CN102199239A - Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure - Google Patents
Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure Download PDFInfo
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Abstract
The invention provides a preparation method for an acrylic acid microemulsion with a self-crosslinking core-shell structure, which sequentially comprises the following steps of: emulsifying a seed microemulsion monomer in advance, preparing seed microemulsion and core-shell part microemulsion, emulsifying a core part microemulsion monomer in advance, and preparing the acrylic acid microemulsion with the self-crosslinking core-shell structure. In the preparation method for the acrylic acid microemulsion with the self-crosslinking core-shell structure, common self-crosslinking monomers are adopted for replacing expensive organo-siloxane monomers and fluoride-containing vinyl monomers, a polymerization technology is used for improving the performance of the emulsion, and therefore, the prepared acrylic acid microemulsion has low cost and can be widely used; the acrylic acid microemulsion with the self-crosslinking core-shell structure, prepared by the invention, has a soft-shell hard-core structure and a self-crosslinking characteristic; the average grain diameter of the microemulsion is 60-100nm; and the acrylic acid microemulsion with the self-crosslinking core-shell structure has good nanometer effects and good grinding performance when being used in aqueous woodware primers, and has advantages of good permeability and wettability to base materials, strong adhesive force, compactness in coating, good transparency, higher gloss and good smoothness.
Description
Technical field
The present invention relates to vinylformic acid microemulsion preparation method, relate in particular to a kind of vinylformic acid microemulsion preparation method of self-crosslinking nucleocapsid structure.
Background technology
The coating Water-borne modification is one of important directions of coating development.And the Water-borne modification of woodwork coating, on the one hand to go into overdrive to improve water-borne wood coating performance, dwindle the gap with the oiliness wood lacquer; Be the cost that will reduce water-borne wood coating on the other hand, only in this way just can make water-borne wood coating be easy to be accepted by consumers in general.
At present, because that ACRYLIC EMULSION and other water-borne coatingss are compared price with resin is lower and rate of drying is very fast, ACRYLIC EMULSION still particularly has a wide range of applications in aqueous wooden ware priming paint field at water-borne wood coating.But common ACRYLIC EMULSION is difficult to satisfy water-borne wood coating to such as hardness, water tolerance, and therefore the requirement of aspects such as anti-contamination need carry out modification to improve its performance to common ACRYLIC EMULSION.
Modified measures one is to adopt organosilane monomer or fluorinated vinyl monomer that ACRYLIC EMULSION is carried out modification.But the present price of these monomers is all very high, and the few performance of add-on improves the not obvious modification requirement that do not reach; Though the many performances of add-on can be significantly improved, the price increase rate also can be bigger, and cost performance again can variation.Therefore consider from the price angle, adopt organosilane monomer or fluorinated vinyl monomer that ACRYLIC EMULSION is carried out modification and also be difficult to promote at present at least.
Modified measures two is to utilize the self-crossing emulsion polymerization technique that ACRYLIC EMULSION is carried out modification.All there are certain problem in its water tolerance of thermoplastic ACRYLIC EMULSION, solvent resistance, thermotolerance etc.If when emulsion is synthetic, introduce and crosslinked monomer can take place under certain condition, in film process or film forming can produce to a certain degree crosslinked after for some time, have the performance of portion of hot thermosetting resin thereby making films, then can overcome above deficiency to a great extent.But owing to utilize the self-crosslinking technology that ACRYLIC EMULSION is carried out product that modification obtains is a liquid type, and the self-cross linking monomer add-on will certainly reduce performances such as the freeze-thaw stability of emulsion and stability in storage when big.Be subjected to the restriction of this respect, adopt the self-crosslinking technology that ACRYLIC EMULSION is carried out modification merely and be difficult to reach the ideal use properties.
Modified measures three is to utilize the advanced emulsion polymerization technology of monomer pre-emulsification technology, seeded emulsion polymerization technology and nuclear/comparisons such as shell emulsion polymerization technology that ACRYLIC EMULSION is carried out modification.Adopt the monomer pre-emulsification technology, emulsifying agent is not once to add when the reaction beginning, but except initial reaction stage adds partial emulsifier, in the reaction process afterwards along with pre-emulsion is brought a part again into, the emulsion particle reduced number that generates in the polymerization process can be made like this, therefore the emulsion particle distribution of sizes can be effectively controlled.Seeded emulsion polymerization is exactly to add entry, emulsifying agent, monomer, initiator etc. earlier in reactor to carry out letex polymerization, generates the emulsion particle that number is abundant, particle diameter is enough little, and such emulsion is called seed emulsion; Emulsion particle with seed emulsion is a core, proceeds polyreaction on its surface, and emulsion particle is constantly grown up.Adopt the seeded emulsion polymerization technology can effectively control latex particle size size and distribution thereof.The core/shell type polymer emulsion is compared with the common polymer emulsion with equal phase structure, significant superiority is arranged, as raising is in various degree all arranged at aspects such as rheological, minimum film-forming temperature, second-order transition temperature, tensile strength, shock strength, bonding strength, water tolerance, processibilities on performance.But only utilize the advanced emulsion polymerization technology of monomer pre-emulsification technology, seeded emulsion polymerization technology and nuclear/comparisons such as shell emulsion polymerization technology that ACRYLIC EMULSION is carried out modification, the synthetic emulsion still is thermoplastic in itself, therefore as solvent resistance, also there is deficiency in aspects such as hardness.
