CN109651550A - A kind of fatty acid modified acrylic emulsion and preparation method thereof - Google Patents
A kind of fatty acid modified acrylic emulsion and preparation method thereof Download PDFInfo
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- CN109651550A CN109651550A CN201811488356.9A CN201811488356A CN109651550A CN 109651550 A CN109651550 A CN 109651550A CN 201811488356 A CN201811488356 A CN 201811488356A CN 109651550 A CN109651550 A CN 109651550A
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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
- C08F212/08—Styrene
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- 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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- 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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- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- 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
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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Abstract
The present invention provides a kind of fatty acid modified acrylic emulsions and preparation method thereof, belong to synthetic resin material technical field, its component and component mass parts number are as follows: fatty acid modified glycidyl methacrylate or 25~35 parts of fatty acid modified glycidyl acrylate, first 2~6 parts of emulsifier, second 0.5~3.5 part of emulsifier, first 12~18 parts of soft monomer, second 1~8 part of soft monomer, first 40~50 parts of hard monomer, second 3~9 parts of hard monomer, 0~15 part of functional monomer, 0.5~2 part of chain-transferring agent, 0.1~0.5 part of initiator, 0.1~1 part of buffer, 150~180 parts of water, fatty acid modified acrylic emulsion rate of drying provided by the invention is fast, coating film gloss degree is high, adhesive force is excellent, water-tolerant, its preparation process The reproducible energy, abundance are used.
Description
Technical field
The invention belongs to synthetic resin material technical field, more particularly to a kind of fatty acid modified acrylic emulsion and
Preparation method.
Background technique
Acrylic emulsion is a kind of important coating resin, using safe, VOC content is low, pollution is low, it is wide in variety,
Formula variation is big, facilitates chemical modification and better performances；Coating made of it has the characteristics that application property is good, stemness is good again,
It is widely used in the decoration and protection of steel construction, woodenware, mixed mud etc..
The hardness of film of the acrylic emulsion of the prior art is low, gloss is low, and water resistance is poor, and needs to be added during painting
A large amount of coalescing agent could obtain preferable film effect, and the addition of coalescing agent will certainly improve the VOC content of paint vehicle
And paint film property is had adverse effect on.
Summary of the invention
It is an object of the invention to provide a kind of fatty acid modified acrylic emulsion, films fast with rate of drying
The features such as glossiness is high, and late hardness is high, and adhesive force is excellent, water-tolerant, another object of the present invention is just to provide a kind of rouge
The preparation method of the modified acrylic emulsion of fat acid, energy safety and stability produces above-mentioned acrylic emulsion, and use can be again
Green material, reaction slag yield is low, more environmentally friendly.
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester or 25~35 parts of fatty acid modified glycidyl acrylate, 2~6 parts of the first emulsifier, the second emulsification
0.5~3.5 part of agent, 12~18 parts of the first soft monomer, 1~8 part of the second soft monomer, 40~50 parts of the first hard monomer, the second hard list
3~9 parts of body, 0~15 part of functional monomer, 0.5~2 part of chain-transferring agent, 0.1~0.5 part of initiator, 0.1~1 part of buffer,
150~180 parts of water.
Further, the fatty acid modified glycidyl methacrylate or fatty acid modified glycidyl
Ester the preparation method is as follows:
By unsaturated fatty acid, glycidyl methacrylate or glycidyl acrylate, catalyst and polymerization inhibitor
Mix in a kettle, reaction temperature control at 90~130 DEG C, reaction to acid value less than 2 after be down to 30~50 DEG C, obtain fat
Sour modified methacrylic acid ethylene oxidic ester or fatty acid modified glycidyl acrylate；
The wherein unsaturated fatty acid, glycidyl methacrylate or glycidyl acrylate, catalyst, resistance
The mass parts number of poly- agent are as follows: 10~15 parts of unsaturated fatty acid, glycidyl methacrylate or glycidyl
10~20 parts of ester, 0.1~0.5 part of catalyst, 0.05~0.5 part of polymerization inhibitor.
Preferably, the unsaturated fatty acid is soybean oleic acid, linolenic acid, linoleic acid, ricinoleic acid, dehydrated castor
The combination of one or more of oleic acid, eleostearic acid, tall oil acid；
The catalyst be tetrabutylammonium bromide, tetraethylammonium bromide, triphenylphosphine, p-methyl benzenesulfonic acid, dimethylaniline,
The combination of one or more of dimethyl Bian amine, benzyltriethylammoinium chloride；
The polymerization inhibitor is the combination of one or more of methylnaphthohydroquinone, hydroquinone, p-hydroxyanisole.
Preferably, first soft monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, acrylic acid ten
The combination of one or more of octaester；
Second soft monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, one in octadecyl acrylate
Kind or several combinations.
Preferably, first hard monomer is styrene, acrylonitrile, methyl methacrylate, isobornyl acrylate
One or more of combination；
Second hard monomer be one of styrene, acrylonitrile, methyl methacrylate, isobornyl acrylate or
Several combinations.
Preferably, the functional monomer is acrylic or methacrylic acid.
Preferably, the functional monomer further includes hydroxypropyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxyl second
Ester, vinyl three (2- methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, vinyl front three
The combination of one or more of oxysilane, vinyl silane triisopropoxide.
Preferably, first emulsifier be OP-10, NP-10, lauryl sodium sulfate, neopelex,
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, nonylphenol polyoxyethylene ether ammonium sulfate, the reactive emulsifier containing allyl, phosphorous phosphorus
The combination of one or more of acid esters emulsifier；
Second emulsifier is OP-10, NP-10, lauryl sodium sulfate, neopelex, dodecyl
Diphenyl oxide disulfonate, nonylphenol polyoxyethylene ether ammonium sulfate, the reactive emulsifier containing allyl, phosphorous phosphate emulsification
The combination of one or more of agent.
Preferably, the initiator is the combination of one or both of potassium peroxydisulfate, ammonium persulfate；
The buffer is the combination of one or both of sodium bicarbonate, disodium hydrogen phosphate；
The chain-transferring agent is the combination of one or both of lauryl mercaptan, mercaptoethanol.
