bubble | Bubble | |
| Stability in storage (50 ℃, 7d) | No abnormal | No abnormal | No abnormal | No abnormal | Precipitation | No abnormal | |
(4) advantage of the present invention:
(1) the present invention films by the thermoset interpenetrating(polymer)networks that form hybrid, solve that the hardness that thermoplastic propene's acid esters emulsion coating exists is low, water tolerance not enough and high temperature such as after-tacks at problem, the hardness of coating, anti-scratch property, water tolerance, chemical-resistant, weathering resistance, resistance to deterioration and mechanical property etc. are greatly improved.
(2) the prepared self-crossing emulsion of the present invention belongs to single-component package, and labour intensity is low; Crosslinking reaction can at room temperature be carried out smoothly, and energy consumption is low.
(3) the present invention has low cost, high performance competitive edge, produces three-waste free discharge, compliance with environmental protection requirements.
(4) applied range can be used for the decoration of woodenware, metal, stone implement, plastics, glass, leather surface and anticorrosion, building inside and outside wall coating, fabric treating, the protection of cultural artifact surface etc.Be particularly useful for the application on woodenware surface and anticorrosion.
(5) can realize large-scale industrialization production, satisfy the demand of relevant industries.
[description of drawings]:
Further set forth preparation method of the present invention below in conjunction with description of drawings and specific embodiments.
Accompanying drawing 1 mini-emulsion polymerization prepares emulsion polymer I principle.
The accompanying drawing 2 hybrid thermoset latex interpenetrating(polymer)networks formation principle of filming.
Accompanying drawing 3 is preparation method's process flow sheet of the present invention.
Wherein abbreviation is expressed as respectively: sodium lauryl sulphate (SDS); Triton X-100 (OP); Methyl methacrylate (MMA); Butyl acrylate (BA); 1,6 hexanediol diacrylate (HDDA); Methacrylic acid (MAA); Diacetone-acryloamide(DAA) (DAAM); Ammonium persulphate ((NH
4)
2S
2O
8).
Preparation technology's schema of accompanying drawing 4 aqueous woodware paints.
[specific embodiments]:
Embodiment 1:
With methyl methacrylate 21.6.g, butyl acrylate 23.4g, 1,6-hexanediyl ester 1.5g, nano silicon 5.0g, n-Hexadecane 1.5g mix, behind the ultra-sonic dispersion under high-speed stirring, be poured in the 120mL water that is dissolved with 0.49g sodium lauryl sulphate, 1.45g Triton X-100 and the agent of 0.15g sodium bicarbonate buffer, pre-emulsification 15min, and then ultra-sonic dispersion 30min, obtain pre-dispersed nuclear monomer.In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add above-mentioned pre-dispersed nuclear mix monomer, stirring at low speed, be warmed up to 76 ℃, add initiator ammonium persulfate 0.15g initiated polymerization, it is blue that the question response system becomes, and after monomers flow back disappears, continues reaction 2h and obtain emulsion polymer I.
Diacetone-acryloamide(DAA) 5.8g is dissolved in the mixing solutions of methyl methacrylate 28.5g, butyl acrylate 16.9g, vinylformic acid 1.2g, stir, be poured in the 20mL water that is dissolved with 0.263g sodium lauryl sulphate and 0.788g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.In above-mentioned emulsion polymkeric substance I, add initiator ammonium persulfate 0.15g initiated polymerization, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain emulsion polymer II, cooling, with the ammoniacal liquor pH=7.5 that neutralizes, add linking agent adipic dihydrazide 2.9g, obtain nanometer particle-modified crosslinkable semi-interpenetrating network polymer emulsion.