Modified measures four is to utilize the micro-emulsion polymerization technology to reduce the particle diameter of ACRYLIC EMULSION particle.The vinylformic acid microemulsion that adopts the micro-emulsion polymerization technology to obtain has following characteristics in the middle of being applied to aqueous wooden ware priming paint: (1) is good to perviousness, the wettability of base material, strong adhesion; (2) particle diameter is little, the densification of filming of formation, and filming, the transparency is good, gloss is higher, smoothness good; (3) molecular chain of micro-emulsion polymerization thing has higher conformational energy, and the shock resistance of filming, snappiness, hardness, wear resistance are good.But conventional synthetic microemulsion technology to use a large amount of emulsifying agents (greater than total inventory 10%), so just will certainly reduce water tolerance, so also limit in industrial application.The add-on that is reduced in emulsifying agent when synthesizing microemulsion is the key that the micro-emulsion polymerization technology is able to application.
Summary of the invention
At the problem that prior art exists, technical problem to be solved by this invention provides a kind of preparation method of ACRYLIC EMULSION of self-crosslinking nucleocapsid structure.
Technical scheme of the present invention is as follows: a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method may further comprise the steps:
Step 1, the monomeric pre-emulsification of seed microemulsion
With account for the emulsifying agent of vinyl monomer quality total amount 2～6%, the deionized water that accounts for the pH value buffer reagent of vinyl monomer quality total amount 0.5～3% and account for vinyl monomer quality total amount 30～90% mixed 3～20 minutes under 500～2000 rev/mins of agitation conditions; Under 2000～30000 rev/mins of emulsify at a high speed conditions, at the uniform velocity splash into the vinyl monomer that accounts for vinyl monomer quality total amount 5～40%, 10～60 minutes dropping time; Drip off the back and continued emulsify at a high speed 10～60 minutes, promptly get the monomeric pre-emulsion of seed microemulsion;
Step 2, preparation seed microemulsion
Letting nitrogen in and deoxidizing in the monomeric pre-emulsion of prepared seed microemulsion is warmed up to 65～90 ℃ then in step 1; Under 50～300 rev/mins of agitation conditions, add the initiator initiated polymerization that accounts for vinyl monomer quality total amount 0.02～1%, the polyreaction heat release finishes back insulation 10～60 minutes, obtains the seed microemulsion;
Step 3, preparation nuclear part microemulsion
Under 50～300 rev/mins of agitation conditions, in step 2, splash into the vinyl monomer that accounts for vinyl monomer quality total amount 30～45% in the obtained seed microemulsion, splash into the initiator that accounts for monomer vinyl monomer mass total amount 0.02～1% simultaneously, 1～5 hour dropping time; After dripping, insulation reaction 30～90 minutes; Add the initiator that accounts for vinyl monomer quality total amount 0.01～0.5% again, insulation reaction 0.5～5 hour obtains examining the part microemulsion;
Step 4, the monomeric pre-emulsification of shell part microemulsion
Get the emulsifying agent that accounts for vinyl monomer quality total amount 1～4% and account for vinyl monomer quality total amount 5～30% deionized waters and add in the emulsor, under 500～2000 rev/mins of agitation conditions, mixed 3～20 minutes; With account for the vinyl monomer of vinyl monomer quality total amount 20～60%, the alkyl acrylic that accounts for the self-crosslinking function monomer of vinyl monomer quality total amount 1～6% and account for vinyl monomer quality total amount 0.5～4% mixed 3～20 minutes under 50～300 rev/mins of agitation conditions; Under 2000～30000 rev/mins of emulsify at a high speed conditions, the vinyl monomer mixed solution is at the uniform velocity splashed in the emulsor 10～60 minutes dropping time; Drip off the back and continued emulsify at a high speed 10～60 minutes, promptly get the monomeric pre-emulsion of shell part microemulsion;
Step 5, preparation self-crosslinking nucleocapsid structure vinylformic acid microemulsion
Under 50～300 rev/mins of agitation conditions, the monomeric pre-emulsion of prepared shell part microemulsion in the step 4 is at the uniform velocity splashed in the step 3 in the prepared nuclear part microemulsion, splash into the initiator that accounts for vinyl monomer quality total amount 0.02～1% simultaneously, 1～5 hour dropping time; After dripping, insulation reaction 30～90 minutes; Add the initiator that accounts for vinyl monomer quality total amount 0.01～0.5% again; After dripping, be incubated 0.5～3 hour; Be added dropwise to remove behind the free vinyl monomer and remove reaction after initiator carries out, continue insulation 1～5 hour; Cooling is adjusted into 7～10 with pH value conditioning agent with the pH value, and pH value conditioning agent drips 10～40 minutes time; Above-mentioned product is filtered, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion;
Wherein, described self-crosslinking function monomer is 1～15 acrylate functional monomer for the alkyl carbon atoms number;
Wherein, described vinyl monomer is mixed by the material of following mass percent and gets: 10%～20% alkyl carbon atoms number is that 1～15 alkyl methacrylate, 10%～20% alkyl carbon atoms number are 1～15 alkyl acrylate and 10%～20% vinyl aromatic compound;
Wherein, the buffer reagent of pH value described in the described step 1 is a sodium bicarbonate;
Wherein, remove agent for to constitute behind the described vinyl monomer by 0.01～0.1% tertbutyl peroxide and 0.01～0.1% 2 hydration sodium bisulphite formaldehyde.
