CN108570123A - A kind of acrylic acid ester emulsion and preparation method thereof for plastic basis material - Google Patents
A kind of acrylic acid ester emulsion and preparation method thereof for plastic basis material Download PDFInfo
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- CN108570123A CN108570123A CN201810168150.1A CN201810168150A CN108570123A CN 108570123 A CN108570123 A CN 108570123A CN 201810168150 A CN201810168150 A CN 201810168150A CN 108570123 A CN108570123 A CN 108570123A
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- acrylic acid
- acid ester
- ester emulsion
- basis material
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
Abstract
The present invention discloses a kind of acrylic acid ester emulsion for plastic basis material, by weight, including following raw material：40 60 parts of deionized water, 10 20 parts of butyl acrylate, 25 35 parts of methyl methacrylate, 5 10 parts of styrene, 25 parts of hydrophily unsaturated organic acid, 13 parts of function monomer, 13 parts of surfactant, 0.1 1 parts of initiator, 13 parts of pH adjusting agent；Additionally provide the preparation method of above-mentioned acrylic acid ester emulsion.Acrylic acid ester emulsion, which is made, in the present invention has excellent adhesive force, excellent solvent resistance, excellent chemical-resistance and water resistance and excellent gloss plumpness and with paint tolerance.
Description
Technical field
The present invention relates to a kind of acrylic acid ester emulsion, specifically a kind of acrylate for plastic basis material haveing excellent performance
Lotion and preparation method thereof.
Background technology
With the continuous improvement of people's living standards, the coating type for industrial plastic is also increasing, by moulding
Coating can play plastic products protection, decoration on material, enhance product performance, extend its service life.It is wide currently on the market
The general paint for plastics used is solvent type, and in solvent based coating, play crucial decisive role is solvent type resin, this
In a little solvent type resin systems, environmental pollution is serious in oleaginous system film forming procedure, irritation taste is big, organic volatile
VOC content height etc., and two-component system with paint after be then unfavorable for storage stability, need it is now with the current, and swash nature and flavor road
Greatly, organic volatile VOC content is high.
With the enhancing of consumer's environmental consciousness and formulating and implementing for environmental law, solvent type plastic paint is because containing a large amount of
Organic volatile VOC and be restricted；Two-component system, then it is poor to match paint tolerance, needs now with the current, while be easy to causeing object
The waste of material, thus, the single-component water-based paint for plastics of low VOC is favored by consumer.
Current one-component plastics encounter great technical bottleneck with acrylate paint in performance shows, i.e., aqueous painting
The use problem of lotion in material.Existing one-component acrylic resin is frequently run onto that poor water resistance, solvent resistance be poor, chemical resistance
Can it is poor, to plastic basis material poor adhesive force, glossiness it is low, with the problems such as stability is poor is painted, therefore, how to develop one kind and have excellent performance
The acrylic acid ester emulsion for plastic basis material, be one of significant technology issues of current industrial plastic coating industry.
Invention content
There is excellent adhesive force in view of the above existing problems in the prior art, the present invention provides a kind of, excellent is resistance to molten
Agent performance, excellent chemical-resistance and water resistance and excellent gloss plumpness and with paint tolerance acrylate breast
Liquid.
It is another object of the present invention to provide it is a kind of it is simple for process prepare it is above-mentioned have excellent performance be used for plastics base
The method of the acrylic acid ester emulsion of material.
To achieve the goals above, a kind of acrylic acid ester emulsion for plastic basis material that the present invention uses, by weight
Meter, which includes following raw material：40-60 parts of deionized water, 10-20 parts of butyl acrylate, methyl methacrylate
25-35 parts of ester, 5-10 parts of styrene, 2-5 parts of hydrophily unsaturated organic acid, 1-3 parts of function monomer, 1-3 parts of surfactant,
0.1-1 parts of initiator, 1-3 parts of pH adjusting agent.
The hydrophily unsaturated organic acid using acrylic acid, methacrylic acid, one kind in itaconic acid or it is above-mentioned at
Divide and is mixed with arbitrary proportion.
The function monomer using vinyltrimethoxysilane, methacryloxypropyl trimethoxy silane,
Vinyl three ('beta '-methoxy ethyoxyl) silane, allyl methacrylate silicon polymers in one kind or mentioned component with arbitrary
Ratio mixes.
