CN108690163A - Water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof - Google Patents
Water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof Download PDFInfo
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- CN108690163A CN108690163A CN201810652106.8A CN201810652106A CN108690163A CN 108690163 A CN108690163 A CN 108690163A CN 201810652106 A CN201810652106 A CN 201810652106A CN 108690163 A CN108690163 A CN 108690163A
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- room temperature
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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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to technical field of high-molecular polymer more particularly to water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof, are formed by the polymerizable raw material of following parts by weight:Methyl methacrylate 12-38, a- methyl styrenes 3-35, acrylic monomers 0.5-5, N monohydroxy acrylamides 0.5-2.5, hydroxyethyl methacrylate 1.5-3, butyl methacrylate 1-20, emulsifier 1-3, initiator 0.3-1, sodium bicarbonate 0.2-0.5, neutralizer 3-10, water 30-50, inhibit stabilizer 0.2-0.8, crosslinking agent 0.05-1.5, when polymerization, introducing crosslinked monomer (modified monomer) acrylic acid, methacrylic acid, N monohydroxies propionamide carries out carboxyl crosslinking with copolymer, hydroxyl is crosslinked, amide groups is crosslinked, make the cohesive strength of lotion, heat resistance and ageing-resistant performance significantly improve, also improve emulsion intercalation method simultaneously.
Description
Technical field:
The present invention relates to technical field of high-molecular polymer more particularly to water-based room temperature crosslinking acrylic acid emulsion and its preparations
Method.
Background technology:
The film forming matter applied currently on the market is broadly divided into organic solvent type, powder-type and aqueous three categories, organic
Solvent type mainly makees solvent with pure benzene,toluene,xylene, industrial naptha, tenth of the twelve Earthly Branches purport, ketone.This kind of solvent type film forming matter makes
With a large amount of organic solvent, a large amount of non-renewable petroleum resources are consumed, of high cost, inflammable and explosive, production and transport makes
With being absolutely unsafe, it can also cause serious environmental pollution.But it has rate of drying fast, and good combination property still makes extensively at present
With.
Powder-type film forming matter is free of solvent, and without volatile ingredient, percent face film forming does not consume valuable organic solvent
Resource, does not cause environmental pollution, but it is using needing special apparatus and process, using being subject to certain restrictions.
Waterborne film-forming substance is the product of current Devoting Major Efforts To Developing, and the important feature of this kind of film forming matter is using water as solvent, no
It is free from environmental pollution using the petroleum resources with water pump preciousness, do not cause fire, it is safe and environment-friendly.
The waterborne film-forming substance of existing market has the following disadvantages:
Product comprehensive performance is poor compared with solvent, and especially wear-resisting, scratch resistance, water resistance and gloss all exist certain poor
Away from.Crosslinking agent hardness is added in product, and wear-resisting, scratch resistance performance can improve, but bi-component, can only be added when application, retention period
It is short.
Invention content:
The purpose of the present invention provides a kind of water-based room temperature crosslinking acrylic acid breast aiming at the shortcomings of the prior art
Liquid has splendid water resistance, and chemical-resistant, temperature tolerance, shelf life of products also provide this aqueous up to half a year
The preparation method of room temperature crosslinking acrylic acid emulsion.
To achieve the goals above, the technical solution adopted by the present invention is:
Water-based room temperature crosslinking acrylic acid emulsion is formed by the polymerizable raw material of following parts by weight:Methyl methacrylate 12-
38, a- methyl styrenes 3-35, acrylic monomers 0.5-5, N monohydroxy acrylamide 0.5-2.5, hydroxyethyl methacrylate
1.5-3, butyl methacrylate 1-20, emulsifier 1-3, initiator 0.3-1, sodium bicarbonate 0.2-0.5, neutralizer 3-10, water
30-50, inhibit stabilizer 0.2-0.8, crosslinking agent 0.05-1.5.
The acrylic monomers is acrylic acid, methacrylic acid or their mixture.
The emulsifier is compounded by anion emulsifier and nonionic emulsifier;Anion emulsifier is dodecyl
Phenyl-hydrogen-sulfate sodium, lauryl sodium sulfate, two sodium sulphate of dodecyl diphenyl oxide, one kind in ethoxy alcohol sulphur chess disodium succinate
Or two kinds or more of mixture;Nonionic emulsifier is nonylphenol polyoxyethylene ether, one kind or two of octylphenol polyethylene nitrogen vinethene
The mixture of kind.
The initiator is one or two or more kinds of compositions in benzoyl peroxide, ammonium peroxide or potassium peroxydisulfate.