The preparation method of fatty acid modified acrylic emulsion, preparation step described in a kind of any one as above are as follows:
S1. a container is taken, fatty acid modified glycidyl methacrylate or fatty acid modified acrylic acid are shunk sweet
Grease, the first soft monomer, the first hard monomer, functional monomer, chain-transferring agent after mixing, are slowly added into containing the first cream
In the water of agent, while carry out pre-emulsification is stirred, mixing speed is 200~2000 revs/min, and it is stand-by that pre-emulsion is made；
S2. a container is separately taken, initiator, buffer are added to the water, sufficiently dissolves, it is stand-by that initiator solution is made；
S3. a container is separately taken, the second soft monomer, the second hard monomer are uniformly mixed, it is stand-by that monomer mixed solution is made；
S4. be added in another reaction kettle the second emulsifier, water, monomer mixed solution and 1/3 initiator solution, stirring simultaneously
80~90 DEG C are warming up to, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise, is at the uniform velocity added dropwise, pre-emulsion
It drips off within 2.5~3.5 hours, drips off within initiator solution 3~4 hours, keep the temperature 0.5~1 hour after dripping off, be warming up to 85~92 DEG C,
Cool down after 0.5 hour；
S5. after being cooled to 40 DEG C, pH adjusting agent is added, adjustment pH value is 8~9, and preparation is completed.
Acrylic emulsion provided by the invention, its dried coating film is fast after fatty acid is cross-linking modified, glossiness is high, hardness
It is high, adhesive force is excellent, water-tolerant, when painting makees ingredient, it is possible to reduce or even cancel addition film auxiliary agent, reduce VOC's
Amount, improves paint film property；The preparation method of fatty acid modified acrylic emulsion provided by the invention, step is succinct, reaction
Slag yield is low, the above-mentioned fatty acid modified acrylic emulsion of the stable production of energy, and has used the reproducible energy, and source is rich
Richness reduces production cost.
Specific embodiment
Following embodiment is merely to illustrate the present invention, but does not limit the scope of the invention.
Embodiment one
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester 25g, the first emulsifier (OP-10, lauryl sodium sulfate) 2g, the second emulsifier (dodecyl sulphate
Sodium) 0.5g, the first soft monomer (ethyl acrylate) 13g, the second soft monomer (butyl acrylate) 1g, the first hard monomer (styrene)
48g, the second hard monomer (acrylonitrile) 3g, functional monomer (acrylic acid) 1g, chain-transferring agent (lauryl mercaptan) 0.5g, initiator
(potassium peroxydisulfate) 0.1g, buffer (sodium bicarbonate) 0.1g, water 150g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (20 parts of soybean oleic acid), 20 parts of glycidyl methacrylate, catalyst (tetrabutyl bromine
Change 0.2 part of ammonium) and polymerization inhibitor (0.1 part of methylnaphthohydroquinone) mix in a kettle, reaction temperature is controlled at 90 DEG C, is reacted to acid value
It is down to 30 DEG C after less than 2, obtains fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 25g, the first soft monomer (ethyl acrylate 13g), first
Hard monomer (styrene 48g), functional monomer (acrylic acid 1g), chain-transferring agent (lauryl mercaptan 0.5g) after mixing, slowly
It is added in the 34g water containing the first emulsifier (lauryl sodium sulfate 1g, OP-10 1g), while stirring carry out pre-emulsification,
Mixing speed is 200 revs/min, and it is stand-by that pre-emulsion is made；
S2. initiator (potassium peroxydisulfate 0.1g), buffer (sodium bicarbonate 0.1g) are added in 30g water, are sufficiently dissolved,
It is stand-by that initiator solution is made；
S3. the second soft monomer (butyl acrylate 1g), the second hard monomer (acrylonitrile 3g) are uniformly mixed, it is mixed that monomer is made
It is stand-by to close liquid；
S4. the second emulsifier (lauryl sodium sulfate 0.5g), water 86g, monomer mixed solution and 1/3 are added in a kettle
Initiator solution, stir and be warming up to 80 DEG C, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise,
It is at the uniform velocity added dropwise, drips off within pre-emulsion 2.5 hours, drip off within initiator solution 3 hours, keep the temperature 0.5 hour after dripping off, be warming up to 85 DEG C,
Cool down after 0.5 hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8, and preparation is completed.
Embodiment two
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester 25g, the first emulsifier (NP-10, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate) 2g, the second emulsifier are (phosphorous
Phosphate emulsifier) 0.5g, the first soft monomer (Isooctyl acrylate monomer) 12g, the second soft monomer (butyl acrylate) 1g, first
Hard monomer (methyl methacrylate) 40g, the second hard monomer (isobornyl acrylate) 3g, functional monomer (methacrylic acid)
1g, chain-transferring agent (mercaptoethanol) 0.5g, initiator (ammonium persulfate) 0.1g, buffer (sodium bicarbonate) 0.1g, water 150g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (20 parts of linolenic acid), 20 parts of glycidyl methacrylate, catalyst (triphenylphosphine
0.2 part) and polymerization inhibitor (0.1 part of Isooctyl acrylate monomer) mix in a kettle, reaction temperature is controlled at 90 DEG C, and reaction is to acid value
It is down to 30 DEG C after less than 2, obtains fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 25g, the first soft monomer (Isooctyl acrylate monomer 12g),
One hard monomer (methyl methacrylate 40g), functional monomer (methacrylic acid 1g), chain-transferring agent (mercaptoethanol 0.5g) are mixed
After closing uniformly, it is slowly added into the 34g water containing the first emulsifier (NP-10 1g, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 1g)
In, while carry out pre-emulsification is stirred, mixing speed is 200 revs/min, and it is stand-by that pre-emulsion is made；
S2. initiator (ammonium persulfate 0.1g), buffer (sodium bicarbonate 0.1g) are added in 30g water, are sufficiently dissolved,
It is stand-by that initiator solution is made；
S3. the second soft monomer (butyl acrylate 1g), the second hard monomer (isobornyl acrylate 3g) are uniformly mixed, system
It is stand-by at monomer mixed solution；
S4. the second emulsifier (phosphorous phosphate emulsifier 0.5g), water 86g, monomer mixed solution are added in a kettle
Initiator solution with 1/3, stirs and is warming up to 80 DEG C, after system becomes basket, while pre-emulsion and remaining initiator is added dropwise
Solution is at the uniform velocity added dropwise, and drips off within pre-emulsion 2.5 hours, drips off within initiator solution 3 hours, keeps the temperature 0.5 hour after dripping off, is warming up to
Cool down after 85 DEG C, 0.5 hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8, and preparation is completed.
