CN1086193C - Solid acrylic resin for paint and its preparation - Google Patents
Solid acrylic resin for paint and its preparation Download PDFInfo
- Publication number
- CN1086193C CN1086193C CN96116564A CN96116564A CN1086193C CN 1086193 C CN1086193 C CN 1086193C CN 96116564 A CN96116564 A CN 96116564A CN 96116564 A CN96116564 A CN 96116564A CN 1086193 C CN1086193 C CN 1086193C
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- China
- Prior art keywords
- monomer
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- acrylic resin
- resin
- acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
Abstract
The present invention relates to solid acrylic resin which is convenient for transportation and storage. The resin can be dissolved in component solvent which mainly contains tasteless aliphatic hydrocarbon with low toxicity, and can be prepared into various solvent based coatings with low toxicity. The solid acrylic resin which can be dissolved in aliphatic hydrocarbon is copolymerized by acrylic acid monomers through the methods of suspension polymerization and emulsion polymerization. The present invention is used for preparing coatings for interior and exterior walls.
Description
The present invention relates to solid acrylic resin.
The method for making of solvent-type acrylic resin and prescription are known in this area, it can be used for coating such as external wall, interior wall and ground, its principal feature is: all adopt solvent-borne type polymeric acrylic resin soln as base-material (tackiness agent), the resin solution transportation is relatively more difficult with storage, such acrylic resin is not dissolved in aliphatic solvents, the coating that is mixed with contains aromatic solvents such as a large amount of toluene, dimethylbenzene, and toxicity is bigger.
The objective of the invention is to the novel solid acrylic resin of synthetic and be convenient to transportation and store, this resin can be dissolved in low toxicity, tasteless aliphatic hydrocarbon is in master's the mixed solvent, can prepare all kinds of low-toxicity solvent coating.
Solid acrylic resin is formed by the Acrylic Acid Monomer copolymerization.Described solid resin is dissolvable in water in the aliphatic hydrocarbon, intrinsic viscosity 28.5-115.2 in the butanone; Acrylic Acid Monomer is made up of soft monomer, hard monomer, adjustment monomer, functional monomer; Described soft monomer is selected from: one or more in ethyl propenoate, butyl acrylate, 2-EHA, decyl acrylate, the methacrylic acid 2-ethylhexyl; Described hard monomer is selected from: one or more in vinylbenzene, vinyl toluene, the methyl methacrylate; Described adjustment monomer is selected from: one or more in methyl acrylate, isobutyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate, the Propenoic acid, 2-methyl, isobutyl ester; Described functional monomer is selected from: one or more in vinylformic acid, methacrylic acid, the Vinylstyrene; Various monomeric weight percents are:
Hard monomer accounts for 20-80%;
Soft monomer accounts for 19.8-50%;
The property adjusted monomer accounts for 20-50%;
Functional monomer accounts for 2-10%;
Preparation method of the present invention has suspension polymerization, emulsion polymerization.
Method I: suspension polymerization is disperse phase with water, adds suspension dispersive agent, monomer mixture high-speed stirring, heated polymerizable.Described suspension dispersive agent is divided into two kinds: inorganic suspension agent and organic suspending agent.Inorganic suspension agent is selected from magnesiumcarbonate, lime carbonate, barium carbonate, diatomite, talcum powder etc., consumption is the water yield 0.1～2.5%, organic dispersing agent is selected from: polyacrylic acid (sodium), polymethyl acrylic acid (sodium), calcium mahogany sulfonate, petroleum sodium sulfonate and various lipid acid barium salt, consumption is the water yield 0.01～2%, water-oil ratio span of control 15-3.5: 1.
Method II: emulsion polymerization, can obtain the differing molecular weight polymers by this method, obtain solid resin by breakdown of emulsion, drying.The selected emulsifying agent of letex polymerization is selected from: (1) anionic: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol-polyethenoxy ammonium sulfate, consumption are 0.25～3% of amount of monomer.(2) non-ionic type can be selected OP series for use, and consumption is 0.5～4% of an amount of monomer.
The solid propenoic acid resin of the invention can be dissolved in aliphatic hydrocarbon and account in the mixed solvent of 65-93%, the exterior coating aromaticity content of preparation is less than 15%, the coating artificial ageing resistance is more than 1000 hours, anti-ultraviolet lamp temper(ing) 1000 hours, the interior wall decorative pattern paint aromaticity content of preparation is less than 3%, and the coating abrasion resistance is more than 8000 times.