Embodiment 2:
With methyl methacrylate 21.6g, butyl acrylate 23.4g, 1,6-hexanediyl ester 1.5g, nano titanium oxide 5.0g, hexadecanol 1.5g mix, behind the ultra-sonic dispersion under high-speed stirring, be poured in the 120mL water that is dissolved with 0.49g sodium lauryl sulphate, 1.45g Triton X-100 and 0.15g buffer reagent sodium bicarbonate, pre-emulsification 15min, and then ultra-sonic dispersion 30min, obtain pre-dispersed nuclear monomer.In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add above-mentioned pre-dispersed nuclear monomer, stirring at low speed, be warmed up to 76 ℃, add initiator ammonium persulfate 0.1 5g initiated polymerization, it is blue that the question response system becomes, and after monomers flow back disappears, continues reaction 2h and obtain emulsion polymer I.
Diacetone-acryloamide(DAA) 6.5g is dissolved in the mixing solutions of methyl methacrylate 28.2g, butyl acrylate 16.5g, vinylformic acid 1.2g, stir, be poured in the 20mL water that is dissolved with 0.263g sodium lauryl sulphate and 0.778g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.In above-mentioned emulsion polymkeric substance I, add initiator ammonium persulfate 0.15g, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain emulsion polymer II, cooling, with the ammoniacal liquor pH=7.5 that neutralizes, add linking agent adipic dihydrazide 3.25g, obtain nanometer particle-modified crosslinkable semi-interpenetrating network polymer emulsion.
Embodiment 3:
Methyl methacrylate 21.6g, butyl acrylate 23.4g, Triethylene glycol diacrylate 1.5g, nano silicon 5.0g, n-Hexadecane 1.5g are mixed, behind the ultra-sonic dispersion under high-speed stirring, be poured in the 120mL water that is dissolved with 0.49g sodium lauryl sulphate, 1.45g Triton X-100 and 0.15g buffer reagent sodium bicarbonate, pre-emulsification 15min, and then ultra-sonic dispersion 30min, obtain pre-dispersed nuclear monomer.In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add above-mentioned pre-dispersed nuclear monomer, stirring at low speed, be warmed up to 76 ℃, add initiator ammonium persulfate 0.15g initiated polymerization, it is blue that the question response system becomes, and after monomers flow back disappears, continues reaction 2h and obtain emulsion polymer I.
Methacrylic acid acetoacetoxy groups ethyl ester 6.2 g are dissolved in the mixing solutions of methyl methacrylate 28.5g, butyl acrylate 16.5g, vinylformic acid 1.2g, stir, impouring is dissolved with in the 20mL water of 0.263g sodium lauryl sulphate and 0.778g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.In above-mentioned emulsion polymkeric substance I, add initiator ammonium persulfate 0.15g, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain emulsion polymer II, cooling, with the ammoniacal liquor pH=7.5 that neutralizes, add linking agent hexanediamine 1.6g, obtain nanometer particle-modified crosslinkable semi-interpenetrating network polymer emulsion.
Comparative Examples 1:
In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add anionic emulsifier sodium lauryl sulphate 0.49g, non-ionic emulsifier polyethylene glycol octyl phenyl ether 1.45g, buffer reagent sodium bicarbonate 0.15g and water 120mL, the heated and stirred dissolving.Methyl methacrylate 23.6g, butyl acrylate 26.4g are mixed, under high-speed stirring, the above-mentioned three mouthfuls of reactor high speeds of impouring are disperseed 15min, reduce stirring velocity to 300r/min, be warmed up to 76 ℃, add initiator ammonium persulfate 0.15g initiated polymerization, it is blue that the question response system becomes, after monomers flow back disappears, continue reaction 2h and obtain seeded emulsion polymerization thing I.
The mixing solutions of methyl methacrylate 31.6g, butyl acrylate 16.9g, vinylformic acid 1.2g is stirred, impouring is dissolved with in the 20mL water of 0.263g sodium lauryl sulphate and 0.778g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.Add initiator ammonium persulfate 0.15g in above-mentioned seeded emulsion polymerization thing, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain the shell structure emulsion polymerization thing, cooling with the ammoniacal liquor pH=7.5 that neutralizes, obtains the thermoplastic polymer emulsion.
