CN1546544A - Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method - Google Patents
Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method Download PDFInfo
- Publication number
- CN1546544A CN1546544A CNA2003101168020A CN200310116802A CN1546544A CN 1546544 A CN1546544 A CN 1546544A CN A2003101168020 A CNA2003101168020 A CN A2003101168020A CN 200310116802 A CN200310116802 A CN 200310116802A CN 1546544 A CN1546544 A CN 1546544A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- synolac
- ester
- preparation
- vinyl monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 34
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 33
- 150000002148 esters Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 31
- 239000004816 latex Substances 0.000 title abstract description 7
- 229920000126 latex Polymers 0.000 title abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000839 emulsion Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- -1 C 10Alcohol ester Chemical class 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 235000019394 potassium persulphate Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 229960000541 cetyl alcohol Drugs 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 229920000180 alkyd Polymers 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 230000003028 elevating effect Effects 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000012703 microemulsion polymerization Methods 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000002464 physical blending Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229940040145 liniment Drugs 0.000 description 1
- 239000000865 liniment Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a process for preparing alcohol acid-polyacrylic acid (ester) hybrid latex by using alkyd resin and vinyl monomer as primary material through the steps of, (1) charging emulsifying agent, water-soluble initiating agent and catalyst into deionized water till complete dissolution, charging vinyl monomer, agitating to obtain pre-emulsion, (2) charging emulsifier and water-soluble initiating agent into deionized water, after complete dissolution, letting in nitrogen 20 minutes, elevating the temperature to 75-85 deg. C, dropping pre-emulsion continuously for 2-5 hours, after finishing the dropping, elevating the temperature to 90-100 deg. C, for continuous reaction of 2-5 hours.
Description
Technical field
The present invention relates to the preparation method of a kind of alkyd-polyacrylic acid (ester) hybridisation emulsion.
Background technology
At present, save energy, exploit natural resources, reduce the task of top priority that pollution has become industrial development.Be determined to win with water milk type coating replace organic solvent type coating.But water milk type coating now has more shortcoming, has limited its all-round popularization and application.To fundamentally improve the film forming situation and the film properties of water milk type coating, just the polymer emulsion that can not form with different chemical simply carries out composite (physical blending), effective means should be synthetic aqueous polymer dispersion with specific function group the most, perhaps by suitable synthesis technique, preparation is formed similar and water miscible liquid (as core-shell emulsion, emulsion interpenetrating polymer networks etc.) that the emulsion particle morphological structure is special to existing water miscible liquid.Alkide resin emulsion has advantages such as good film-forming property, high gloss, but its dried coating film is slow, and hardness is low.And polyacrylic acid (ester) emulsion has soon the advantage of the not yellowing of doing, film, but film chemical proof and water tolerance are relatively poor.If with the two combination, utilize the physics quick-drying and the Synolac autoxidation of polyacrylic acid (ester) emulsion to solidify combination, can reduce negative impact separately, make in conjunction with after the rate of doing of filming be better than Synolac, water tolerance and chemical proof are better than polyacrylic acid (ester) emulsion.
Method of modifying commonly used is alkide resin emulsion and polyacrylic acid (ester) emulsion physical blending, but poor effect.After reason was such blend, the uniformity of emulsion was poor.This is because the mixture of alkide resin emulsion and polyacrylic acid (ester) emulsion, similar with the polyacrylic acid with the high Tg of low Tg/ (ester) composite emulsion, after the film forming, the polyacrylic acid of high Tg (ester) particle is embedded in during also not oxidation cross-linked soft Synolac films, and the uniformity of filming is poor.