Embodiment 1:
The band stirred reactor that 2100 gram deionized waters and 42 gram suspension dispersive agents are housed is heated to 50 ℃ under nitrogen atmosphere, in reactor, add 700 gram monomer mixtures then, use 20 gram water flushing feeding lines, wash reactor, 200～800 rev/mins of mixing speed, material is risen to 85 ℃, kept 2 hours at 85 ± 2 ℃, measure free monomer content, reach below 2%, finish reaction, be cooled to 45 ℃, discharging, after filtration, washing, dry, obtain the solid sold resin, water content＜0.5%, Tg:23 ℃, intrinsic viscosity 28.5 in the butanone, have good weather, can prepare outdoor coating.Prescription:
Dispersion agent: CaCO
3(powder): 21 grams
Polyvinyl alcohol: 10 grams
Gelatin: 11 grams
Monomer: vinylformic acid: 14 grams
Vinylbenzene: 210 grams
Methyl methacrylate: 140 grams
Butyl acrylate: 70 grams
Butyl methacrylate: 175 grams
Isooctyl acrylate monomer: 91 grams
Initiator: dibenzoyl peroxide (BPO): 7 grams
Embodiment 2:
Press embodiment 1 technical process, change monomer prescription and dispersion agent.
Dispersion agent: MgCO
3(powder): 30 grams
Dodecyl sodium sulfonate calcium: 4 grams
Polyacrylic acid: 8 grams
Monomer: vinylformic acid: 14 grams
Vinylbenzene: 476 grams
Butyl acrylate: 140 grams
Isooctyl acrylate monomer: 70 grams
Initiator: azobisisobutyronitrile: 5 grams
Gained resin water ratio＜0.5%, Tg:28.4 ℃, intrinsic viscosity: 30.4, solvability is good, can prepare the low indoor coating of multi-colour pattern of aromatic hydrocarbons, indoor anticorrosion and decorative paint etc.
Embodiment 3:
Letex polymerization, the band stirred reactor that 1000g water and 20g tensio-active agent are housed is heated to 60 ℃ under nitrogen atmosphere, emulsification was warming up to 87 ± 2 ℃ in 0.5 hour, begin to drip monomer mixture and initiator solution, monomer dropwised in 2.5 hours, and initiator added in 3 hours. be incubated 0.5 hour then, be cooled to 45 ℃, add in the sodium chloride aqueous solution, stir breakdown of emulsion, after filtration, washing, drying.Gained resin water ratio＜0.5%, Tg:30 ℃, intrinsic viscosity: 100.1, have viscosity higher, good weather.Cooperate with embodiment 1 resin, can prepare exterior coating.Prescription:
Emulsifying agent: OP-10: 15 grams
Sodium lauryl sulphate: 5 grams
Initiator: ammonium persulphate (5% water liquid): 200 grams
Monomer: vinylformic acid: 20 grams
Vinylbenzene: 300 grams
Methyl methacrylate: 230 grams
Butyl acrylate: 100 grams
Butyl methacrylate: 250 grams
Isooctyl acrylate monomer: 100 grams
Vinylstyrene (40%): 10 gram emulsion splitter: NaCL: 300 grams
Water: 3000 grams
Embodiment 4:
Technology and monomer prescription are with embodiment 3, and Vinylstyrene does not add, and add molecular weight regulator, lauryl mercaptan 1 gram, and the gained resin has suitable viscosity, intrinsic viscosity: 29.1, cooperate with embodiment 3 resins, can prepare outdoor coating, weather resisteant is good.
Embodiment 5:
Letex polymerization adds 400 gram water in the reactor, tensio-active agent 20 grams stir, and monomer mixture dropwises in 1 hour, gets pre-emulsion.The band stirred reactor that 600 gram water and 5 gram tensio-active agents are housed is heated to 87 ± 2 ℃ under nitrogen atmosphere, emulsification 0.5 hour, add 1/4 monomer pre-emulsion and 1/4 initiator solution, reacted 1 hour, the monomer pre-emulsion with remainder in 1.5 hours dropwises, in 2 hours initiator is added, be incubated 0.5 hour, be cooled to 45 ℃, add in the breakdown of emulsion liquid, through washing, drying, get the resin finished product.Water ratio＜0.5%, Tg:30 ℃, intrinsic viscosity in butanone: 115.2, have fabulous weathering resistance and embodiment 1, the cooperation of embodiment 4 resins, can prepare exterior coating.Proportioning:
Pre-emulsification emulsifying agent: OP-10: 10 grams
Alkylphenol-polyethenoxy ammonium sulfate: 10 grams
Polyreaction partial emulsifier: OP-10: 3 grams
Sodium lauryl sulphate: 3 grams
Initiator water liquid (ammonium persulphate 5%): 200 grams
Monomer ratio is with embodiment 3.
Embodiment 6:
Technology and monomer prescription are with embodiment 5, and the linking agent Vinylstyrene does not add, and add 1 gram molecular weight conditioning agent, lauryl mercaptan, and the suitable viscosity of gained resin tool, intrinsic viscosity in butanone: 31, Tg:30 ℃, can prepare outdoor coating.