The surfactant is anion emulsifier and nonionic emulsifier (1-10) in mass ratio：After (1-5) mixing
The combined emulsifier formed.
The anion emulsifier is using lauryl sulfate, dialkyl group -2- sodium sulfosuccinates, succinic acid sulfonic acid
One kind or mentioned component in sodium, dodecyl sodium sulfate, neopelex mix in any proportion.
The nonionic emulsifier is poly- using octadecanoic acid ester of polyethylene glycol, alkyl phenol polyoxyethylene ether, alkylol
One kind or mentioned component in ethylene oxide ethers mix in any proportion.
The initiator is that ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or mentioned component are mixed with arbitrary proportion
It closes.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 10-
0.5-1 parts of 30 parts of deionized waters, surfactant, 80-85 DEG C is raised to by temperature in the kettle；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 0.5-2 parts of hydrophily unsaturated organic acid, 5-10 parts of deionized water, mixing
At uniform solution, and stir 20-30 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 80-85 DEG C, 1-5 parts of monomer solution B made in step b) is added into reaction kettle,
After stirring 1min, start the made initiator solution C of a dropping step c), after reacting 15-40min, maintains temperature in the kettle in 80-85
DEG C, and residual monomer solution B is added dropwise into reaction kettle, time for adding is 3-5 hours, controls initiator solution C time for adding ratios
The time for adding of monomer solution B is 5-10 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 83-87 DEG C, keeps the temperature 1-3 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 45-50 DEG C, and pH adjusting agent is added and adjusts pH to 7-9, stirring
20-30 minutes, filtering and discharging was to get required acrylic acid ester emulsion.
Compared with prior art, the beneficial effects of the invention are as follows：
1, in the acrylic acid ester emulsion for plastic basis material of the invention, butyl acrylate, methyl methacrylate are utilized
Hybrid reaction system is constituted with siliceous function monomer, and is risen into chain reaction by hydrophily unsaturated organic acid, strand is improved
Between the degree of cross linking.First, butyl acrylate is capable of providing the toughness of paint film as soft monomer, and methyl methacrylate is as hard
Monomer can improve hardness of paint film, and the two can provide hard and tough performance by organosilicon crosslinked for paint film, and organosilicon is same
When silicon oxygen bond can be provided, since silica bond energy is big, wear-resisting paint film, solvent resistant and water-fast effect can be greatly improved.
2, in the acrylic acid ester emulsion for plastic basis material of the invention, the activated double bonds of styrene can be in reaction system
Middle formation small molecule polymerisation.Above-mentioned small molecule by polymerisation make emulsion particle during the reaction can rapid polymerization at
Small molecule chain structure can prevent lotion from macromolecular chain polymerisation occurs, effectively refine the grain size of latex particle, greatly in this way
The gloss plumpness of lotion is improved greatly, while after so that lotion is added to aqueous industrial coating, had well with paint tolerance,
The adhesive force of paint film is greatly improved simultaneously.
3, in the acrylic acid ester emulsion for plastic basis material of the invention, anion emulsifier and non-ionic emulsifier are used
The mixed combined emulsifier of agent example in mass ratio.First, anion emulsifier can stablize latex particle, while can also
The grain size of lotion is refined, stablizes polymerization, substantially increases the conversion ratio of monomer, reduce gel fraction；And dialkyl group -2- sulfo group ambers
Meticortene Solu-Delta-cortef, succinic acid sodium sulfonate, dodecyl sodium sulfate, neopelex can form single or composite emulsifying system.
First, mentioned emulsifier all has the stronger group of polarity, stronger that can assign silicon atom when polymerizeing with siliceous function monomer
Antipolarity, be allowed to butyl acrylate, methyl methacrylate, siliceous function monomer be easy to happen into chain reaction, significantly
The consistency for improving paint film makes water be not easy infiltration and enters.Secondly, the addition of nonionic emulsifier, due to non-ionic emulsifier
Hydroxyl or the amphiphilic structure molecule that ehter bond is hydrophilic group further stabilize emulsification in agent, enhance the polymerization-stable of lotion
Property.
4, in the acrylic acid ester emulsion for plastic basis material of the invention, using methyl methacrylate and styrene as
Hard monomer, since methyl methacrylate has an efficient reactivity worth, and styrene, the efficient block polymerization of butyl acrylate,
Under the premise of making the macromolecule of chaining that there is excellent hardness, certain toughness can also be provided, while three kinds of monomer molecules pass through
Reaction forms cross-linked network, substantially increases water resistance, alkali resistance and weatherability.