If in the presence of Synolac, polymerization by Acrylic Acid Monomer, make the good hybridisation emulsion of uniformity, the film performance of gained emulsion should be better than single alkide resin emulsion or polyacrylic acid (ester) emulsion, also is better than the physical blending body of alkide resin emulsion and polyacrylic acid (ester) emulsion.Alkyd-polyacrylic acid (ester) hybridisation emulsion, under the ideal situation, Synolac and polyacrylic acid (ester) molecular chain is to be dispersed in each emulsion particle in the hybridisation emulsion, so after the solvent evaporates film forming, polyacrylic acid (ester) is that the form with chain molecule is evenly dispersed in during also not oxidation cross-linked soft Synolac films.But, because emulsion with the ordinary method preparation, the polyacrylic acid that when emulsion polymerization, generates (ester) may not necessarily with the Synolac intimate mixing, so, in polyreaction, have the trend that is separated by the particle of acrylic acid polymer generation and the particle that generates by Synolac, and can not reach gratifying film performance.The general method that addresses this problem is: because Synolac and polyacrylic acid (ester) consistency are poor, when the preparation hybridisation emulsion, if can add the organic solvent, softening agent of excessive membrane-forming agent and so on etc., polyacrylic acid of generation (ester) and Synolac just can form the latex particle that homogenizes.But there is shortcoming in this method: use excessive outer adding assistant can cause the emulsion system instability, very difficult practical application of paying, so improve Synolac and polyacrylic acid (ester) consistency with outer adding assistant merely, can not satisfy application need, the expectation of current maximum is exactly to improve production technology---promptly solve the homogeneous problem (uniform distribution of two kinds of polymkeric substance and consistency) of emulsion and emulsion particle.
Summary of the invention
The invention provides the preparation method of a kind of alkyd-polyacrylic acid (ester) hybridisation emulsion.
The preparation method of a kind of alkyd-polyacrylic acid of the present invention (ester) hybridisation emulsion is a major ingredient with Synolac and vinyl monomer, Synolac and vinyl monomer weight ratio be 2～50: 98～50, be preferably 10～35: 90～65.Preparation process may further comprise the steps successively:
(1), pre-emulsification: emulsifying agent, water soluble starter and catalyzer are put in the deionized water, after treating to dissolve fully, are added the vinyl monomer that is dissolved with Synolac, oil-soluble initiator and auxiliary agent and mixes, stir pre-emulsion;
(2), polyreaction: emulsifying agent and water soluble starter are put in the deionized water, after the dissolving, led to nitrogen 20 minutes fully, be warmed up to 75～85 ℃, dripped pre-emulsion continuously 2～5 hours, after being added dropwise to complete, be warming up to 90～100 ℃, continue reaction 2～8 hours.
The air-drying property Synolac with unsaturated link(age) of Synolac for adopting siccative oil or semi-drying oil to make, its acid number be less than 10mgKOH/g, oil content 30-85%.Its preparation can be adopted following ordinary method: in turn behenic acid, glycerine, tetramethylolmethane, Tetra hydro Phthalic anhydride, band aqua (dimethylbenzene) etc. are put in the reaction flask by measuring requirement.Logical carbon dioxide, heating be the control heat-up rate also, 205～210 ℃ of insulations, up to viscosity and acid number detect meet the requirements after, pressure reducing and steaming band aqua (dimethylbenzene).
Polyreaction is undertaken by micro-emulsion polymerization mechanism.Used vinyl monomer is methacrylic acid and C thereof
1～C
10Alcohol ester, vinylformic acid and C thereof
1～C
10In alcohol ester or the vinylbenzene one or more.
Emulsifying agent is the moon/nonionic compound emulsifier, and the ratio of the moon/nonionic emulsifying agent is 1: 0.5～3, and consumption is 0.8～5% (reasonable opinion solid content weight percent), and wherein the consumption of pre-emulsion process is 1/5～4/5 of whole consumptions.
Preferred, emulsifying agent is 2～4 kinds in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, polyoxyethylene nonyl phenyl Vinyl Ether, ethoxylated alkylphenol ammonium sulfate, the octylphenol polyethylene ethylene oxide ether.
Water soluble starter is one or both of Potassium Persulphate, ammonium persulphate; Oil-soluble initiator is one or both in benzoyl peroxide, the Diisopropyl azodicarboxylate, the total consumption of initiator is 0.5～2% (accounting for the weight percent of vinyl monomer), wherein oil-soluble initiator accounts for 0～50% of total consumption, and the consumption of pre-emulsion process is 1/5～4/5 of whole consumptions.
Auxiliary agent is one or more in n-Hexadecane, cetyl alcohol, 1-amylalcohol, the polymethyl acrylate, and the total consumption of auxiliary agent is 0～5% (accounting for the polymerization single polymerization monomer weight percent).