Comparative Examples 2:
Methyl methacrylate 21.6.g, butyl acrylate 23.4g, nano silicon 5.0g are mixed, behind the ultra-sonic dispersion under high-speed stirring, be poured in the 120mL water that is dissolved with 0.49g sodium lauryl sulphate, 1.45g Triton X-100 and the agent of 0.15g sodium bicarbonate buffer, pre-emulsification 15min, and then ultra-sonic dispersion 30min, obtain pre-dispersed nuclear monomer.In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add above-mentioned pre-dispersed nuclear mix monomer, stirring at low speed, be warmed up to 76 ℃, add initiator ammonium persulfate 0.15g initiated polymerization, it is blue that the question response system becomes, and after monomers flow back disappears, continues reaction 2h and obtain emulsion polymer I.
The mixing solutions of methyl methacrylate 28.6g, butyl acrylate 20.2g, vinylformic acid 1.5g is stirred, impouring is dissolved with in the 20mL water of 0.263g sodium lauryl sulphate and 0.778g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.Add initiator ammonium persulfate 0.15g in above-mentioned emulsion polymkeric substance I, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain emulsion polymer II, cooling with the ammoniacal liquor pH=7.5 that neutralizes, obtains nanometer particle-modified polymer emulsion.
Comparative Examples 3:
Methyl methacrylate 21.6g, butyl acrylate 23.4g, Triethylene glycol diacrylate 1.5g, nano silicon 5.0g, n-Hexadecane 1.5g are mixed, behind the ultra-sonic dispersion under high-speed stirring, be poured in the 120mL water that is dissolved with 0.49g sodium lauryl sulphate, 1.45g Triton X-100 and 0.15g buffer reagent sodium bicarbonate, pre-emulsification 15min, and then ultra-sonic dispersion 30min, obtain pre-dispersed nuclear monomer.In three mouthfuls of reactors of the 500mL that mechanical stirrer, prolong and constant pressure funnel are housed, add above-mentioned pre-dispersed nuclear monomer, stirring at low speed, be warmed up to 76 ℃, add initiator ammonium persulfate 0.15g initiated polymerization, it is blue that the question response system becomes, and after monomers flow back disappears, continues reaction 2h and obtain emulsion polymer I.
Triethylene glycol diacrylate 1.5g is dissolved in the mixing solutions of methyl methacrylate 28.5g, butyl acrylate 16.5g, vinylformic acid 1.2g, stir, impouring is dissolved with in the 20mL water of 0.263g sodium lauryl sulphate and 0.778g Triton X-100, the pre-emulsification 15min of high speed dispersion obtains pre-emulsified shell monomer.In above-mentioned emulsion polymkeric substance I, add initiator ammonium persulfate 0.15g, drip pre-emulsified shell monomer, after monomer adds, continue reaction 1h and obtain emulsion polymer II, cooling with the ammoniacal liquor pH=7.5 that neutralizes, obtains nanometer particle-modified non-crosslinked interpenetrating network polymer emulsion.
Can find out significantly that from above detailed introduction those skilled in the art are not difficult the present invention is made some change and modification.Yet all that does not exceed the change of essence spirit of the present invention and revises the scope of the invention all be considered to belong to exclusive appended claims and limited.
Claims (10)
1. one kind at room temperature can form the aqueous composition that hybrid thermoset interpenetrating(polymer)networks film and comprises:
(1) can form the emulsion polymer of hybrid thermoset interpenetrating(polymer)networks coating under a kind of room temperature that obtains by following steps;
I will comprise the olefinic compounds that has two unsaturated groups in (a) molecule at least, (b) has a unsaturated group in a molecule olefinic compounds, (c) inorganic nano-particle and (d) co-stabilizer obtain the inorganic nano particle modified crosslinking structure emulsion polymer I that has by the mini-emulsion polymerization method;
Ii with emulsion polymer I as seed, on the basis of this emulsion with (e) have at least a olefinic compounds that has the unsaturated compound of carboxyl or anhydride group and (b) in a molecule, have a unsaturated group of unsaturated compound, (f) that the crosslinking reaction group at room temperature can take place and obtain the semi-interpenetrating network structure emulsion polymkeric substance II that shell has reactive group by conventional emulsion polymerization.