After with pH value conditioning agent the pH value being adjusted into 7～10 in the described step 5, can also splash into auxiliary self-crosslinking agent, auxiliary self-crosslinking agent drips 20～60 minutes time, drips off the back and continues to stir 10～30 minutes; Filter, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion; Wherein, described auxiliary self-crosslinking agent is 1～15 hydrazine class compound for the alkyl carbon atoms number.
Described auxiliary self-crosslinking agent is one or more in hexanodioic acid two hydrazines, carbonic acid two hydrazides, oxalic acid two hydrazides, the succinic acid hydrazide ii.
Described alkyl methacrylate is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the 2-EHA;
Described vinyl aromatic compound is one or more in vinylbenzene, vinyl toluene, 3-t-butyl styrene, the 2-chlorostyrene.
Described acrylate functional monomer is one or more in hydroxyethyl methylacrylate, Rocryl 410, N hydroxymethyl acrylamide, glycidyl methacrylate, diacetone-acryloamide(DAA), methylene diacrylamine, aminimide, the acrylamide glycolic acid esters.
Described alkyl acrylic is one or more in vinylformic acid, methacrylic acid or the methylene-succinic acid.
Described emulsifying agent is that 0.01～0.1% anionic emulsifier and 0.01～0.1% nonionic emulsifying agent carry out composite blending emulsifiers;
Wherein, used anionic emulsifier is selected from sodium lauryl sulphate, ammonium lauryl sulfate, sodium laurylsulfonate and the Sodium dodecylbenzene sulfonate one or more in the step 1; Used nonionic emulsifying agent is selected from one or more in the mixture, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene of alkylphenol polyoxyethylene in the step 1;
Wherein, used anionic emulsifier is selected from alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sodium sulfonate, tributyl phenol Soxylat A 25-7 sodium sulfonate, allyl polyethenoxy ether derivative ammonium sulfate and the allyl polyethenoxy ether ammonium sulfate one or more in the step 4; Used nonionic emulsifying agent is selected from one or more in alkyl polyoxyethylene ether phosphoric acid ester, tributyl phenol Soxylat A 25-7, alkyl polyoxyethylene ether, allyl polyethenoxy ether, the vinyl polyoxyethylene polyoxypropylene ether in the step 4.
Described initiator is a persulfuric acid salt initiator.
Remove agent for to constitute behind the vinyl monomer described in the described step 5 by 0.01～0.1% tertbutyl peroxide and 0.01～0.1% 2 hydration sodium bisulphite formaldehyde.
The described pH value of described step 5 conditioning agent is one or more the mixture in triethylamine, Isopropylamine, Tri N-Propyl Amine, n-Butyl Amine 99, dimethylamine, dimethyl amine, diethyl methylamine, dimethylethanolamine, trimethylammonium thanomin, amino methyl propyl alcohol, the ammoniacal liquor.
Wherein, the mixture of alkylphenol polyoxyethylene is called for short OP-10; Two hydration sodium bisulphite formaldehydes also are two water sodium formaldehyde sulphoxylate or rongalites; The amino methyl propyl alcohol is called for short AMP-95.
The present invention will combine with vinyl monomer pre-emulsification technology, seed and nuclear/shell emulsion polymerization technology, self-crossing emulsion polymerization technique and micro-emulsion polymerization technology, by adopting the pre-emulsification of seed microemulsion monomer, the nuclear partial monosomy directly drips and the pre-emulsification of shell partial monosomy, nuclear, shell part select for use different anions emulsifying agent and nonionic emulsifying agent to carry out composite unique technology respectively, effectively control emulsion particle diameter and emulsifying stability.Nuclear, the emulsifying agent that partly adopts of shell is to the requirement difference of aspect of performance, and the nuclear part emphasizes that the wetting ability of emulsifying agent and low micelle-forming concentration are so that the latex particle number that forms is abundant and enough little; Shell is partly emphasized the emulsifying property of emulsifying agent, and the pre-emulsion that obtains will be stablized.Make the self-crosslinking nucleocapsid structure vinylformic acid microemulsion of preparation by above technology, have tangible nucleocapsid structure and self-crosslinking characteristic, weight-average molecular weight is 13～150,000, and the molecular weight distribution degree is 2～2.5; Latex particle size is distributed in 40nm～120nm, and median size is 60～100nm; Nuclear segment glass temperature is 50～100 ℃, and shell segment glass temperature is 0～30 ℃.
The present invention effectively combines vinyl monomer pre-emulsification technology, seeded emulsion polymerization technology, nuclear/shell emulsion polymerization technology, self-crossing emulsion polymerization technique, micro-emulsion polymerization technology, adopt the pre-emulsification of monomer of seeded emulsion polymerization part, the monomer of nuclear letex polymerization part directly drips and the shell letex polymerization pre-emulsified technology of monomer partly, and in nuclear, shell emulsion polymerization process, select different initiator rate of addition respectively for use, and nuclear, shell select for use the anionic emulsifier of different performance and nonionic emulsifying agent composite, have effectively controlled emulsion particle diameter and distribution; In building-up process, do not produce or only produce under the situation of minute quantity gum deposit, make the synthetic middle emulsifying agent that adds of microemulsion account for below 6% of vinyl monomer total amount (accounting for below 3% of institute's synthetic emulsion total amount).