Outstanding feature of the present invention is: (1) has consistency preferably for making Synolac and polyacrylic acid (ester), just needs to introduce unsaturated link(age) in the alkyd molecular chain, that is to say and will make the air-drying property Synolac with siccative oil or semi-drying oil.This on the one hand, when vinyl monomer generation Raolical polymerizable, just can with the air-drying property Synolac generation in-situ grafting polymerization that contains unsaturated link(age), Synolac-g-polyacrylic acid (ester) the graft copolymerization deposits yields of some amount is arranged.Graft copolymer is as compatilizer, thereby can improve the consistency of Synolac and vinyl polymer.On the other hand, the Synolac in the hybridisation emulsion is the unsaturated link(age) of remaining some amount still, film form after, Synolac is through oxidation cross-linked and make to film and have half-inierpeneirating network structure, thereby improves the performance of filming, and remedies the weak point of water-borne coatings.(2) the micro-emulsion polymerization technology is adopted in the preparation of alkyd-polyacrylic acid (ester) hybridisation emulsion, has reduced the diffusive migration of vinyl monomer in polymerization process to greatest extent, thereby polyreaction is occurred in the specific polymerization place (drop).Like this, because the generation of Synolac-g-polyacrylic acid (ester) graft copolymer in specific polymerization place and the polymerization process, can obtain Synolac and vinyl polymer intimate mixing and consistency latex particle preferably, therefore, emulsion has fabulous stably dispersing performance.In a word, adopt the technology of the present invention to prepare alkyd-polyacrylic acid (ester) hybridisation emulsion, in polyreaction, do not have Synolac latex particle and the isolating problem of vinyl polymer latex particle, also do not have the uneven problem of emulsion system.
The air-drying property Synolac is not done any structural modification, directly presses micro-emulsion polymerization mechanism, it is carried out modification with polyacrylic acid (ester), and reach Water-borne modification (hybridisation emulsion), and obtaining having the aqueous coating emulsion of premium properties, this is a kind of economy, the method for modifying of Synolac efficiently.Compare with polyacrylic acid (ester) emulsion film with single alkide resin emulsion, alkyd-polyacrylic acid (ester) hybridisation emulsion of the present invention's preparation is with the two combination, utilize the physics quick-drying and the Synolac autoxidation of polyacrylic acid emulsion to solidify combination, can make the high-performance that is better than single latex films, make in conjunction with after emulsion film do rate and be better than Synolac, water tolerance and chemical proof are better than polyacrylic acid (ester) emulsion, as metal, the carpenter, leather, the liniment of goods such as plastics is extremely useful, and expection will have very big development prospect from now on.
Embodiment
For better explanation the present invention, the spy enumerates following embodiment, but the present invention is not limited in following embodiment.
Embodiment one:
1) preparation of Synolac:
Behenic acid: 44.8g; Diethylene Glycol: 25.7g; Tetra hydro Phthalic anhydride: 77.5g; Phenylformic acid: 18.2g; Tetramethylolmethane: 45.3g; Trimellitic acid 1,2-anhydride: 15.0g; Band aqua (dimethylbenzene): an amount of.
In the reaction flask that disposes thermometer, agitator, reflux exchanger, feed intake by said sequence and consumption.Heat temperature raising, crawl stirs, and 80 ℃ stop to stir, and logical carbon dioxide starts and stirs and intensification.When temperature is raised to after 160 ℃, control heat-up rate, at 185 ℃ of insulation 1h,,,, meet the requirements up to viscosity and acid number detection again 205～210 ℃ of insulations again at 200 ℃ of insulation 2h again at 193 ℃ of insulation 1.5h.Pressure reducing and steaming dimethylbenzene.Acid number: 9.6mgKOH/g; Oil content: 34%.
2) preparation of hybridisation emulsion
A) the above-mentioned synthetic Synolac of 40.0g, 0.3g benzoyl peroxide, 2.0g cetyl alcohol and 3.0g polymethylmethacrylate are dissolved in 36.0g butyl acrylate, 36.0g methyl methacrylate, the acrylic acid mix monomer of 1.0g.