The preparation method of above-mentioned water-based room temperature crosslinking acrylic acid emulsion, it includes following steps:
(1) emulsifier of emulsifier total amount 0-30% and the water for accounting for water gross weight 0-5% in formula are weighed, pre-emulsification is placed in
In kettle, stirring;Weigh the methyl methacrylate for accounting for total weight of monomer 0-30%, a- methyl styrenes, methacrylic acid, propylene
Acid, N monohydroxies acrylamide, hydroxyethyl methacrylate, butyl methacrylate, are slowly added to carry out pre- breast in pre-emulsification kettle
Change, emulsification times 30-60min is spare;
(2) it weighs and accounts for the emulsifier of emulsifier total amount 80-100% in formula and account for the water of water gross weight 15-30%, monomer
Methyl methacrylate, a- methyl styrenes, methacrylic acid, acrylic acid, the N monohydroxy acryloyls of total weight 70-100%
Amine, hydroxyethyl methacrylate, butyl methacrylate are slowly added to carry out pre-emulsification in pre-emulsification kettle, emulsification times 30-
60min, it is spare;
(3) in a kettle, it is added in formula and accounts for the water of water total weight 40050% and the sodium bicarbonate of formula ratio, account for and draw
The initiator for sending out agent total amount 30040% is used as kettle liquid, and raising reaction temperature is to 70085 DEG C while stirring;
(4) after kettle liquid stirring 30min, the good seed monomer of step (1) pre-emulsification is added, is then protected in 70-85 DEG C
Temperature to blue streak occurs.
(5) after keeping the temperature half an hour, the initiator for accounting for initiator total amount 40-50% is dissolved in the water for accounting for water 20-30%
In, it is respectively placed in head tank with the ready pre-emulsification monomer of step (2) and is added dropwise simultaneously, time for adding 3-4h, then
70-85 DEG C keeps the temperature 1 hour, is cooled to 35 DEG C hereinafter, with neutralizer tune pH value in 7.5-8.5 ranges, inhibition stabilizer is added
Then stirring 10-20 minutes is added propyleneimine derivative, obtains single component room temperature crosslinked polymer, i.e. water-based room temperature crosslinking
Lotion.
Advantageous effect of the present invention is:The present invention is formed by the polymerizable raw material of following parts by weight:Methyl methacrylate 12-
38, a- methyl styrenes 3-35, acrylic monomers 0.5-5, N monohydroxy acrylamide 0.5-2.5, hydroxyethyl methacrylate
1.5-3, butyl methacrylate 1-20, emulsifier 1-3, initiator 0.3-1, sodium bicarbonate 0.2-0.5, neutralizer 3-10, water
30-50, inhibit stabilizer 0.2-0.8, crosslinking agent 0.05-1.5, when polymerization, introducing crosslinked monomer (modified monomer) acrylic acid, first
Base acrylic acid, N monohydroxies propionamide carry out carboxyl crosslinking, hydroxyl crosslinking, amide groups crosslinking with copolymer, keep the cohesion of lotion strong
Degree, heat resistance and ageing-resistant performance significantly improve, while also improving emulsion intercalation method, and have used inhibition stabilizer,
It makes water-based emulsion addition crosslinking agent keep stablizing in room temperature under stored condition, and the shelf-life up to 6 months, makes the comprehensive of water-based emulsion
It closes performance to be greatly improved, application process is also convenient for handy.
Specific implementation mode:
With reference to preferred embodiment, the invention will be further described.
Water-based room temperature crosslinking acrylic acid emulsion is formed by the polymerizable raw material of following parts by weight:Methyl methacrylate 12-
38, a- methyl styrenes 3-35, acrylic monomers 0.5-5, N monohydroxy acrylamide 0.5-2.5, hydroxyethyl methacrylate
1.5-3, butyl methacrylate 1-20, emulsifier 1-3, initiator 0.3-1, sodium bicarbonate 0.2-0.5, neutralizer 3-10, water
30-50, inhibit stabilizer 0.2-0.8, crosslinking agent 0.05-1.5.
The acrylic monomers is acrylic acid, methacrylic acid or their mixture.
The emulsifier is compounded by anion emulsifier and nonionic emulsifier;Anion emulsifier is dodecyl
Phenyl-hydrogen-sulfate sodium, lauryl sodium sulfate, two sodium sulphate of dodecyl diphenyl oxide, one kind in ethoxy alcohol sulphur chess disodium succinate
Or two kinds or more of mixture;Nonionic emulsifier is nonylphenol polyoxyethylene ether, one kind or two of octylphenol polyethylene nitrogen vinethene
The mixture of kind.
Initiator is one or two or more kinds of compositions in benzoyl peroxide, ammonium peroxide or potassium peroxydisulfate.Crosslinking agent
For methylaziridine.Neutralizer is the composition of inorganic amine and organic amine, and inorganic amine is ammonium hydroxide, and organic amine is monoethanolamine, two
Ethanol amine.Inhibition stabilizer is octadecyl trimethyl ammonium nitrides.