The present invention has following advantage:
(1), cheap, vinylformic acid microemulsion preparation method of the present invention adopts more common self-cross linking monomer to replace expensive organo-siloxane monomer and fluorine-containing vinyl monomer, utilize advanced polymerization technique to improve emulsion property, make the vinylformic acid microemulsion that makes cheap, can be widely used in the aqueous wooden ware priming paint;
(2), the freeze-thaw stability and the stability in storage of emulsion have been improved;
(3), synthetic emulsion right and wrong of the present invention are thermoplastic, physical and chemical performance such as its solvent resistance, water-fast, solvent resistance, thermotolerance, resistant all improves a lot;
(4), the emulsifying agent consumption is little, only accounts for below 6% of monomer total amount, accounts for below 3% of emulsion.
The vinylformic acid microemulsion of the present invention's preparation has soft shell stone structure, can add or not add the film forming auxiliary agent less in use, very environmental protection; The vinylformic acid microemulsion emulsion particle median size of the present invention's preparation is 60～100nm, has nano effect, and it is good to be used for aqueous wooden ware priming paint grinability, perviousness, wettability to base material are good, strong adhesion, the densification of filming, transparent good, gloss is higher, and smoothness is good.
Embodiment
For further understanding feature of the present invention, technique means and the specific purposes that reached, function, the invention will be further described and explanation below in conjunction with specific embodiment.
Embodiment 1
Select for use each component composition and content as shown in table 1 in this enforcement:
Table 1 embodiment 1 each component composition and contain scale
A kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method comprises the following steps of carrying out in order:
Step 1, the monomeric pre-emulsification of seed microemulsion
1.00g anionic emulsifier sodium laurylsulfonate and 0.50gOP-10,0.60gpH value damping fluid sodium bicarbonate and 32.45g deionized water are added in the emulsor, under 1000 rev/mins of agitation conditions, mixed 10 minutes; Get vinyl monomer, promptly the butyl acrylate of 2.40g methyl methacrylate, 1.50g vinylbenzene, 0.40g mixes, and at the uniform velocity splashes in the emulsor 30 minutes dropping time under 7500 rev/mins of emulsify at a high speed conditions; Drip off the back and continued emulsify at a high speed 30 minutes, obtain the monomeric pre-emulsion of seed microemulsion;
Step 2, preparation seed microemulsion
The monomeric pre-emulsion of the obtained seed microemulsion of step 1 is dropped in the reactor, under 150 rev/mins stirring velocity, be warmed up to 80 ℃; Logical nitrogen in reactor removes oxygen, after temperature reaches 80 ℃, is 10% disposable the joining in the system of persulfate aqueous solution with 0.60g concentration; After treating that blue light and exothermic peak end appear in emulsion, continue insulation 30 minutes, obtain the seed microemulsion;
Step 3, preparation nuclear part microemulsion
Get vinyl monomer, after promptly the butyl acrylate of the vinylbenzene of the methyl methacrylate of 9.76g, 6.10g, 1.57g mixes, under 150 rev/mins of agitation conditions, at the uniform velocity splash in the obtained seed microemulsion of step 2; Splash into 1.50g concentration simultaneously and be 10% persulfate aqueous solution; Be controlled in 3 hours and drip off; After dripping, insulation reaction 60 minutes; Disposable to add into containing 0.15g concentration be 10% persulfate aqueous solution, and insulation reaction 3 hours obtains examining the part microemulsion;
Step 4, the monomeric pre-emulsification of shell microemulsion
Get 1.00g concentration and be 50% alkyl polyoxyethylene acyl sodium sulfonate solution, 0.50g concentration and be 50% alkoxyl group polyoxyethylene ethereal solution and 14.35g deionized water and add in the emulsor, under 1000 rev/mins of agitation conditions, mixed 10 minutes; Get vinyl monomer, be that the methyl methacrylate of 3.84g, the vinylbenzene of 2.40g, butyl acrylate and self-crosslinking function monomer 0.80g hydroxyethyl methylacrylate, 1.20gN-n-methylolacrylamide and other function monomers 0.80g methacrylic acid of 9.23g mix, under 7500 rev/mins of emulsify at a high speed conditions, splash in the emulsor 30 minutes dropping time; Drip off the back and continued emulsify at a high speed 30 minutes, get the monomeric pre-emulsion of shell microemulsion;
Step 5, preparation self-crosslinking nucleocapsid structure vinylformic acid microemulsion
Under 150 rev/mins of agitation conditions, the monomeric pre-emulsion of step 4 gained shell part microemulsion is at the uniform velocity splashed in the step 3 gained nuclear part microemulsion, splash into 3.00g concentration simultaneously and be 10% persulfate aqueous solution, dripped off in 5 hours; After dripping, insulation reaction 1 hour; Add 0.15g concentration again and be 10% persulfate aqueous solution; Insulation reaction 1 hour; Cool to 70 ℃, be added dropwise to 0.50g concentration and be 10% the tertbutyl peroxide aqueous solution, 20 minutes dropping time, drip off back insulation 30 minutes, be added dropwise to 0.50g concentration again and be 10% rongalite (the two hydration sodium bisulphite formaldehydes) aqueous solution and remove reaction after carrying out, continued insulation reaction 2 hours; Treat that the vinyl monomer transformation efficiency reaches 98% when above, cooling is added dropwise to the pH value that the triethylamine aqueous solution of 2.60g10% is regulated product; Cool to room temperature and filter discharging, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion.