Embodiment 7:
Cooperate the preparation exterior coating with embodiment 1, embodiment 3 resins.
Prescription: embodiment 1 resin: 7
Embodiment 3 resins: 3
902 titanium dioxides: 20
Lime carbonate: 23
Talcum powder: 9
Dispersion agent: 3
200
#Solvent oil: 27
200
#Tar: 8
The coating of preparing carries out performance test by GB9757-88, and anti-ultraviolet lamp is more than 1000 hours, and artificial accelerated aging is more than 1000 hours, and contamination resistance＜9% all by detecting, has very excellent performance.
Embodiment 8:
With embodiment 2 resins preparation multicolor finish.
Embodiment 2 resins: 36
No aromatic hydrocarbons aliphatic hydrocarbon: 60
200
#Tar: 4
Be mixed with varnish, press the multi-color lacquer preparation method, prepare various multicolor finishes, with reference to the JG/T3003-93 standard testing, abrasion resistance is greater than 8000 times, and alkali resistance was greater than 48 hours, and water tolerance was greater than 96 hours.
Claims (2)
1. solid acrylic resin for paint is formed by the Acrylic Acid Monomer copolymerization; Described solid resin is dissolvable in water in the aliphatic hydrocarbon, intrinsic viscosity 28.5-115.2 in the butanone; Acrylic Acid Monomer is made up of soft monomer, hard monomer, adjustment monomer, functional monomer; Described soft monomer is selected from: one or more in ethyl propenoate, butyl acrylate, 2-EHA, decyl acrylate, the methacrylic acid 2-ethylhexyl; Described hard monomer is selected from: one or more in vinylbenzene, vinyl toluene, the methyl methacrylate; Described adjustment monomer is selected from: one or more in methyl acrylate, isobutyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate, the Propenoic acid, 2-methyl, isobutyl ester; Described functional monomer is selected from: one or more in vinylformic acid, methacrylic acid, the Vinylstyrene; Various monomeric weight percents are:
Hard monomer accounts for 20-80%;
Soft monomer accounts for 19.8-50%;
The property adjusted monomer accounts for 20-50%;
Functional monomer accounts for 2-10%.
2. the preparation method of the solid acrylic resin of claim 1 is characterized in that: the Acrylic Acid Monomer in the utilization claim 1, employing suspension polymerization or emulsion polymerisation process preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116564A CN1086193C (en) | 1996-11-06 | 1996-11-06 | Solid acrylic resin for paint and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116564A CN1086193C (en) | 1996-11-06 | 1996-11-06 | Solid acrylic resin for paint and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181389A CN1181389A (en) | 1998-05-13 |
| CN1086193C true CN1086193C (en) | 2002-06-12 |
Family
ID=5123661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116564A Expired - Fee Related CN1086193C (en) | 1996-11-06 | 1996-11-06 | Solid acrylic resin for paint and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1086193C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104767B (en) * | 2007-07-18 | 2010-06-23 | 紫荆花制漆（成都）有限公司 | Oiliness environmental protection self-cleaning exterior wall paint |
| CN101880349B (en) * | 2010-08-16 | 2012-05-02 | 上海东和胶粘剂有限公司 | Cross linking type methyl acrylate and vinyl acetate emulsion and preparation method thereof |
| CN102443098B (en) * | 2011-10-27 | 2013-11-06 | 中国海洋石油总公司 | High molecular weight acrylic resin for polyvinylidene fluoride coiled material finish paint |
| CN102718918B (en) * | 2011-12-21 | 2014-04-02 | 天津灯塔涂料工业发展有限公司 | Ultra-low-acid value pure acrylic resin and preparation method thereof |
| CN105331150A (en) * | 2015-12-01 | 2016-02-17 | 江苏汇源拉链制造有限公司 | Weather resistant zipper |
| CN115010846A (en) * | 2022-06-23 | 2022-09-06 | 安徽尚德轨道设备制造有限公司 | Synthesis of special resin for cold spray zinc and preparation method of cold spray zinc |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5763316A (en) * | 1980-10-02 | 1982-04-16 | Dainippon Ink & Chem Inc | Multicomponent copolymer latex |
| EP0103118A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | High solids primer-guidecoats based on t-butyl acrylate and styrene |
-
1996
- 1996-11-06 CN CN96116564A patent/CN1086193C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5763316A (en) * | 1980-10-02 | 1982-04-16 | Dainippon Ink & Chem Inc | Multicomponent copolymer latex |
| EP0103118A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | High solids primer-guidecoats based on t-butyl acrylate and styrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181389A (en) | 1998-05-13 |
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