The preparation method of above-mentioned water-based room temperature crosslinking acrylic acid emulsion, it includes following steps:
(1) emulsifier of emulsifier total amount 0-30% and the water for accounting for water gross weight 0-5% in formula are weighed, pre-emulsification is placed in
In kettle, stirring;Weigh the methyl methacrylate for accounting for total weight of monomer 0-30%, a- methyl styrenes, methacrylic acid, propylene
Acid, N monohydroxies acrylamide, hydroxyethyl methacrylate, butyl methacrylate, are slowly added to carry out pre- breast in pre-emulsification kettle
Change, emulsification times 30-60min is spare;
(2) it weighs and accounts for the emulsifier of emulsifier total amount 80-100% in formula and account for the water of water gross weight 15-30%, monomer
Methyl methacrylate, a- methyl styrenes, methacrylic acid, acrylic acid, the N monohydroxy acryloyls of total weight 70-100%
Amine, hydroxyethyl methacrylate, butyl methacrylate are slowly added to carry out pre-emulsification in pre-emulsification kettle, emulsification times 30-
60min, it is spare;
(3) in a kettle, it is added in formula and accounts for the water of water total weight 40050% and the sodium bicarbonate of formula ratio, account for and draw
The initiator for sending out agent total amount 30040% is used as kettle liquid, and raising reaction temperature is to 70085 DEG C while stirring;
(4) after kettle liquid stirring 30min, the good seed monomer of step (1) pre-emulsification is added, is then protected in 70-85 DEG C
Temperature to blue streak occurs.
(5) after keeping the temperature half an hour, the initiator for accounting for initiator total amount 40-50% is dissolved in the water for accounting for water 20-30%
In, it is respectively placed in head tank with the ready pre-emulsification monomer of step (2) and is added dropwise simultaneously, time for adding 3-4h, then
70-85 DEG C keeps the temperature 1 hour, is cooled to 35 DEG C hereinafter, with neutralizer tune pH value in 7.5-8.5 ranges, inhibition stabilizer is added
Then stirring 10-20 minutes is added propyleneimine derivative, obtains single component room temperature crosslinked polymer, i.e. water-based room temperature crosslinking
Lotion.
Introduce a- methyl styrenes in synthesizing component formula, partial alternative styrene, by the way of polymerisation in solution,
The influence of initiator in polymerization process, temperature, the dosage of solvent, rate of addition to lotion molecular weight and its distribution is combined, is closed
At low molecular weight narrow ditribution, structure-controllable high-performance can widely applied aqueous acrylic emulsion, oil polish prepared therefrom
The advantages that with high glaze, flow leveling is good, and mill performance is good.
Emulsifier is compounded using a kind of anion emulsifier and a kind of nonionic emulsifier, and anion emulsifier is molten in alkalinity
It is more stable in liquid, behind match glue when alkali thickening, can make lotion more stablize;Nonionic emulsifier can improve the freeze thawing of lotion
Performance, and the grain size and particle diameter distribution of polymer can be adjusted.When polymerization, both emulsifier molecules meeting alternating sorbent is in emulsion particle
Surface, reduce latex particle must charge density, make negatively charged free radical be easier enter emulsion particle, improving breast
While liquid polymerization speed, the dosage of total emulsifiers is also reduced, avoids negative effect of the emulsifier to Laminating adhesive performance as possible.
When polymerization, introducing crosslinked monomer (modified monomer) acrylic acid, methacrylic acid, N monohydroxies propionamide and copolymer
Carboxyl crosslinking, hydroxyl crosslinking, amide groups crosslinking are carried out, the cohesive strength of lotion, heat resistance and ageing-resistant performance is made to significantly improve,
Emulsion intercalation method is also improved simultaneously, and has used inhibition stabilizer, it makes water-based emulsion that crosslinking agent be added in storage shape
It keeps stablizing in room temperature under state, the shelf-life up to 6 months, makes the comprehensive performance of water-based emulsion be greatly improved, application process is also convenient for
It is handy.
Certainly, the above is only presently preferred embodiments of the present invention, therefore all structures according to described in present patent application range
It makes, the equivalent change or modification that feature and principle are done, is included within the scope of present patent application.
Claims (5)
1. water-based room temperature crosslinking acrylic acid emulsion, which is characterized in that formed by the polymerizable raw material of following parts by weight:Methacrylic acid
Methyl esters 12-38, a- methyl styrene 3-35, acrylic monomers 0.5-5, N monohydroxy acrylamide 0.5-2.5, methacrylic acid
Hydroxyl ethyl ester 1.5-3, butyl methacrylate 1-20, emulsifier 1-3, initiator 0.3-1, sodium bicarbonate 0.2-0.5, neutralizer 3-
10, water 30-50, inhibition stabilizer 0.2-0.8, crosslinking agent 0.05-1.5.