Embodiment 2
Select for use each component composition and content as shown in table 2 in this enforcement:
Table 2 embodiment 2 each component composition and contain scale
A kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method comprises the following steps of carrying out in order:
Step 1, the monomeric pre-emulsification of seed microemulsion add 1.20g anionic emulsifier sodium laurylsulfonate and 0.40g fatty alcohol-polyoxyethylene ether (AEO-7), 0.40gpH value damping fluid sodium bicarbonate and 27.11g deionized water in the emulsor, mix 5 minutes under 1200 rev/mins of agitation conditions; Get vinyl monomer, promptly the butyl acrylate of 1.38g methyl methacrylate, 1.50g vinylbenzene, 0.19g mixes, and at the uniform velocity splashes in the emulsor 20 minutes dropping time under 10000 rev/mins of emulsify at a high speed conditions; Drip off the back and continued emulsify at a high speed 20 minutes, obtain the monomeric pre-emulsion of seed microemulsion;
Step 2, preparation seed microemulsion
The monomeric pre-emulsion of the obtained seed microemulsion of step step 1 is dropped in the reactor, under 200 rev/mins stirring velocity, be warmed up to 70 ℃; Logical nitrogen in reactor removes oxygen, after temperature reaches 70 ℃, is 10% disposable the joining in the system of persulfate aqueous solution with 0.40g concentration; After treating that blue light and exothermic peak end appear in emulsion, continue insulation 20 minutes, obtain the seed microemulsion;
Step 3, preparation nuclear part microemulsion
Get vinyl monomer, after promptly the butyl acrylate of the vinylbenzene of the methyl methacrylate of 8.39g, 9.15g, 1.18g mixes, under 100 rev/mins of agitation conditions, at the uniform velocity splash in the obtained seed microemulsion of step 2; Splash into 1.00g concentration simultaneously and be 10% persulfate aqueous solution; Be controlled in 3 hours and drip off; After dripping, insulation reaction 60 minutes; Disposable adding into 0.10g concentration is 10% persulfate aqueous solution, and insulation reaction 3 hours obtains examining the part microemulsion;
Step 4, the monomeric pre-emulsification of shell microemulsion
Getting 1.20g concentration and be 50% alkyl polyoxyethylene acyl sodium sulfonate solution, 0.40g concentration is that 50% alkoxyl group polyoxyethylene ethereal solution and 18.64g deionized water add in the emulsor, mixes 5 minutes under 1200 rev/mins of agitation conditions; Get vinyl monomer, be that the butyl acrylate of vinylbenzene, 7.07g of methyl methacrylate, the 4.35g of 3.99g and self-crosslinking function monomer 1.20g diacetone-acryloamide(DAA) and other function monomers 1.20g methacrylic acid mix, under 10000 rev/mins of emulsify at a high speed conditions, splash in the emulsor 20 minutes dropping time; Drip off the back and continued emulsify at a high speed 20 minutes, get the monomeric pre-emulsion of shell microemulsion;
Step 5, preparation self-crosslinking nucleocapsid structure vinylformic acid microemulsion
Under 200 rev/mins of agitation conditions, the monomeric pre-emulsion of step 4 gained shell part microemulsion is at the uniform velocity splashed in the step 3 gained nuclear part microemulsion, splash into 2.00g concentration simultaneously and be 10% persulfate aqueous solution, dripped off in 4 hours; After dripping, insulation reaction 1 hour; Add 0.10g concentration again and be 10% persulfate aqueous solution; Insulation reaction 1 hour; Cool to 70 ℃, be added dropwise to 0.30g concentration and be 10% the tertbutyl peroxide aqueous solution, 20 minutes dropping time, dripping off back insulation, to be added dropwise to 0.30g concentration after 30 minutes be to remove reaction after the aqueous solution of 10% rongalite (two hydration sodium bisulphite formaldehydes) carries out, and continued insulation reaction 2 hours; Treat that the vinyl monomer transformation efficiency reaches 98% when above, cooling is added dropwise to 3.26g concentration and is the pH value that 10% ammonia aqueous solution is regulated product; Be added dropwise to 4.00g concentration and be the aqueous solution of 10% auxiliary self-crosslinking function monomer hexanodioic acid two hydrazines; Drip off back 250 rev/mins and stirred 30 minutes, filter discharging, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion.