Embodiment three
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester 25g, the first emulsifier (nonylphenol polyoxyethylene ether ammonium sulfate, neopelex) 2g, second
Emulsifier (phosphorous phosphate emulsifier) 0.5g, the first soft monomer (octadecyl acrylate) 12g, the second soft monomer (acrylic acid
Octadecyl ester) 1g, the first hard monomer (isobornyl acrylate) 40g, the second hard monomer (acrylonitrile) 3g, functional monomer (propylene
Acid, γ-methacryloxypropyl trimethoxy silane) 2g, chain-transferring agent (mercaptoethanol) 0.5g, initiator (persulfuric acid
Ammonium) 0.1g, buffer (sodium bicarbonate) 0.1g, water 150g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (20 parts of eleostearic acid), 20 parts of glycidyl methacrylate, catalyst (benzyl triethyl ammonium
0.2 part of ammonium chloride) and polymerization inhibitor (0.1 part of p-hydroxyanisole) mix in a kettle, reaction temperature control at 90 DEG C, reaction
To acid value less than 2 after be down to 30 DEG C, obtain fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 25g, the first soft monomer (octadecyl acrylate 12g),
One hard monomer (isobornyl acrylate 40g), functional monomer (acrylic acid 1g, γ-methacryloxypropyl trimethoxy
Silane 1g), chain-transferring agent (mercaptoethanol 0.5g) after mixing, be slowly added into containing the first emulsifier (dodecyl sulphur
Sour sodium 1g, neopelex 1g) 34g water in, while stirring carry out pre-emulsification, mixing speed is 200 revs/min, system
It is stand-by at pre-emulsion；
S2. initiator (ammonium persulfate 0.1g), buffer (sodium bicarbonate 0.1g) are added in 30g water, are sufficiently dissolved,
It is stand-by that initiator solution is made；
S3. the second soft monomer (octadecyl acrylate 1g), the second hard monomer (acrylonitrile 3g) are uniformly mixed, monomer is made
Mixed liquor is stand-by；
S4. the second emulsifier (phosphorous phosphate emulsifier 0.5g), water 86g, monomer mixed solution are added in a kettle
Initiator solution with 1/3, stirs and is warming up to 80 DEG C, after system becomes basket, while pre-emulsion and remaining initiator is added dropwise
Solution is at the uniform velocity added dropwise, and drips off within pre-emulsion 2.5 hours, drips off within initiator solution 3 hours, keeps the temperature 0.5 hour after dripping off, is warming up to
Cool down after 85 DEG C, 0.5 hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8, and preparation is completed.
Example IV
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester 35g, the first emulsifier (reactive emulsifier containing allyl, phosphorous phosphate emulsifier) 6g,
Two emulsifiers (lauryl sodium sulfate) 3.5g, the first soft monomer (Isooctyl acrylate monomer) 18g, the second soft monomer (acrylic acid fourth
Ester) 8g, the first hard monomer (methyl methacrylate) 50g, the second hard monomer (acrylonitrile) 9g, functional monomer (acrylic acid, first
Base hydroxy-ethyl acrylate, hydroxypropyl acrylate) it is 15g, chain-transferring agent (lauryl mercaptan) 2g, initiator (ammonium persulfate) 0.5g, slow
Electuary (sodium bicarbonate) 1g, water 200g.
Wherein fatty acid modified glycidyl methacrylate the preparation method comprises the following steps:
By unsaturated fatty acid (30 parts of tall oil acid), 40 parts of glycidyl methacrylate, catalyst (dimethyl Bian
1 part of amine) and polymerization inhibitor (1 part of hydroquinone) mix in a kettle, reaction temperature control at 130 DEG C, reaction to acid value less than 2
After be down to 50 DEG C, obtain fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 35g, the first soft monomer (Isooctyl acrylate monomer 18g),
One hard monomer (methyl methacrylate 50g), functional monomer (acrylic acid 2g, hydroxyethyl methacrylate 9g, acrylic acid hydroxypropyl
Ester 4g), chain-transferring agent (lauryl mercaptan 2g) after mixing, be slowly added into containing (the reaction containing allyl of the first emulsifier
Property emulsifier 3g, phosphorous phosphate emulsifier 3g) 50g water in, while stirring carry out pre-emulsification, mixing speed 2000
Rev/min, it is stand-by that pre-emulsion is made；
S2. initiator (ammonium persulfate 0.5g), buffer (sodium bicarbonate 1g) are added in 30g water, are sufficiently dissolved, system
It is stand-by at initiator solution；
S3. the second soft monomer (butyl acrylate 8g), the second hard monomer (acrylonitrile 9g) are uniformly mixed, it is mixed that monomer is made
It is stand-by to close liquid；
S4. the second emulsifier (lauryl sodium sulfate 3.5g), water 120g, monomer mixed solution and 1/ are added in a kettle
3 initiator solution stirs and is warming up to 90 DEG C, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise,
It is at the uniform velocity added dropwise, drips off within pre-emulsion 3.5 hours, drip off within initiator solution 4 hours, keep the temperature 1 hour after dripping off, be warming up to 92 DEG C, half
Cool down after hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 9, and preparation is completed.
Embodiment five
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
Olefin(e) acid ethylene oxidic ester 35g, the first emulsifier (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, nonylphenol polyoxyethylene ether ammonium sulfate)
6g, the second emulsifier (lauryl sodium sulfate) 3.5g, the first soft monomer (Isooctyl acrylate monomer, octadecyl acrylate) 18g,
Two soft monomers (butyl acrylate) 8g, the first hard monomer (acrylonitrile, methyl methacrylate) 50g, the second hard monomer (propylene
Nitrile) 9g, functional monomer (acrylic acid, hydroxy-ethyl acrylate, vinyl three (2- methoxy ethoxy) silane) 15g, chain tra nsfer
Agent (lauryl mercaptan) 2g, initiator (potassium peroxydisulfate) 0.5g, buffer (sodium bicarbonate) 1g, water 200g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (30 parts of ricinoleic acid), 40 parts of glycidyl methacrylate, catalyst (to toluene sulphur
0.5 part of acid) and polymerization inhibitor (1 part of p-hydroxyanisole) mix in a kettle, reaction temperature is controlled at 130 DEG C, is reacted to acid
Value less than 2 after be down to 50 DEG C, obtain fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 35g, the first soft monomer (Isooctyl acrylate monomer 10g, third
Olefin(e) acid octadecyl ester 8g), the first hard monomer (acrylonitrile 30g, methyl methacrylate 20g), functional monomer (acrylic acid 1.5g,
Hydroxy-ethyl acrylate 10g, vinyl three (2- methoxy ethoxy) silane 3.5g), chain-transferring agent (lauryl mercaptan 2g) mixing it is equal
After even, it is slowly added into containing the first emulsifier (disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 3g, nonylphenol polyoxyethylene ether ammonium sulfate
In 50g water 3g), while carry out pre-emulsification is stirred, mixing speed is 2000 revs/min, and it is stand-by that pre-emulsion is made；
S2. initiator (potassium peroxydisulfate 0.5g), buffer (sodium bicarbonate 1g) are added in 30g water, are sufficiently dissolved, system
It is stand-by at initiator solution；
S3. the second soft monomer (butyl acrylate 8g), the second hard monomer (acrylonitrile 9g) are uniformly mixed, it is mixed that monomer is made
It is stand-by to close liquid；
S4. the second emulsifier (lauryl sodium sulfate 3.5g), water 120g, monomer mixed solution and 1/ are added in a kettle
3 initiator solution stirs and is warming up to 90 DEG C, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise,
It is at the uniform velocity added dropwise, drips off within pre-emulsion 3.5 hours, drip off within initiator solution 4 hours, keep the temperature 1 hour after dripping off, be warming up to 92 DEG C, half
Cool down after hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 9, and preparation is completed.