2. water-based room temperature crosslinking acrylic acid emulsion according to claim 1, it is characterised in that:The acrylic monomers is third
Olefin(e) acid, methacrylic acid or their mixture.
3. water-based room temperature crosslinking acrylic acid emulsion according to claim 1, it is characterised in that:The emulsifier is by anion
Emulsifier and nonionic emulsifier compound;Anion emulsifier is sodium dodecyl benzene sulfonate, lauryl sodium sulfate, ten
Two sodium sulphate of dialkyl diphenyl ether, one or two or more kinds of mixtures in ethoxy alcohol sulphur chess disodium succinate;Nonionic
Emulsifier is nonylphenol polyoxyethylene ether, one kind or two kinds of mixture of octylphenol polyethylene nitrogen vinethene.
4. water-based room temperature crosslinking acrylic acid emulsion according to claim 1, which is characterized in that the initiator is peroxidating
In benzoyl, ammonium peroxide or potassium peroxydisulfate, one or two or more kinds of compositions.
5. the preparation method of any one of the claim 1-4 water-based room temperature crosslinking acrylic acid emulsions, which is characterized in that it
Include following steps:
(1) emulsifier of emulsifier total amount 0-30% and the water for accounting for water gross weight 0-5% in formula are weighed, is placed in pre-emulsification kettle,
Stirring;Weigh the methyl methacrylate for accounting for total weight of monomer 0-30%, a- methyl styrenes, methacrylic acid, acrylic acid, N mono-
Hydroxyacrylamide, hydroxyethyl methacrylate, butyl methacrylate are slowly added to carry out pre-emulsification in pre-emulsification kettle, breast
Change time 30-60min, it is spare;
(2) it weighs and accounts for the emulsifier of emulsifier total amount 80-100% in formula and account for the water of water gross weight 15-30%, total weight of monomer
The methyl methacrylate of amount 70-100%, a- methyl styrenes, methacrylic acid, acrylic acid, N monohydroxies acrylamide, first
Base hydroxy-ethyl acrylate, butyl methacrylate are slowly added to carry out pre-emulsification in pre-emulsification kettle, emulsification times 30-60min,
It is spare;
(3) in a kettle, it is added in formula and accounts for the water of water total weight 40050% and the sodium bicarbonate of formula ratio, account for initiator
For the initiator of total amount 30040% as kettle liquid, stirring while, increases reaction temperature to 70085 DEG C;
(4) after kettle liquid stirring 30min, the good seed monomer of step (1) pre-emulsification is added, then 70-85 DEG C of inside holding extremely
Blue streak occurs;
(5) after keeping the temperature half an hour, the initiator for accounting for initiator total amount 40-50% is dissolved in the water for accounting for water 20-30%, with
The ready pre-emulsification monomer of step (2) is respectively placed in head tank while being added dropwise, time for adding 3-4h, then 70-85 DEG C
Heat preservation 1 hour is cooled to 35 DEG C hereinafter, with neutralizer tune pH value in 7.5-8.5 ranges, stirring 10- is added in inhibition stabilizer
20 minutes, then propyleneimine derivative is added, obtains single component room temperature crosslinked polymer, i.e. water-based room temperature crosslinking lotion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810652106.8A CN108690163A (en) | 2018-06-22 | 2018-06-22 | Water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597355A (en) * | 2009-05-27 | 2009-12-09 | 彭文表 | A kind of water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof |
| CN102993353A (en) * | 2012-10-12 | 2013-03-27 | 张家港市永法涂料有限公司 | Acrylic ester waterproof paint copolymerization emulsion and preparation method thereof |
| CN106589213A (en) * | 2016-12-15 | 2017-04-26 | 佛山海特化工科技有限公司 | Self-crosslinkingacrylic emulsion for water-based metallic paint and preparation method thereof |
-
2018
- 2018-06-22 CN CN201810652106.8A patent/CN108690163A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597355A (en) * | 2009-05-27 | 2009-12-09 | 彭文表 | A kind of water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof |
| CN102993353A (en) * | 2012-10-12 | 2013-03-27 | 张家港市永法涂料有限公司 | Acrylic ester waterproof paint copolymerization emulsion and preparation method thereof |
| CN106589213A (en) * | 2016-12-15 | 2017-04-26 | 佛山海特化工科技有限公司 | Self-crosslinkingacrylic emulsion for water-based metallic paint and preparation method thereof |
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Application publication date: 20181023 |