5, in the acrylic acid ester emulsion for plastic basis material of the invention, the preparation side of unsaturated organic acid is added dropwise after
Formula.First, unsaturated organic acid contains very hydrophilic carboxyl, and a large amount of hydrophilic radical is introduced on lotion surface layer, therefore can be with
It provides paint film high gloss plumpness, while can be engaged with plastic basis material film forming by carboxylic group, it is further provided paint
The adhesive force of film.Secondly, the rear addition of unsaturated organic acid also further enhances the crosslinking degree of lotion, provides compactness,
It is allowed to better water resistance, water can not permeate into.
6, in the acrylic acid ester emulsion for plastic basis material of the invention, after hydrophily unsaturated organic acid uses pre-emulsification
The mode of addition.By the way that hydrophily unsaturated organic acid homogenizing is distributed in macromolecular chain surface layer, lotion can be effectively reduced
Surface tension increases hydrophilicity, is easy film forming in surface cross linking densification, can be effectively reduced film-forming temperature, can make in this way
Obtaining lotion has high glass transition temperature, hardness, while having lower film-forming temperature, promotes film forming efficiency.
7, the present invention is a aqueous acrylic acid ester emulsion, greatly reduces the discharge of VOC using water as solvent,
Meet environmental requirement, therefore in film forming procedure, volatilization is water, not will produce penetrating odor, will not discharge Toxic
Matter is the acrylic acid ester emulsion of a safety non-pollution.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by embodiment, to the present invention into
Row is further described.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
In limiting the scope of the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with the technology for belonging to the present invention
The normally understood meaning of technical staff in domain is identical, and used term is intended merely to retouch in the description of the invention herein
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
A kind of acrylic acid ester emulsion for plastic basis material provided by the invention, by weight, the acrylic acid ester emulsion
Including following raw material：40-60 parts of deionized water, 10-20 parts of butyl acrylate, 25-35 parts of methyl methacrylate, styrene 5-
10 parts, 2-5 parts of hydrophily unsaturated organic acid, 1-3 parts of function monomer, 1-3 parts of surfactant, 0.1-1 parts of initiator, pH tune
Save 1-3 parts of agent.The present invention by using butyl acrylate, methyl methacrylate, styrene and siliceous function monomer mixing
Reaction, and risen into chain reaction by hydrophily unsaturated organic acid, improve the degree of cross linking of molecule interchain.Butyl acrylate is as soft
Monomer is capable of providing the toughness of paint film, and methyl methacrylate is then used as hard monomer, can be to improve hardness of paint film, the two is logical
It crosses organosilicon crosslinked, then can provide hard and tough performance for paint film, organosilicon can provide silicon oxygen bond simultaneously, due to silica bond energy
Greatly, wear-resisting paint film, solvent resistant and water-fast effect can be greatly improved.Styrene phenyl ring has active double bond, chemical anti-
Formation ordering reaction structure in system is answered, makes to form small molecule chain hydrophilic-structure in lotion, the grain of lotion can be effectively reduced
Diameter；It is risen into chain reaction by hydrophily unsaturated organic acid, improves the degree of cross linking of molecule interchain.
The hydrophily unsaturated organic acid of the controllable acrylic acid ester emulsion of reactivity of the present invention is using acrylic acid, methyl
One kind or mentioned component in acrylic acid, itaconic acid are mixed with arbitrary proportion.More hydrophily base is all had in said components
Group, and it is small molecule unsaturated organic acid, quickly hydrophilic radical can be connected in the reaction system the molecule of lotion
On chain, the hydrophily of lotion strand is improved.
The function monomer using vinyltrimethoxysilane, methacryloxypropyl trimethoxy silane,
Vinyl three ('beta '-methoxy ethyoxyl) silane, allyl methacrylate silicon polymers in one kind or mentioned component with arbitrary
Ratio mixes.Said components contain silicone molecules, and silicon oxygen bond is provided in chemical reaction, and silicon oxygen bond passes through addition, polymerization
Reaction forming does not allow easy fracture since the bond energy of silicon oxygen bond is big to high molecular chain in strand, can effectively consolidate height
Strand, to provide excellent wear-resisting, solvent resistant and water-fast performance.