B) with 1.0g sodium lauryl sulphate, 1.0g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 0.8g ethoxylated alkylphenol ammonium sulfate (RHODAPEX CO-436,58%), the 0.20g Potassium Persulphate is dissolved in the 120.0g deionized water, after stirring, add the monomer solution in the A step, stir pre-emulsion.
C) in the reaction flask that disposes thermometer, agitator, reflux exchanger and dropping funnel, with 0.4g sodium lauryl sulphate, 1.0g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 0.6g ethoxylated alkylphenol ammonium sulfate (RHODAPEXCO-634,58%), the 0.20g Potassium Persulphate adds in the 50g deionized water, stir, logical nitrogen is warmed up to 80 ℃ after 20 minutes, begin to drip the pre-emulsion of B step preparation, drip in 3 hours, insulation is warmed up to 95 ℃ of reactions 3.5 hours after half an hour.Can make solid content is 40.3%, pH6.0, the emulsion of viscosity 11.26 seconds (being coated with-4 glasss).In above-mentioned emulsion, add an amount of 2-butoxy-1-alcohol, acetic acid ester and make membrane-forming agent, coat on the sheet glass, drying at room temperature 2 hours, what get final product transparently films.
Embodiment two
1) preparation of Synolac: behenic acid: 40.68g; Glycerine: 2.26g; Tetramethylolmethane: 12.47g; Tetra hydro Phthalic anhydride: 18.16g; Band aqua (dimethylbenzene): an amount of.
In the reaction flask that disposes thermometer, agitator, reflux exchanger, feed intake by said sequence and consumption.Logical carbon dioxide is warming up to 180 ℃ in 1.5h, and wherein in the time of 120～140 ℃, crawl stirs, and rises to 245 ℃ with the about 5h of 14 ℃/h speed later on, and insulation meets the requirements up to viscosity and acid number detection.Pressure reducing and steaming dimethylbenzene.Acid number: 8.8mgKOH/g; Oil content: 65%
2) preparation of hybridisation emulsion:
A) the above-mentioned synthetic Synolac of 30.0g, 0.25g Diisopropyl azodicarboxylate, 3.5g polymethylmethacrylate are dissolved in 40.0g butyl acrylate, 25.0g methyl methacrylate, 17.0g vinylbenzene, the acrylic acid mix monomer of 1.0g.
B) with 2.0g polyoxyethylene nonyl phenyl vinyl ether (IGEPAL CO-897,65%) 1.5g ethoxylated alkylphenol ammonium sulfate (RHODAPEX CO-436,, 58%), the 0.25g Potassium Persulphate is dissolved in the 120.0g deionized water, after stirring, add the monomer solution in the A step, stir pre-emulsion.
C) in the reaction flask that disposes thermometer, agitator, reflux exchanger and dropping funnel, with 1.8g polyoxyethylene nonyl phenyl vinyl ether (IGEPAL CO-897,65%) 1.5g ethoxylated alkylphenol ammonium sulfate (RHODAPEX CO-634,, 58%), the 0.20g Potassium Persulphate adds in the 50g deionized water, stir, logical nitrogen is warmed up to 80 ℃ after 20 minutes, begin to drip the pre-emulsion of B step preparation, drip in 3 hours, insulation is warmed up to 90 ℃ of reactions 2 hours after half an hour, and then 100 ℃ of reactions 1 hour.Can make solid content is 40.8%, pH6.0, the emulsion of viscosity 10.47 seconds (being coated with-4 glasss).In above-mentioned emulsion, add an amount of 2-butoxy-1-alcohol, acetic acid ester and make membrane-forming agent, coat on the sheet glass, drying at room temperature 2 hours, what get final product transparently films.
Embodiment three:
1) preparation of Synolac:
Preparation with Synolac in the example two.
2) preparation of hybridisation emulsion:
A) the above-mentioned synthetic Synolac of 22.0g, 3.0g cetyl alcohol are dissolved in 40.0g butyl acrylate, 50.0g methyl methacrylate, the acrylic acid mix monomer of 1.0g.