Embodiment six
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified methyl-prop
(nonylphenol polyoxyethylene ether ammonium sulfate, contains the reactive emulsifier containing allyl for olefin(e) acid ethylene oxidic ester 35g, the first emulsifier
The phosphate emulsifier of phosphorus) 6g, the second emulsifier (reactive emulsifier containing allyl) 3.5g, the first soft monomer (acrylic acid
Butyl ester, Isooctyl acrylate monomer, octadecyl acrylate) 18g, the second soft monomer (butyl acrylate) 8g, the first hard monomer (propylene
Nitrile, methyl methacrylate, isobornyl acrylate) 50g, the second hard monomer (methyl methacrylate) 9g, functional monomer
(acrylic acid, hydroxy-ethyl acrylate, vinyl three (2- methoxy ethoxy) silane) 15g, chain-transferring agent (lauryl mercaptan) 2g, draw
Send out agent (ammonium persulfate) 0.5g, buffer (sodium bicarbonate) 1g, water 180g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (30 parts of talloleic acid), 40 parts of glycidyl methacrylate, catalyst (triphenylphosphine
0.6 part) and polymerization inhibitor (1 part of hydroquinone) mix in a kettle, reaction temperature control at 130 DEG C, reaction to acid value less than 2
After be down to 50 DEG C, obtain fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl methacrylate 35g, the first soft monomer (butyl acrylate 5g, acrylic acid
Different monooctyl ester 5g, octadecyl acrylate 8g), the first hard monomer (acrylonitrile 15g, methyl methacrylate 15g, isobomyl acrylate
Ester 20g), functional monomer (acrylic acid 1.5g, hydroxy-ethyl acrylate 10g, vinyl three (2- methoxy ethoxy) silane
3.5g), chain-transferring agent (lauryl mercaptan 2g) after mixing, is slowly added into containing the first emulsifier (Nonyl pheno
Ether ammonium sulfate 2g, the reactive emulsifier 2g containing allyl, phosphorous phosphate emulsifier 2g) 50g water in, while stir into
Row pre-emulsification, mixing speed are 2000 revs/min, and it is stand-by that pre-emulsion is made；
S2. initiator (ammonium persulfate 0.5g), buffer (sodium bicarbonate 1g) are added in 30g water, are sufficiently dissolved, system
It is stand-by at initiator solution；
S3. the second soft monomer (butyl acrylate 8g), the second hard monomer (methyl methacrylate 9g) are uniformly mixed, system
It is stand-by at monomer mixed solution；
S4. it is mixed that the second emulsifier (the reactive emulsifier 3.5g containing allyl), water 120g, monomer are added in a kettle
The initiator solution for closing liquid and 1/3 stirs and is warming up to 90 DEG C, after system becomes basket, while pre-emulsion is added dropwise and remaining draws
Agent solution is sent out, is at the uniform velocity added dropwise, drips off within pre-emulsion 3.5 hours, drip off within initiator solution 4 hours, keep the temperature 1 hour after dripping off, is heated up
To 92 DEG C, cool down after half an hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 9, and preparation is completed.
Embodiment seven
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified acrylic acid
Ethylene oxidic ester 30g, the first emulsifier (NP-10, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate) 4g, the second emulsifier (phosphorous phosphorus
Acid esters emulsifier) 2g, the first soft monomer (Isooctyl acrylate monomer) 15g, the second soft monomer (butyl acrylate) 5g, the first hard monomer
(methyl methacrylate) 45g, the second hard monomer (isobornyl acrylate) 6g, functional monomer (acrylic acid, acrylic acid hydroxypropyl
Ester, hydroxyethyl methacrylate) 7g, chain-transferring agent (mercaptoethanol) 1.2g, initiator (ammonium persulfate) 0.3g, buffer (phosphorus
Sour disodium hydrogen) 0.6g, water 165g.
Wherein fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid (25 parts of linolenic acid), 30 parts of glycidyl acrylate, catalyst (triphenylphosphine 0.8
Part) and polymerization inhibitor (0.5 part of hydroquinone) mix in a kettle, reaction temperature control at 100 DEG C, react to acid value less than 2
After be down to 40 DEG C, obtain fatty acid modified glycidyl acrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. firmly by fatty acid modified glycidyl acrylate 30g, the first soft monomer (Isooctyl acrylate monomer 15g), first
Monomer (methyl methacrylate 45g), functional monomer (acrylic acid 1g, hydroxypropyl acrylate 3g, hydroxyethyl methacrylate
3g), chain-transferring agent (mercaptoethanol 1.2g) after mixing, is slowly added into containing the first emulsifier (NP-10 2g, dodecane
Yl diphenyl ether sodium disulfonate 2g) 49g water in, while stirring carry out pre-emulsification, mixing speed is 1100 revs/min, and pre- cream is made
Liquid is stand-by；
S2. initiator (ammonium persulfate 0.3g), buffer (disodium hydrogen phosphate 0.6g) are added in 30g water, it is sufficiently molten
Solution, it is stand-by to be made initiator solution；
S3. the second soft monomer (butyl acrylate 5g), the second hard monomer (isobornyl acrylate 6g) are uniformly mixed, system
It is stand-by at monomer mixed solution；
S4. be added in a kettle the second emulsifier (phosphorous phosphate emulsifier 2g), water 86g, monomer mixed solution and
1/3 initiator solution stirs and is warming up to 85 DEG C, after system becomes basket, while pre-emulsion is added dropwise and remaining initiator is molten
Liquid is at the uniform velocity added dropwise, and drips off within pre-emulsion 3 hours, drips off within initiator solution 3.5 hours, keeps the temperature 0.75 hour after dripping off, is warming up to 89
DEG C, cool down after half an hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8.5, has been prepared
At.
Embodiment eight
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified acrylic acid
Ethylene oxidic ester 30g, the first emulsifier (lauryl sodium sulfate, nonylphenol polyoxyethylene ether ammonium sulfate) 4g, the second emulsifier
(phosphorous phosphate emulsifier) 2g, the first soft monomer (Isooctyl acrylate monomer, octadecyl acrylate) 15g, the second soft monomer (third
Olefin(e) acid butyl ester) 5g, the first hard monomer (acrylonitrile, methyl methacrylate) 45g, the second hard monomer (isobornyl acrylate)
6g, functional monomer (acrylic acid, hydroxy-ethyl acrylate, vinyl three (2- methoxy ethoxy) silane) 7g, chain-transferring agent (mercapto
Base ethyl alcohol) 1.2g, initiator (potassium peroxydisulfate) 0.3g, buffer (sodium bicarbonate) 0.6g, water 165g.