Embodiment 3
Select for use each component composition and content as shown in table 3 in this enforcement:
Table 3 embodiment 3 each component composition and contain scale
A kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method comprises the following steps of carrying out in order:
Step 1, the monomeric pre-emulsification of seed microemulsion
0.80g anionic emulsifier ammonium lauryl sulfate and 0.80g nonionic emulsifying agent alkylphenol polyoxyethylene (TX-100), 0.60gpH damping fluid sodium bicarbonate and 30.59g deionized water are added in the emulsor, under 800 rev/mins of agitation conditions, mixed 15 minutes; Get vinyl monomer, promptly the butyl acrylate of 7.50g methyl methacrylate, 0.50g mixes, and at the uniform velocity splashes in the emulsor 20 minutes dropping time under 6000 rev/mins of emulsify at a high speed conditions; Drip off the back and continued emulsify at a high speed 40 minutes, obtain the monomeric pre-emulsion of seed microemulsion;
Step 2, preparation seed microemulsion
The monomeric pre-emulsion of the obtained seed microemulsion of step 1 is dropped in the reactor, under 300 rev/mins stirring velocity, be warmed up to 85 ℃; Logical nitrogen in reactor removes oxygen, after temperature reaches 85 ℃, is 10% disposable the joining in the system of ammonium persulfate aqueous solution with 0.33g concentration; After treating that blue light and exothermic peak end appear in emulsion, continue insulation 30 minutes, obtain the seed microemulsion;
Step 3, preparation nuclear part microemulsion
Get vinyl monomer, after promptly the butyl acrylate of the methyl methacrylate of 13.12g, 0.88g mixes, under 150 rev/mins of agitation conditions, at the uniform velocity splash in the obtained seed microemulsion of step 2; Splash into 2.50g concentration simultaneously and be 10% ammonium persulfate aqueous solution; Be controlled in 3 hours and drip off; After dripping, insulation reaction 60 minutes; Disposable adding into 0.17g concentration is 10% ammonium persulfate aqueous solution, and insulation reaction 3 hours obtains examining the part microemulsion;
Step 4, the monomeric pre-emulsification of shell microemulsion
Getting 0.80g concentration and be 50% alkyl polyoxyethylene acyl sodium sulfonate solution, 0.80gg concentration is that 50% alkoxyl group polyoxyethylene ethereal solution and 7.61g deionized water add in the emulsor, mixes 15 minutes under 800 rev/mins of agitation conditions; Get vinyl monomer, be that the butyl acrylate of methyl methacrylate, 10.50g of 5.50g and self-crosslinking function monomer 1.20g methylene diacrylamine and other function monomers 0.80g methacrylic acid mix, under 6000 rev/mins of emulsify at a high speed conditions, splash in the emulsor 20 minutes dropping time; Drip off the back and continued emulsify at a high speed 40 minutes, get the monomeric pre-emulsion of shell microemulsion;
Step 5, preparation self-crosslinking nucleocapsid structure vinylformic acid microemulsion
Under 200 rev/mins of agitation conditions, the monomeric pre-emulsion of step 4 gained shell part microemulsion is at the uniform velocity splashed in the step 3 gained nuclear part microemulsion, splash into 2.50g concentration simultaneously and be 10% the ammonium persulfate aqueous solution, dripped off in 5 hours; After dripping, insulation reaction 1 hour; Add 0.17g g concentration again and be 10% the ammonium persulfate aqueous solution; Insulation reaction 1 hour; Cool to 70 ℃, be added dropwise to 0.30g concentration and be 10% the tertbutyl peroxide aqueous solution, 20 minutes dropping time, dripping off back insulation, to be added dropwise to 0.30g concentration after 30 minutes be to remove reaction after the aqueous solution of 10% rongalite (two hydration sodium bisulphite formaldehydes) carries out, and continued insulation reaction 2 hours; Treat that the vinyl monomer transformation efficiency reaches 98% when above, be added dropwise to 7.40g concentration and be the pH value that 10% AMP-95 (amino methyl propyl alcohol) aqueous solution is regulated product; Be added dropwise to the aqueous solution of the auxiliary self-crosslinking function monomer succinic acid hydrazide ii of 4.00g10%; Drip off back 250 rev/mins and stirred 30 minutes, filter discharging, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion.