(2) a kind of water-soluble and the compound (g) of chemically crosslinked can at room temperature can take place with (e);
(3) contain the mixture of a kind of additive or additive at least.
2. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, the alkene that wherein said compound (a) is characterized in that being selected from two (methyl) acrylate or three (methyl) acrylate or contains two unsaturated double-bonds at least comprises (alkoxide) cyclohexane dimethanol diacrylate, (alkoxide) hexanediyl ester, (alkoxide) bisphenol a diacrylate, diethylene glycol diacrylate, butylene glycol diacrylate, (alkoxide) neopentylglycol diacrylate, polyethyleneglycol diacrylate, the tetraethylene-glycol diacrylate, the Triethylene glycol diacrylate, (alkoxide) Viscoat 295, three (2-hydroxyethyl) isocyanuric acid triacrylate, pentaerythritol triacrylate, wherein a kind of of (alkoxide) glycerol triacrylate and fourth (penta) diene, two or more composition.
3. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (b) is characterized in that being selected from (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) ethyl propenoate, (methyl) Hydroxyethyl acrylate, (methyl) glycidyl acrylate, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, (methyl) acrylamide, propenal, vinylchlorid, vinylidene chloride, vinyl pyridine, vinylbenzenesulfonic acid sodium a kind of, two or more composition wherein.
4. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (c) is characterized in that being selected from wherein a kind of, two or more composition of silicon-dioxide, aluminium sesquioxide, ferric oxide, Z 250, titanium oxide, polynite, lime carbonate, carbon pipe and mineral dye.
5. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (d) is characterized in that being selected from long chain aliphatic alcohol, and its molecular structural formula is C
nH
2n+1OH (n=8～20), long chain alkane, its molecular structural formula is C
nH
2n+2(n=8～20), long-chain fat mercaptan, its molecular structural formula are C
nH
2n+1SH (n=8～20), poly-(methyl) methyl acrylate, polystyrene, wherein a kind of, two or more composition of polyvinyl alcohol.
6. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (e) is characterized in that being selected from (methyl) propenal, methyl vinyl ketone, (methyl) vinylformic acid acetoacetoxy groups ethyl ester, diacetone-acryloamide(DAA), (methyl) vinylformic acid acetoacetyl amido ethyl ester a kind of, two or more composition wherein.
7. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (f) is characterized in that being selected from (methyl) vinylformic acid, MALEIC ANHYDRIDE, (methyl) tetrahydrophthalic anhydride a kind of, two or more composition wherein.
8. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said compound (g) is hydrazides and the binary and polyamine a kind of, two or more the composition wherein of water-soluble binary and polycarboxylic acid, it is characterized in that the hydrazides of water-soluble binary and polycarboxylic acid is selected from carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, N (CH
2CH
2CONHNH
2)
3, H
2NHNCOCH
2CH
2)
2NCH
2CH
2N (CHCHCONHNH
2) and the polynary hydrazides of polymkeric substance; Water-soluble binary and polyamine is characterized in that water-soluble binary and polyamine select in quadrol, hexanediamine, butanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and polymkeric substance polyamine.
9. according to the described acrylic acid series aqueous emulsion of claim 1 polymkeric substance, wherein said emulsion polymer II is characterized in that being selected from the half interpenetrating network structure that shell has reactive group, its nuclear is that emulsion polymer I is the polymkeric substance of nanometer particle-modified cross-linked structure, and its shell polymeric is the linear molecule non-crosslinked structure with reactive group.
10. according to the described acrylic acid series aqueous emulsion of claim 1 polymer composition, wherein also contain at least a following additive that is selected from: metal inhibitor, mill base, wax slurry, wax powder, thickening material, defoamer, flow agent, sterilant, anti-settling agent, wetting agent, film coalescence aid, mineral dye, pigment dyestuff, organic mill base or inorganic mill base.
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