The surfactant is anion emulsifier and nonionic emulsifier (1-10) in mass ratio：After (1-5) mixing
The combined emulsifier formed.
The anion emulsifier is using lauryl sulfate, dialkyl group -2- sodium sulfosuccinates, succinic acid sulfonic acid
One kind or mentioned component in sodium, dodecyl sodium sulfate, neopelex mix in any proportion.Due to anion
With excellent emulsifying effectiveness, the molecular mass and molecular vibrational temperature of polymer, the present latex particulate of generation can be effectively controlled
Granularity it is smaller, latex stability is good, does not allow to be also easy to produce cohesion block in polymerization process, reduces gel content, and Simultaneous Stabilization polymerization is anti-
It answers, refines latex particle, reduce grain size, improve adhesive force, enhancing is with paint stability.
The nonionic emulsifier is poly- using octadecanoic acid ester of polyethylene glycol, alkyl phenol polyoxyethylene ether, alkylol
One kind or mentioned component in ethylene oxide ethers mix in any proportion.Since hydroxyl in nonionic emulsifier or ehter bond are hydrophilic
The amphiphilic structure molecule of base, further stabilizes emulsification, enhances the polymerization stability of lotion.
The initiator is that ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or mentioned component are mixed with arbitrary proportion
It closes.It is readily decomposed to free radical after above-mentioned initiator is heated, and free radical can be produced from activated double bonds in the reaction system
By base grafting, copolymerization, crosslinking etc. reactions, and due to the free radical after decomposition of initiator itself have it is more highly polar, can be effective
Reinforce the stability of chemical reaction.
The pH adjusting agent is ammonium hydroxide.Ammonium hydroxide can effectively neutralize the carboxyl in acrylic emulsion, and not influence lotion
The water resistance of script, and system has better Calcium ion stability and freeze-thaw stability after reconciliation.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 10-
0.5-1 parts of 30 parts of deionized waters, surfactant, 80-85 DEG C is raised to by temperature in the kettle；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 0.5-2 parts of hydrophily unsaturated organic acid, 5-10 parts of deionized water, mixing
At uniform solution, and stir 20-30 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 80-85 DEG C, 1-5 parts of monomer solution B made in step b) is added into reaction kettle,
After stirring 1min, start the made initiator solution C of a dropping step c), after reacting 15-40min, maintains temperature in the kettle in 80-85
DEG C, and residual monomer solution B is added dropwise into reaction kettle, time for adding is 3-5 hours, controls initiator solution C time for adding ratios
The time for adding of monomer solution B is 5-10 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 83-87 DEG C, keeps the temperature 1-3 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 45-50 DEG C, and pH adjusting agent is added and adjusts pH to 7-9, stirring
20-30 minutes, filtering and discharging was to get required acrylic acid ester emulsion.
Embodiment 1
A kind of acrylic acid ester emulsion for plastic basis material, by weight, the acrylic acid ester emulsion include following raw material：
40 parts of deionized water, 10 parts of butyl acrylate, 25 parts of methyl methacrylate, 5 parts of styrene, hydrophily unsaturated organic acid 2
Part, 1 part of function monomer, 1 part of surfactant, 0.1 part of initiator, 1.5 parts of pH adjusting agent.
The hydrophily unsaturated organic acid is the mixed liquor of 1 part of acrylic acid, 1 part of methacrylic acid.
The function monomer uses vinyltrimethoxysilane.
The surfactant is anion emulsifier and nonionic emulsifier in mass ratio 1:The combination formed after 1 mixing
Type emulsifier.The anion emulsifier uses dodecyl sodium sulfate；The nonionic emulsifier uses alkyl phenol polyoxy second
Alkene ether.
The initiator is ammonium persulfate.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 10 parts
Temperature in the kettle is raised to 80 DEG C by 0.5 part of deionized water, surfactant；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 0.5 part of hydrophily unsaturated organic acid, 5 parts of deionized water are mixed into uniformly
Solution, and stir 20 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 80 DEG C, 1 part of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 15min, maintain temperature in the kettle at 80 DEG C, and to anti-
It answers and residual monomer solution B is added dropwise in kettle, time for adding is 3 hours, and control initiator solution C time for adding is than monomer solution B's
Time for adding is 5 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 83 DEG C, keeps the temperature 1 hour；
G) to the end of heat preservation, temperature of reaction kettle is down to 45 DEG C, and pH adjusting agent ammonium hydroxide is added and adjusts pH to 7, stirring 20
Minute, filtering and discharging is to get required acrylic acid ester emulsion.