Wherein fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid (10 parts of ricinoleic acid, 15 parts of dehydrated castor oleic acid), 30 parts of glycidyl acrylate, urge
Agent (0.7 part of benzyltriethylammoinium chloride) and polymerization inhibitor (0.5 part of p-hydroxyanisole) mix, reaction temperature in a kettle
Control at 100 DEG C, reaction to acid value less than 2 after be down to 40 DEG C, obtain fatty acid modified glycidyl acrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl acrylate 30g, the first soft monomer (Isooctyl acrylate monomer 10g, acrylic acid
Octadecyl ester 5g), the first hard monomer (acrylonitrile 20g, methyl methacrylate 25g), functional monomer (acrylic acid 1g, acrylic acid
Hydroxyl ethyl ester 3g, vinyl three (2- methoxy ethoxy) silane 3g), chain-transferring agent (mercaptoethanol 1.2g) after mixing, delay
Slowly it is added in the 49g water containing the first emulsifier (lauryl sodium sulfate 2g, nonylphenol polyoxyethylene ether ammonium sulfate 2g), together
When stirring carry out pre-emulsification, mixing speed be 1100 revs/min, it is stand-by that pre-emulsion is made；
S2. initiator (potassium peroxydisulfate 0.3g), buffer (sodium bicarbonate 0.6g) are added in 30g water, are sufficiently dissolved,
It is stand-by that initiator solution is made；
S3. the second soft monomer (butyl acrylate 5g), the second hard monomer (isobornyl acrylate 6g) are uniformly mixed, system
It is stand-by at monomer mixed solution；
S4. be added in a kettle the second emulsifier (phosphorous phosphate emulsifier 2g), water 86g, monomer mixed solution and
1/3 initiator solution stirs and is warming up to 85 DEG C, after system becomes basket, while pre-emulsion is added dropwise and remaining initiator is molten
Liquid is at the uniform velocity added dropwise, and drips off within pre-emulsion 3 hours, drips off within initiator solution 3.5 hours, keeps the temperature 0.75 hour after dripping off, is warming up to 89
DEG C, cool down after half an hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8.5, has been prepared
At.
Embodiment nine
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: fatty acid modified acrylic acid
Ethylene oxidic ester 30g, the first emulsifier (nonylphenol polyoxyethylene ether ammonium sulfate, neopelex, dodecyl hexichol
Ether sodium disulfonate) 4g, the second emulsifier (lauryl sodium sulfate) 2g, (butyl acrylate, acrylic acid are different pungent for the first soft monomer
Ester, octadecyl acrylate) 15g, the second soft monomer (butyl acrylate) 5g, the first hard monomer (acrylonitrile, methyl methacrylate
Ester, isobornyl acrylate) 45g, the second hard monomer (isobornyl acrylate) 6g, functional monomer (acrylic acid, acrylic acid hydroxyl
Ethyl ester, vinyl three (2- methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane) 7g, chain tra nsfer
Agent (mercaptoethanol) 1.2g, initiator (ammonium persulfate) 0.3g, buffer (sodium bicarbonate) 0.6g, water 165g.
Wherein fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid (10 parts of linolenic acid, 10 parts of linoleic acid, 5 parts of ricinoleic acid), glycidyl acrylate
30 parts, catalyst (0.8 part of dimethyl Bian amine) and polymerization inhibitor (0.5 part of p-hydroxyanisole) mix in a kettle, reaction temperature
Degree control at 100 DEG C, reaction to acid value less than 2 after be down to 40 DEG C, obtain fatty acid modified glycidyl acrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. by fatty acid modified glycidyl acrylate 30g, the first soft monomer, (butyl acrylate 5g, acrylic acid are different pungent
Ester 5g, octadecyl acrylate 5g), the first hard monomer (acrylonitrile 15g, methyl methacrylate 15g, isobornyl acrylate
15g), functional monomer (acrylic acid 2g, hydroxy-ethyl acrylate 3g, vinyl three (2- methoxy ethoxy) silane 1g, γ-first
Base acryloyloxypropyltrimethoxysilane 1g), chain-transferring agent (mercaptoethanol 1.2g) after mixing, be slowly added into and contain
There are the first emulsifier (nonylphenol polyoxyethylene ether ammonium sulfate 2g, neopelex 1g, dodecyl diphenyl oxide disulfonic acid
Sodium 1g) 49g water in, while stirring carry out pre-emulsification, mixing speed is 1100 revs/min, and it is stand-by that pre-emulsion is made；
S2. initiator (ammonium persulfate 0.3g), buffer (sodium bicarbonate 0.6g) are added in 30g water, are sufficiently dissolved,
It is stand-by that initiator solution is made；
S3. the second soft monomer (butyl acrylate 5g), the second hard monomer (isobornyl acrylate 6g) are uniformly mixed, system
It is stand-by at monomer mixed solution；
S4. second emulsifier (lauryl sodium sulfate 2g), water 86g, monomer mixed solution and 1/3 are added in a kettle
Initiator solution stirs and is warming up to 85 DEG C, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise, even
Speed is added dropwise, and drips off within pre-emulsion 3 hours, drips off within initiator solution 3.5 hours, keeps the temperature 0.75 hour after dripping off, be warming up to 89 DEG C, and half
Cool down after hour；
S5. it after being cooled to 40 DEG C, is added pH adjusting agent (25%~28% ammonium hydroxide), adjustment pH value is 8.5, has been prepared
At.
Embodiment ten
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: the first emulsifier (OP-10,
Nonylphenol polyoxyethylene ether ammonium sulfate) 4.1g, fatty acid modified glycidyl acrylate 27.5g, the first soft monomer (acrylic acid
Butyl ester, Isooctyl acrylate monomer) 16.2g, the first hard monomer (styrene, methyl methacrylate, isobornyl acrylate) 43g,
Functional monomer (acrylic acid, hydroxyethyl methacrylate, vinyltrimethoxysilane) 9.7g, chain-transferring agent (lauryl mercaptan)
1g, initiator (ammonium persulfate) 0.3g, buffer (sodium bicarbonate) 0.6g, the second soft monomer (butyl acrylate) 3g, second are firmly
Monomer (styrene) 7g, the second emulsifier (OP-10, neopelex) 1.3g, water 164g.