B) 0.8g sodium lauryl sulphate, 1.5g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 0.35g Potassium Persulphate are dissolved in the 120.0g deionized water, after stirring, add the monomer solution in the A step, stir pre-emulsion.
C) in the reaction flask that disposes thermometer, agitator, reflux exchanger and dropping funnel, 0.6g sodium lauryl sulphate, 1.0g polyoxyethylene nonyl phenyl vinyl ether (OP-10), 0.25g Potassium Persulphate are added in the 50g deionized water, stir, logical nitrogen is warmed up to 85 ℃ after 20 minutes, begin to drip the pre-emulsion of B step preparation, dripped in 3 hours, insulation is warmed up to 100 ℃ of reactions 2.5 hours after half an hour.Can make solid content is 39.7%, pH6.5, the emulsion of viscosity 10.18 seconds (being coated with-4 glasss).In above-mentioned emulsion, add an amount of 2-butoxy-1-alcohol, acetic acid ester and make membrane-forming agent, coat on the sheet glass, drying at room temperature 2 hours, what get final product transparently films.
Claims (8)
1, the preparation method of a kind of alkyd-polyacrylic acid (ester) emulsion is a major ingredient with Synolac and vinyl monomer, it is characterized in that preparation process may further comprise the steps successively:
(1), pre-emulsification: emulsifying agent, water soluble starter and catalyzer are put in the deionized water, after treating to dissolve fully, are added the vinyl monomer that is dissolved with Synolac, oil-soluble initiator and auxiliary agent and mixes, stir pre-emulsion;
(2), polyreaction: emulsifying agent and water soluble starter are put in the deionized water, after the dissolving, led to nitrogen 20 minutes fully, be warmed up to 75～85 ℃, dripped pre-emulsion continuously 2～5 hours, after being added dropwise to complete, be warming up to 90～100 ℃, continue reaction 2～8 hours;
Wherein: the air-drying property Synolac with unsaturated link(age) of Synolac for adopting siccative oil or semi-drying oil to make, its acid number be less than 10mgKOH/g, oil content 30-85%.
2, according to the described preparation method of claim 1, the weight ratio that it is characterized in that described Synolac and vinyl monomer is 2～50: 98～50.
3, according to the described preparation method of claim 1, the weight ratio that it is characterized in that described Synolac and vinyl monomer is 10～35: 90～65.
4,, it is characterized in that described vinyl monomer is methacrylic acid and C thereof according to the described preparation method of claim 1
1～C
10Alcohol ester, vinylformic acid and C thereof
1～C
10In alcohol ester or the vinylbenzene one or more.
5, according to the described preparation method of claim 1, it is characterized in that described emulsifying agent is the moon/nonionic compound emulsifier, the ratio of the moon/nonionic emulsifying agent is 1: 0.5～3, consumption is 0.8～5% (reasonable opinion solid content weight percent), and wherein the consumption of pre-emulsion process is 1/5～4/5 of whole consumptions.
6,, it is characterized in that described emulsifying agent is 2～4 kinds in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, polyoxyethylene nonyl phenyl Vinyl Ether, ethoxylated alkylphenol ammonium sulfate, the octylphenol polyethylene ethylene oxide ether according to the described preparation method of claim 5.
7,, it is characterized in that described water soluble starter is one or both of Potassium Persulphate, ammonium persulphate according to the described preparation method of claim 1; Oil-soluble initiator is one or both in benzoyl peroxide, the Diisopropyl azodicarboxylate, the total consumption of initiator is 0.5～2% (accounting for the weight percent of vinyl monomer), wherein oil-soluble initiator accounts for 0～50% of total consumption, and the consumption of pre-emulsion process is 1/5～4/5 of whole consumptions.