Embodiment 2
A kind of acrylic acid ester emulsion for plastic basis material, by weight, the acrylic acid ester emulsion include following raw material：
45 parts of deionized water, 12 parts of butyl acrylate, 28 parts of methyl methacrylate, 7 parts of styrene, hydrophily unsaturated organic acid
2.5 parts, 1.5 parts of function monomer, 1.5 parts of surfactant, 0.3 part of initiator, 3 parts of pH adjusting agent.
The hydrophily unsaturated organic acid is using acrylic acid, methacrylic acid according to 4:1 mixing.
The function monomer is pressed using vinyltrimethoxysilane, methacryloxypropyl trimethoxy silane
According to 2:1 mixed deterioration.
The surfactant is anion emulsifier and nonionic emulsifier in mass ratio 2:The combination formed after 1 mixing
Type emulsifier.The anion emulsifier uses dialkyl group -2- sodium sulfosuccinates；The nonionic emulsifier uses polyoxy second
Alkene sorbitol monooleate.
The initiator is potassium peroxydisulfate.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 15 parts
Temperature in the kettle is raised to 82 DEG C by 0.7 part of deionized water, surfactant；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 0.7 part of hydrophily unsaturated organic acid, 7 parts of deionized water are mixed into uniformly
Solution, and stir 24 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 82 DEG C, 2 parts of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 20min, maintain temperature in the kettle at 82 DEG C, and to anti-
It answers and residual monomer solution B is added dropwise in kettle, time for adding is 3.5 hours, and control initiator solution C time for adding is than monomer solution B
More 8 minutes of time for adding；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 85 DEG C, keeps the temperature 2 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 45 DEG C, and pH adjusting agent ammonium hydroxide is added and adjusts pH to 7.8, stirring
25 minutes, filtering and discharging was to get required acrylic acid ester emulsion.
Embodiment 3
A kind of acrylic acid ester emulsion for plastic basis material, by weight, the acrylic acid ester emulsion include following raw material：
50 parts of deionized water, 15 parts of butyl acrylate, 30 parts of methyl methacrylate, 7.5 parts of styrene, hydrophily unsaturated organic acid
3.5 parts, 2 parts of function monomer, 2 parts of surfactant, 0.5 part of initiator, 2.5 parts of pH adjusting agent.
The hydrophily unsaturated organic acid is using methacrylic acid, itaconic acid according to 2:3 mixing.
The function monomer is using methacryloxypropyl trimethoxy silane, (the 'beta '-methoxy second of vinyl three
Oxygroup) silane is according to 1:1 mixing.
The surfactant is anion emulsifier and nonionic emulsifier in mass ratio 4：The combination formed after 1 mixing
Type emulsifier.The anion emulsifier using succinic acid sodium sulfonate, dodecyl sodium sulfate, neopelex according to
1:2:1.The nonionic emulsifier uses alkyl phenol polyoxyethylene ether.
The initiator is sodium peroxydisulfate.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 20 parts
Temperature in the kettle is raised to 83 DEG C by 0.75 part of deionized water, surfactant；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 1 part of hydrophily unsaturated organic acid, 8 parts of deionized water are mixed into uniform
Solution, and stir 25 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 83 DEG C, 3 parts of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 25min, maintain temperature in the kettle at 83 DEG C, and to anti-
It answers and residual monomer solution B is added dropwise in kettle, time for adding is 4 hours, and control initiator solution C time for adding is than monomer solution B's
Time for adding is 8 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 85 DEG C, keeps the temperature 2 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 50 DEG C, and pH adjusting agent ammonium hydroxide is added and adjusts pH to 8, stirring 25
Minute, filtering and discharging is to get required acrylic acid ester emulsion.
Embodiment 4
A kind of acrylic acid ester emulsion for plastic basis material, by weight, the acrylic acid ester emulsion include following raw material：
60 parts of deionized water, 20 parts of butyl acrylate, 35 parts of methyl methacrylate, 10 parts of styrene, hydrophily unsaturated organic acid 5
Part, 3 parts of function monomer, 3 parts of surfactant, 1 part of initiator, 3 parts of pH adjusting agent.
The hydrophily unsaturated organic acid is using methacrylic acid, itaconic acid according to 2:3 mixing.
The function monomer uses vinyltrimethoxysilane.