Wherein fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid (eleostearic acid 13.9g), glycidyl acrylate 13g, catalyst (tetrabutylammonium bromide
0.8g, hydroquinone of polymerization retarder 0.3g), it puts into reaction kettle, is warming up to 95 DEG C, keep the temperature 2 hours, be continuously heating to 115 DEG C, protect
Temperature is cooled to 40 DEG C, obtains fatty acid modified glycidyl acrylate to acid value < 2.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. the first emulsifier (OP-10 1.5g, nonylphenol polyoxyethylene ether ammonium sulfate 2.6g), water are added in emulsifying kettle
48g after stirring and dissolving, is slowly added to the fatty acid modified glycidyl acrylate of above-mentioned 27.5g, the first soft monomer (acrylic acid
Butyl ester 12g, Isooctyl acrylate monomer 4.2g), the first hard monomer (styrene 30g, methyl methacrylate 10g, isobomyl acrylate
Ester 3g), functional monomer (acrylic acid 2.7g, hydroxyethyl methacrylate 5g, vinyltrimethoxysilane 2g), chain-transferring agent
(lauryl mercaptan 1g), then high speed emulsification 30 minutes, it is spare to obtain pre-emulsion；
S2. a beaker is separately taken, is added initiator (ammonium persulfate 0.3g), buffer (sodium bicarbonate 0.6g), water 30g is stirred
It mixes and makes it dissolve, it is spare to obtain initiator solution；
S3. a beaker is separately taken, the second soft monomer (butyl acrylate 3g), the second hard monomer (styrene 7g), mixing is added
Uniformly, it is spare to obtain monomer mixed solution；
S4. it is added in a kettle the second emulsifier (OP-10 1g, neopelex 0.3g), water 86g, all
Monomer mixed solution 10g and initiator solution 10.3g, stirring is warming up to 85 DEG C, becomes blue to system, while temperature is no longer
After rising, while pre-emulsion and remaining initiator solution is added dropwise, controls rate of addition, drip off within pre-emulsion 3 hours, initiator is molten
It drips off within liquid 3.5 hours, keeps the temperature 0.5 hour after dripping off, cool down after being warming up to 90 DEG C of heat preservation half an hour；
S5. 40 DEG C are cooled to, ammonium hydroxide is added, adjustment pH value is 8 to get the acrylic emulsion fatty acid modified to one kind.
Embodiment 11
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: the first emulsifier (contains allyl
Reactive emulsifier (SE-10N), the disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate of base) 4.1g, fatty acid modified glycidyl
Ester 27.5g, the first soft monomer (butyl acrylate) 16.2g, the first hard monomer (styrene, methyl methacrylate, metering system
Sour isobornyl thiocyanoacetate) 43g, functional monomer (acrylic acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate, three isopropoxy silicon of vinyl
Alkane) it is 9.7g, chain-transferring agent (lauryl mercaptan) 1g, initiator (ammonium persulfate) 0.3g, buffer (sodium bicarbonate) 0.6g, second soft
Monomer (butyl acrylate) 3g, the second hard monomer (styrene, methyl methacrylate) 7g, the second emulsifier (OP-10,12
Alkyl diphenyl ether disulphonic acid sodium) 1.3g, water 164g.
Wherein fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid (dehydrated castor oleic acid 13.9g), glycidyl acrylate 13g, catalyst (dimethyl Bian
Amine 0.7g), in polymerization inhibitor (hydroquinone 0.2g) investment reaction kettle, be warming up to 95 DEG C, keep the temperature 2 hours, be continuously heating to 115
DEG C, it keeps the temperature to acid value < 2, is cooled to 40 DEG C, obtains fatty acid modified glycidyl acrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. the first emulsifier (reactive emulsifier (SE-10N) 2g, dodecyl containing allyl are added in emulsifying kettle
Diphenyl oxide disulfonate 2.1g), water 48g, after stirring and dissolving, be slowly added to the fatty acid modified acrylic acid of above-mentioned 27.5g shrink it is sweet
Grease, the first soft monomer (butyl acrylate 16.2g), the first hard monomer (styrene 10g, methyl methacrylate 28g, methyl
Isobornyl acrylate 5g), functional monomer (acrylic acid 2.7g, hydroxy-ethyl acrylate 1g, hydroxypropyl acrylate 3g, vinyl
Three isopropoxy silane 3g), chain-transferring agent (lauryl mercaptan 1g), then high speed emulsification 30 minutes, it is spare to obtain pre-emulsion；
S2. a beaker is separately taken, is added initiator (ammonium persulfate 0.3g), buffer (sodium bicarbonate 0.6g), water 30g is stirred
It mixes and makes it dissolve, it is spare to obtain initiator solution；
S3. a beaker is separately taken, the second soft monomer (butyl acrylate 3g), the second hard monomer (styrene 4g, methyl-prop is added
E pioic acid methyl ester 3g), it is uniformly mixed, it is spare to obtain monomer mixed solution；
S4. the second emulsifier (OP-10 0.8g, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.5g), water are added in a kettle
86g, whole monomer mixed solution 10g and initiator solution 10.3g, stirring are warming up to 85 DEG C, become blue to system, temperature
After no longer rising, while pre-emulsion and remaining initiator solution is added dropwise, controls rate of addition, drip off within pre-emulsion 3 hours, causes
It drips off within agent solution 3.5 hours, keeps the temperature 0.5 hour after dripping off, cool down after being warming up to 90 DEG C of heat preservations 0.5 hour；
S5. 40 DEG C are cooled to, ammonium hydroxide is added, adjustment pH value is 8 to get the acrylic emulsion fatty acid modified to one kind.
Embodiment 12
A kind of fatty acid modified acrylic emulsion, component and component mass parts number are as follows: the first emulsifier (band allyl
Reactive emulsifier (PAM-200, adjusted pH value), the disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate of base) 3.7g, fatty acid modified first
Base glycidyl acrylate 28.8g, the first soft monomer (butyl acrylate, Isooctyl acrylate monomer) 16.2g, the first hard monomer
(styrene, isobornyl acrylate) 43g, functional monomer (acrylic acid, hydroxyethyl methacrylate, γ-methacryloxypropyl
Base propyl trimethoxy silicane) 9.7g, chain-transferring agent (lauryl mercaptan) 1g, initiator (ammonium persulfate) 0.3g, buffer (carbonic acid
Hydrogen sodium) 0.6g, the second soft monomer (butyl acrylate) 5g, the second hard monomer (styrene, methyl methacrylate) 5g, the second cream
Agent (OP-10, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate) 2g, water 164g.
Wherein fatty acid modified glycidyl methacrylate the preparation method is as follows:
By unsaturated fatty acid (eleostearic acid 13.9g), glycidyl methacrylate 14.2g, catalyst (three second of benzyl
Ammonium chloride 1.1g, hydroquinone of polymerization retarder 0.3g) it puts into reaction kettle, 95 DEG C are warming up to, 2 hours is kept the temperature, is continuously heating to
It 115 DEG C, keeps the temperature to acid value < 2, is cooled to 40 DEG C, obtains fatty acid modified glycidyl methacrylate.