8, according to the described preparation method of claim 1, it is characterized in that described auxiliary agent is one or more in n-Hexadecane, cetyl alcohol, 1-amylalcohol, the polymethyl acrylate, the total consumption of auxiliary agent is 0～5% (accounting for the polymerization single polymerization monomer weight percent).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310116802 CN1264885C (en) | 2003-11-28 | 2003-11-28 | Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310116802 CN1264885C (en) | 2003-11-28 | 2003-11-28 | Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546544A true CN1546544A (en) | 2004-11-17 |
| CN1264885C CN1264885C (en) | 2006-07-19 |
Family
ID=34337618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310116802 Expired - Lifetime CN1264885C (en) | 2003-11-28 | 2003-11-28 | Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1264885C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101189310B (en) * | 2005-06-01 | 2011-03-02 | 阿克佐诺贝尔国际涂料股份有限公司 | Aqueous coating composition |
| CN102690618A (en) * | 2012-06-11 | 2012-09-26 | 成都瀚江新型建筑材料有限公司 | Preparation method of thermosetting acrylic resin binder |
| CN102888178A (en) * | 2012-11-09 | 2013-01-23 | 重庆三峡油漆股份有限公司 | Water emulsification process of alkyd resin coating |
-
2003
- 2003-11-28 CN CN 200310116802 patent/CN1264885C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101189310B (en) * | 2005-06-01 | 2011-03-02 | 阿克佐诺贝尔国际涂料股份有限公司 | Aqueous coating composition |
| CN102690618A (en) * | 2012-06-11 | 2012-09-26 | 成都瀚江新型建筑材料有限公司 | Preparation method of thermosetting acrylic resin binder |
| CN102690618B (en) * | 2012-06-11 | 2013-12-04 | 成都瀚江新型建筑材料有限公司 | Preparation method of thermosetting acrylic resin binder |
| CN102888178A (en) * | 2012-11-09 | 2013-01-23 | 重庆三峡油漆股份有限公司 | Water emulsification process of alkyd resin coating |
| CN102888178B (en) * | 2012-11-09 | 2015-07-15 | 重庆三峡油漆股份有限公司 | Water emulsification process of alkyd resin coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1264885C (en) | 2006-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100591735C (en) | Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion | |
| EP0712419B1 (en) | Production of polymer emulsions | |
| CN102993387B (en) | Method for directly synthesizing pure solid high-performance polycarboxylate water-reducer in one step | |
| CN1130634A (en) | Encapsulated hydrophilic polymers and their preparation | |
| CN1068124A (en) | Method with preparation of graft copolymers by two staged aqueous emulsion polymerization | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN101092470A (en) | Method for preparing microemulsion with high solid content of crosslinked polystyrene and acrylic (ester) | |
| CN1432582A (en) | Emulsion polymer and its prepn process | |
| CN1515594A (en) | Preparation of polymer emulsion and process using it to form polymer | |
| CN103497272B (en) | A kind of polymer emulsion and preparation method thereof | |
| WO2000068304A1 (en) | Preparation of core-shell polymer particles containing voids | |
| CN104628923A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by oil-soluble initiator | |
| JPH0699666B2 (en) | Composite three-dimensional resin particles and method for producing the same | |
| CN111138603A (en) | Water-based alkyd-acrylate dispersion and preparation method and application thereof | |
| CN1264884C (en) | Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion | |
| CN108570131B (en) | Preparation method of hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin | |
| CN1385447A (en) | Organic silicon-acrylate nano emulsion | |
| CN108570132B (en) | Hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin | |
| CN1654488A (en) | Process for preparing reaction functional macromolecule/Al2O3 nano composite particles | |
| CN1264885C (en) | Alcohol acid-polyacrylic acid (ester) hybrid latex preparation method | |
| JP2648853B2 (en) | Composite three-dimensional resin particles and their manufacturing method | |
| Teng et al. | Synthesis and characterization of cycloaliphatic diepoxide crosslinkable core–shell latexes | |
| CN1132849C (en) | Prepn of nanometer reactive polymer microgel | |
| KR20000077276A (en) | Process for preparing polymers | |
| CN1884327A (en) | Method for promoting grafting efficiency of acrylate core/shell structure latex particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 528329 Taiping Industrial Zone, Junan Town, Shunde District, Foshan, Guangdong Patentee after: Guangdong Hongchang Chemical Co.,Ltd. Address before: 528329 Taiping Industrial Zone, Junan Town, Shunde District, Shunde, Guangdong Patentee before: Shunde Hongchang Chemical Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060719 |
|
| CX01 | Expiry of patent term |