In order to further specify self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method of the present invention, the present invention detects the performance of the vinylformic acid microemulsion of embodiment 1,2 and 3 preparations, and detection method is as follows:
Emulsion solid content is with reference to the GB1725-79 standard;
The pH value uses the glass-calomel electrode pH meter of demarcating with buffered soln to measure;
The viscosity rotary viscosity design determining, the CPS of unit;
Mechanical stability: before the mensuration, earlier emulsion sample is filtered with 100 order filter clothes, in the special whipping appts of packing into then, stirred 10 minutes for 6096 meters/minute with slurry end line speed, and then filter, if gel-free with 100 order filter clothes, the emulsion good mechanical stability is described, judgement is passed through; If gel is arranged, the gel piece that leaches to be weighed after 105 ℃ of dryings, the dry state jello is many more, illustrates that the emulsion mechanical stability is poor more;
Freeze-thaw stability: 10 gram emulsion sample are placed 15 milliliters Plastic Bottle.Placing 2 hours in subzero 20 ℃ refrigerator, take out in room temperature and melted 6 hours, is a circulation, is that freeze-thaw stability is qualified by three circulations, and judgement is passed through;
Calcium ion stability: the calcium chloride solution of preparation 5%, mix with emulsion according to 1: 4 ratio, static 48 hours, if gel-free occurs, and there is not demixing phenomenon, then Calcium ion stability is qualified, and judgement is passed through;
Package stability: placed 7 days in 50 ℃ constant temperature oven, take out and be placed into the room temperature observation, if gel-free occurs, and do not have demixing phenomenon, then package stability is qualified, and judgement is passed through;
Dilution stability: by emulsion: water=mixed was even in 1: 10, placed 48 hours, not stratified, not breakdown of emulsion then dilution stability is qualified, judgement is passed through;
Minimum film-forming temperature uses the test of minimum film-forming temperature instrument;
Emulsion particle particle diameter and distribution are measured with Malvern AutoSizer LocFc963 laser light scattering particles distribution instrument;
Second-order transition temperature with the poor formula scanning calorimeter DSC mensuration of the anti-company of speeding of Germany, characterizes the nucleocapsid structure of emulsion with the different glass transition temperature of nuclear/shell;
Degree of crosslinking test behind the emulsion film forming: with 400 microns blade applicator knifing, placed 7 days under the room temperature, get filming of preparing about 2 grams, soaked 2 hours with acetone, taking out the back is dried to constant weight at 105 ℃, weighs, the per-cent of weight numerical value of filming before this numerical value and acetone soak is the degree of crosslinking behind the emulsion film forming, characterizes the self-crosslinking degree of emulsion with the degree of crosslinking behind the emulsion film forming;
The relative molecular mass of emulsion and molecular weight distribution earlier emulsion coagulation, are washed resulting polymers then, with the tetrahydrofuran (THF) dissolving, measure with gel chromatograph GPC again.
The vinylformic acid microemulsion test result of the various embodiments described above preparation is as shown in table 4.
The vinylformic acid microemulsion The performance test results of form 4 embodiment 1,2 and 3 preparations
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Solid content (%) | 43.3 | 42.6 | 43.5 |
| Emulsion particle median size (nm) and degree of distribution | 83.6/2.4 | 76.8/2.1 | 95.8/2.2 |
| PH value | 8.2 | 7.9 | 8.5 |
| Mechanical stability | By | By | By |
| Freeze-thaw stability | 3 cycle through | 3 cycle through | 3 cycle through |
| Calcium ion stability | By | By | By |
| Package stability | By | By | By |
| Dilution stability | By | By | By |
| Viscosity/CPS | 100 | 90 | 130 |
| Minimum film-forming temperature/℃ | 20.1 | 25.2 | 5.3 |
| The second-order transition temperature of nuclear and shell/℃ | Examine 95.2/ shell 22.5 | Examine 98.3/ shell 29.1 | Examine 96.1/ shell 2.5 |
| Degree of crosslinking/% behind the emulsion film forming | 50.3 | 60.0 | 40.8 |
| The average weight-molecular mass of emulsion and molecular weight distribution degree | 137326/2.43 | 146550/2.23 | 141250/2.48 |
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (10)
1. a self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method is characterized in that, may further comprise the steps:
Step 1, the monomeric pre-emulsification of seed microemulsion
With account for the emulsifying agent of vinyl monomer quality total amount 2～6%, the deionized water that accounts for the pH value buffer reagent of vinyl monomer quality total amount 0.5～3% and account for vinyl monomer quality total amount 30～90% mixed 3～20 minutes under 500～2000 rev/mins of agitation conditions; Under 2000～30000 rev/mins of emulsify at a high speed conditions, at the uniform velocity splash into the vinyl monomer that accounts for vinyl monomer quality total amount 5～40%, 10～60 minutes dropping time; Drip off the back and continued emulsify at a high speed 10～60 minutes, promptly get the monomeric pre-emulsion of seed microemulsion;
Step 2, preparation seed microemulsion
Letting nitrogen in and deoxidizing in the monomeric pre-emulsion of prepared seed microemulsion is warmed up to 65～90 ℃ then in step 1; Under 50～300 rev/mins of agitation conditions, add the initiator initiated polymerization that accounts for vinyl monomer quality total amount 0.02～1%, the polyreaction heat release finishes back insulation 10～60 minutes, obtains the seed microemulsion;
Step 3, preparation nuclear part microemulsion
Under 50～300 rev/mins of agitation conditions, in step 2, splash into the vinyl monomer that accounts for vinyl monomer quality total amount 30～45% in the obtained seed microemulsion, splash into the initiator that accounts for monomer vinyl monomer mass total amount 0.02～1% simultaneously, 1～5 hour dropping time; After dripping, insulation reaction 30～90 minutes; Add the initiator that accounts for vinyl monomer quality total amount 0.01～0.5% again, insulation reaction 0.5～5 hour obtains examining the part microemulsion;