Above-mentioned fatty acid modified acrylic emulsion the preparation method is as follows:
S1. the first emulsifier (reactive emulsifier (PAM-200, adjusted PH with allyl are added in emulsifying kettle
Value) 2.2g), disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 1.5g), water 48g after stirring and dissolving, is slowly added to above-mentioned 28.8g fatty acid
Modified methacrylic acid ethylene oxidic ester, the first soft monomer (butyl acrylate 4g, Isooctyl acrylate monomer 12.2), the first hard monomer
(styrene 39g, isobornyl acrylate 4g), functional monomer (acrylic acid 2.7g, hydroxyethyl methacrylate 2g, γ-methyl
Acryloyloxypropyltrimethoxysilane 5g), chain-transferring agent (lauryl mercaptan 1g), then high speed emulsifies 30 minutes to get arriving
Pre-emulsion, it is spare；
S2. a beaker is separately taken, ammonium persulfate 0.3g is added, sodium bicarbonate 0.6g, water 30g stir to dissolve to get arriving
Initiator solution, it is spare；
S3. a beaker is separately taken, the second soft monomer (butyl acrylate 5g), the second hard monomer (styrene 2g, methyl-prop is added
E pioic acid methyl ester 3g), it is uniformly mixed to get monomer mixed solution is arrived, it is spare；
S4. the second emulsifier (OP-10 1.2g, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.8g), water are added in a kettle
86g, whole monomer mixed solution 10g and initiator solution 10.3g, stirring are warming up to 85 DEG C, become blue to system, simultaneously
After temperature no longer rises, while pre-emulsion and remaining initiator solution is added dropwise, controls rate of addition, drip off within pre-emulsion 3 hours,
It drips off within initiator solution 3.5 hours, keeps the temperature 0.5 hour after dripping off, cool down after being warming up to 90 DEG C of heat preservation half an hour；
S5. 40 DEG C are cooled to, ammonium hydroxide is added, adjustment pH value is 8 to get the acrylic emulsion fatty acid modified to one kind.
The property of product prepared by observation, testing example one to embodiment 12:
Product and comparative sample prepared by selection example one to embodiment 12 is (by Chengdu Jie Shengshu nation new material science and technology
The JCW2645D that Co., Ltd provides, admittedly containing is 40%, 100mpas/25 DEG C of viscosity, PH=8) make to mark according to country respectively
Quasi- GB/T 1728-89 " paint film putty membrane drying time measuring method " tests drying time；GB/T 6739- according to national standards
2006 " paint and varnish pencil method measures hardness of paint film " test hardness；According to national standards GB/T 9286-1998 " colored paint and
The cross cut test of varnish paint film " test adhesive force；Test result is as follows for it shown in table:
From test result it can be seen that there is good stemness, hardness, attached with the fatty acid modified acrylic emulsion of preparation
Put forth effort and gloss, and be not required to that coalescing agent additionally is added in production process, system VOC is very low, meets environmental requirement.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of fatty acid modified acrylic emulsion, it is characterised in that: its component and component mass parts number are as follows: fatty acid changes
25~35 parts of property glycidyl methacrylate or fatty acid modified glycidyl acrylate, 2~6 parts of the first emulsifier,
Second 0.5~3.5 part of emulsifier, 12~18 parts of the first soft monomer, 1~8 part of the second soft monomer, 40~50 parts of the first hard monomer,
Second 3~9 parts of hard monomer, 0~15 part of functional monomer, 0.5~2 part of chain-transferring agent, 0.1~0.5 part of initiator, buffer
0.1~1 part, 150~180 parts of water.
2. acrylic emulsion according to claim 1, it is characterised in that: the fatty acid modified Glycidyl methacrylate is sweet
Grease or fatty acid modified glycidyl acrylate the preparation method is as follows:
By unsaturated fatty acid, glycidyl methacrylate or glycidyl acrylate, catalyst and polymerization inhibitor anti-
Answer in kettle and mix, reaction temperature control at 90~130 DEG C, reaction to acid value less than 2 after be down to 30~50 DEG C, obtain fatty acid and change
Property glycidyl methacrylate or fatty acid modified glycidyl acrylate；
The wherein unsaturated fatty acid, glycidyl methacrylate or glycidyl acrylate, catalyst, polymerization inhibitor
Mass parts number are as follows: 10~15 parts of unsaturated fatty acid, glycidyl methacrylate or glycidyl acrylate 10
~20 parts, 0.1~0.5 part of catalyst, 0.05~0.5 part of polymerization inhibitor.
3. acrylic emulsion according to claim 2, it is characterised in that:
The unsaturated fatty acid be soybean oleic acid, linolenic acid, linoleic acid, ricinoleic acid, dehydrated castor oleic acid, eleostearic acid,
The combination of one or more of tall oil acid；
The catalyst is tetrabutylammonium bromide, tetraethylammonium bromide, triphenylphosphine, p-methyl benzenesulfonic acid, dimethylaniline, diformazan
The combination of one or more of base Bian amine, benzyltriethylammoinium chloride；
The polymerization inhibitor is the combination of one or more of methylnaphthohydroquinone, hydroquinone, p-hydroxyanisole.
4. acrylic emulsion according to claim 1, it is characterised in that: first soft monomer is ethyl acrylate, third
The combination of one or more of olefin(e) acid butyl ester, Isooctyl acrylate monomer, octadecyl acrylate；
Second soft monomer be one of ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, octadecyl acrylate or
Several combinations.
5. acrylic emulsion according to claim 1, it is characterised in that: first hard monomer be styrene, acrylonitrile,
The combination of one or more of methyl methacrylate, isobornyl acrylate；
Second hard monomer is one or more of styrene, acrylonitrile, methyl methacrylate, isobornyl acrylate
Combination.
6. acrylic emulsion according to claim 1, it is characterised in that: the functional monomer is acrylic acid or methyl-prop
Olefin(e) acid.
7. acrylic emulsion according to claim 6, it is characterised in that: the functional monomer further includes acrylic acid hydroxypropyl
Ester, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, vinyl three (2- methoxy ethoxy) silane, γ-methacryloxypropyl
The group of one or more of base propyl trimethoxy silicane, vinyltrimethoxysilane, vinyl silane triisopropoxide
It closes.
8. acrylic emulsion according to claim 1, it is characterised in that: first emulsifier is OP-10, NP-10, ten
Sodium dialkyl sulfate, neopelex, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, nonylphenol polyoxyethylene ether ammonium sulfate,
The combination of one or more of reactive emulsifier, phosphorous phosphate emulsifier containing allyl；
Second emulsifier is OP-10, NP-10, lauryl sodium sulfate, neopelex, dodecyl hexichol
Ether sodium disulfonate, nonylphenol polyoxyethylene ether ammonium sulfate, the reactive emulsifier containing allyl, in phosphorous phosphate emulsifier
One or more of combinations.