Step 4, the monomeric pre-emulsification of shell part microemulsion
Get the emulsifying agent that accounts for vinyl monomer quality total amount 1～4% and account for vinyl monomer quality total amount 5～30% deionized waters and add in the emulsor, under 500～2000 rev/mins of agitation conditions, mixed 3～20 minutes; With account for the vinyl monomer of vinyl monomer quality total amount 20～60%, the alkyl acrylic that accounts for the self-crosslinking function monomer of vinyl monomer quality total amount 1～6% and account for vinyl monomer quality total amount 0.5～4% mixed 3～20 minutes under 50～300 rev/mins of agitation conditions; Under 2000～30000 rev/mins of emulsify at a high speed conditions, the vinyl monomer mixed solution is at the uniform velocity splashed in the emulsor 10～60 minutes dropping time; Drip off the back and continued emulsify at a high speed 10～60 minutes, promptly get the monomeric pre-emulsion of shell part microemulsion;
Step 5, preparation self-crosslinking nucleocapsid structure vinylformic acid microemulsion
Under 50～300 rev/mins of agitation conditions, the monomeric pre-emulsion of prepared shell part microemulsion in the step 4 is at the uniform velocity splashed in the step 3 in the prepared nuclear part microemulsion, splash into the initiator that accounts for vinyl monomer quality total amount 0.02～1% simultaneously, 1～5 hour dropping time; After dripping, insulation reaction 30～90 minutes; Add the initiator that accounts for vinyl monomer quality total amount 0.01～0.5% again; After dripping, be incubated 0.5～3 hour; Be added dropwise to remove behind the free vinyl monomer and remove reaction after initiator carries out, continue insulation 1～5 hour; Cooling is adjusted into 7～10 with pH value conditioning agent with the pH value, and pH value conditioning agent drips 10～40 minutes time; Above-mentioned product is filtered, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion;
Wherein, described self-crosslinking function monomer is 1～15 acrylate functional monomer for the alkyl carbon atoms number;
Wherein, described vinyl monomer is that 1～15 alkyl methacrylate, alkyl carbon atoms number are that 1～15 alkyl acrylate and one or more mixing in the vinyl aromatic compound get by the alkyl carbon atoms number;
Wherein, the buffer reagent of pH value described in the described step 1 is a sodium bicarbonate;
Wherein, remove initiator for to constitute behind the described vinyl monomer by 0.01～0.1% tertbutyl peroxide and 0.01～0.1% 2 hydration sodium bisulphite formaldehyde.
2. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1, it is characterized in that, after with pH value conditioning agent the pH value being adjusted into 7～10 in the described step 5, can also splash into auxiliary self-crosslinking agent, auxiliary self-crosslinking agent drips 20～60 minutes time, drips off the back and continues to stir 10～30 minutes; Filter, promptly obtain self-crosslinking nucleocapsid structure vinylformic acid microemulsion; Wherein, described auxiliary self-crosslinking agent is 1～15 hydrazine class compound for the alkyl carbon atoms number.
3. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 2 is characterized in that described auxiliary self-crosslinking agent is one or more in hexanodioic acid two hydrazines, carbonic acid two hydrazides, oxalic acid two hydrazides, the succinic acid hydrazide ii.
4. a kind of according to claim 1 self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method, it is characterized in that described alkyl methacrylate is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, the Isooctyl methacrylate;
Described alkyl acrylate is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the 2-EHA;
Described vinyl aromatic compound is one or more in vinylbenzene, vinyl toluene, 3-t-butyl styrene, the 2-chlorostyrene.
5. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1, it is characterized in that described acrylate functional monomer is one or more in hydroxyethyl methylacrylate, Rocryl 410, N hydroxymethyl acrylamide, glycidyl methacrylate, diacetone-acryloamide(DAA), methylene diacrylamine, aminimide, the acrylamide glycolic acid esters.
6. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1 is characterized in that described alkyl acrylic is one or more in vinylformic acid, methacrylic acid or the methylene-succinic acid.
7. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1 is characterized in that, described emulsifying agent is that 0.01～0.1% anionic emulsifier and 0.01～0.1% nonionic emulsifying agent carry out composite blending emulsifiers;
Wherein, used anionic emulsifier is selected from sodium lauryl sulphate, ammonium lauryl sulfate, sodium laurylsulfonate and the Sodium dodecylbenzene sulfonate one or more in the step 1; Used nonionic emulsifying agent is selected from one or more in the mixture, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene of alkylphenol polyoxyethylene in the step 1;
Wherein, used anionic emulsifier is selected from alkyl diphenyl ether disodium sulfonate salt, alkyl polyoxyethylene acyl sodium sulfonate, tributyl phenol Soxylat A 25-7 sodium sulfonate, allyl polyethenoxy ether derivative ammonium sulfate and the allyl polyethenoxy ether ammonium sulfate one or more in the step 4; Used nonionic emulsifying agent is selected from one or more in alkyl polyoxyethylene ether phosphoric acid ester, tributyl phenol Soxylat A 25-7, alkyl polyoxyethylene ether, allyl polyethenoxy ether, the vinyl polyoxyethylene polyoxypropylene ether in the step 4.
8. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1 is characterized in that described initiator is a persulfuric acid salt initiator.
9. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1, it is characterized in that, remove initiator for to constitute behind the vinyl monomer described in the described step 5 by 0.01～0.1% tertbutyl peroxide and 0.01～0.1% 2 hydration sodium bisulphite formaldehyde.
10. a kind of self-crosslinking nucleocapsid structure vinylformic acid preparation of microemulsion method as claimed in claim 1, it is characterized in that the described pH value of described step 5 conditioning agent is one or more the mixture in triethylamine, Isopropylamine, Tri N-Propyl Amine, n-Butyl Amine 99, dimethylamine, dimethyl amine, diethyl methylamine, dimethylethanolamine, trimethylammonium thanomin, amino methyl propyl alcohol, the ammoniacal liquor.
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