9. acrylic emulsion according to claim 1, it is characterised in that:
The initiator is the combination of one or both of potassium peroxydisulfate, ammonium persulfate；
The buffer is the combination of one or both of sodium bicarbonate, disodium hydrogen phosphate；
The chain-transferring agent is the combination of one or both of lauryl mercaptan, mercaptoethanol.
10. a kind of preparation method of fatty acid modified acrylic emulsion as in one of claimed in any of claims 1 to 9,
It is characterized in that:
Preparation step is as follows:
S1. take a container, by fatty acid modified glycidyl methacrylate or fatty acid modified glycidyl acrylate,
First soft monomer, the first hard monomer, functional monomer, chain-transferring agent after mixing, are slowly added into containing the first emulsifier
Water in, while stirring carry out pre-emulsification, mixing speed is 200~2000 revs/min, and it is stand-by that pre-emulsion is made；
S2. a container is separately taken, initiator, buffer are added to the water, sufficiently dissolves, it is stand-by that initiator solution is made；
S3. a container is separately taken, the second soft monomer, the second hard monomer are uniformly mixed, it is stand-by that monomer mixed solution is made；
S4. be added in another reaction kettle the second emulsifier, water, monomer mixed solution and 1/3 initiator solution, stir and heat up
To 80~90 DEG C, after system becomes basket, while pre-emulsion and remaining initiator solution is added dropwise, is at the uniform velocity added dropwise, pre-emulsion 2.5~
It drips off within 3.5 hours, drips off within initiator solution 3~4 hours, keep the temperature 0.5~1 hour after dripping off, be warming up to 85~92 DEG C, 0.5 is small
When after cool down；
S5. after being cooled to 40 DEG C, pH adjusting agent is added, adjustment pH value is 8~9, and preparation is completed.
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| CN201811488356.9A CN109651550A (en) | 2018-12-06 | 2018-12-06 | A kind of fatty acid modified acrylic emulsion and preparation method thereof |
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| CN201811488356.9A Pending CN109651550A (en) | 2018-12-06 | 2018-12-06 | A kind of fatty acid modified acrylic emulsion and preparation method thereof |
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| CN110527413A (en) * | 2019-09-25 | 2019-12-03 | 广东衡光新材料科技有限公司 | A kind of acrylic acid modified water alcohol acid dispersion and its preparation method and application |
| CN111172759A (en) * | 2020-02-24 | 2020-05-19 | 成都德美精英化工有限公司 | Acrylic acid finishing emulsion and preparation method thereof |
| CN111978462A (en) * | 2020-08-31 | 2020-11-24 | 苏州建兴化学科技有限公司 | High-reactivity hydroxyl acrylic resin and preparation method thereof |
| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN112625169A (en) * | 2020-12-18 | 2021-04-09 | 上海奇想青晨新材料科技股份有限公司 | Acrylic emulsion for heavy-duty anticorrosive paint and preparation method thereof |
| CN112898479A (en) * | 2021-03-19 | 2021-06-04 | 郑州中科新兴产业技术研究院 | Unsaturated fatty acid modified water-based acrylic resin dispersion and preparation method thereof |
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| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
| CN114044848A (en) * | 2021-11-24 | 2022-02-15 | 武汉工程大学 | Fatty acid modified styrene-acrylic emulsion and preparation method thereof |
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| CN115627655A (en) * | 2022-08-31 | 2023-01-20 | 南京林业大学 | Preparation method of air-drying oil modified amphoteric polyacrylate emulsion surface sizing agent |
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| CN110527413A (en) * | 2019-09-25 | 2019-12-03 | 广东衡光新材料科技有限公司 | A kind of acrylic acid modified water alcohol acid dispersion and its preparation method and application |
| CN111172759A (en) * | 2020-02-24 | 2020-05-19 | 成都德美精英化工有限公司 | Acrylic acid finishing emulsion and preparation method thereof |
| CN111978462A (en) * | 2020-08-31 | 2020-11-24 | 苏州建兴化学科技有限公司 | High-reactivity hydroxyl acrylic resin and preparation method thereof |
| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN112625169A (en) * | 2020-12-18 | 2021-04-09 | 上海奇想青晨新材料科技股份有限公司 | Acrylic emulsion for heavy-duty anticorrosive paint and preparation method thereof |
| CN112625169B (en) * | 2020-12-18 | 2021-08-03 | 上海奇想青晨新材料科技股份有限公司 | Acrylic emulsion for heavy-duty anticorrosive paint and preparation method thereof |
| CN112898479A (en) * | 2021-03-19 | 2021-06-04 | 郑州中科新兴产业技术研究院 | Unsaturated fatty acid modified water-based acrylic resin dispersion and preparation method thereof |
| CN113214420A (en) * | 2021-06-07 | 2021-08-06 | 东莞长联新材料科技股份有限公司 | Vegetable oil-based polyacrylate anionic emulsion and preparation method and application thereof |
| CN113354769A (en) * | 2021-06-07 | 2021-09-07 | 东莞长联新材料科技股份有限公司 | Plant oil-based hydrophilic polymer aqueous dispersion and preparation method and application thereof |
| CN114230717A (en) * | 2021-10-15 | 2022-03-25 | 广汉市科思诺新材料科技有限公司 | Preparation process of water-based acrylic resin |
| CN114149531A (en) * | 2021-11-18 | 2022-03-08 | 南雄西顿化工有限公司 | Water-based acrylic resin capable of transferring and printing gloss oil and preparation method thereof |
| CN113943390A (en) * | 2021-11-18 | 2022-01-18 | 广东科力德新材料有限公司 | High-gloss acrylic resin for water-based ink and preparation method thereof |
| CN114044848A (en) * | 2021-11-24 | 2022-02-15 | 武汉工程大学 | Fatty acid modified styrene-acrylic emulsion and preparation method thereof |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
| CN114478928A (en) * | 2021-12-28 | 2022-05-13 | 江苏三木化工股份有限公司 | Water-based acrylic resin and preparation method thereof |
| CN115627655A (en) * | 2022-08-31 | 2023-01-20 | 南京林业大学 | Preparation method of air-drying oil modified amphoteric polyacrylate emulsion surface sizing agent |
| CN115627655B (en) * | 2022-08-31 | 2023-08-11 | 南京林业大学 | Preparation method of air-drying oil modified amphoteric polyacrylate emulsion surface sizing agent |
| CN115850607A (en) * | 2022-10-28 | 2023-03-28 | 科顺防水科技股份有限公司 | Preparation method of silicone-acrylate latex, silicone-acrylate latex and application |
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