The surfactant is anion emulsifier and nonionic emulsifier in mass ratio 9：The combination formed after 1 mixing
Type emulsifier.The anion emulsifier is using lauryl sulfate, dialkyl group -2- sodium sulfosuccinates according to 1:1 mixing.
The nonionic emulsifier uses alkyl phenol polyoxyethylene ether.
The initiator is ammonium persulfate.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 30 parts
Temperature in the kettle is raised to 85 DEG C by 1 part of deionized water, surfactant；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 2 parts of hydrophily unsaturated organic acid, 10 parts of deionized water are mixed into uniformly
Solution, and stir 30 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 85 DEG C, 5 parts of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 40min, maintain temperature in the kettle at 85 DEG C, and to anti-
It answers and residual monomer solution B is added dropwise in kettle, time for adding is 5 hours, and control initiator solution C time for adding is than monomer solution B's
Time for adding is 10 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, control parent
Aqueous unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 87 DEG C, keeps the temperature 3 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 50 DEG C, and pH adjusting agent ammonium hydroxide is added and adjusts pH to 9, stirring 30
Minute, filtering and discharging is to get required acrylic acid ester emulsion.
Embodiment 5
A kind of acrylic acid ester emulsion for plastic basis material, by weight, the acrylic acid ester emulsion include following raw material：
50 parts of deionized water, 18 parts of butyl acrylate, 32 parts of methyl methacrylate, 8 parts of styrene, hydrophily unsaturated organic acid 4
Part, 3 parts of function monomer, 3 parts of surfactant, 0.8 part of initiator, 2.8 parts of pH adjusting agent.
The hydrophily unsaturated organic acid is the mixed liquor of 2 parts of acrylic acid, 2 parts of methacrylic acid.
The function monomer is 1 part of methacryloxypropyl trimethoxy silane, (the 'beta '-methoxy ethoxy of vinyl three
Base) 1 part of silane, 1 part of allyl acrylate.
The surfactant is anion emulsifier and nonionic emulsifier example 2 in mass ratio：Combination is formed after 1 mixing
Type emulsifier.
The anion emulsifier is using 0.5 part of dodecyl sodium sulfate, 1.5 parts of neopelex.
The nonionic emulsifier uses 1 part of octadecanoic acid ester of polyethylene glycol.
The initiator is ammonium persulfate 0.1,0.2 part of potassium peroxydisulfate.
The pH adjusting agent is ammonium hydroxide.
In addition, the present invention also provides a kind of preparation methods of the acrylic acid ester emulsion for plastic basis material, specifically
Include the following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 25 parts
Temperature in the kettle is raised to 84 DEG C by 0.8 part of deionized water, surfactant；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, benzene
Ethylene, function monomer and residual surface activating agent, 1.8 parts of hydrophily unsaturated organic acid, 8 parts of deionized water are mixed into uniformly
Solution, and stir 28 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is standby
With；
D) it waits for that temperature in the kettle reaches 84 DEG C, 4 parts of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 30min, maintain temperature in the kettle at 84 DEG C, and to anti-
It answers and residual monomer solution B is added dropwise in kettle, time for adding is 4 hours, and control initiator solution C time for adding is than monomer solution B's
Time for adding is 10 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise and (stirs in advance
Mix mixing), control hydrophily unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 86 DEG C, keeps the temperature 2.5 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 45 DEG C, and pH adjusting agent ammonium hydroxide is added and adjusts pH to 8.5, stirring
25 minutes, filtering and discharging was to get required acrylic acid ester emulsion.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of acrylic acid ester emulsion for plastic basis material, which is characterized in that by weight, which includes
Following raw material：40-60 parts of deionized water, 10-20 parts of butyl acrylate, 25-35 parts of methyl methacrylate, styrene 5-10
Part, 2-5 parts of hydrophily unsaturated organic acid, 1-3 parts of function monomer, 1-3 parts of surfactant, 0.1-1 parts of initiator, pH are adjusted
1-3 parts of agent.
2. a kind of acrylic acid ester emulsion for plastic basis material according to claim 1, which is characterized in that described is hydrophilic
Property unsaturated organic acid uses one kind in acrylic acid, methacrylic acid, itaconic acid or mentioned component to be mixed with arbitrary proportion.
3. a kind of acrylic acid ester emulsion for plastic basis material according to claim 1, which is characterized in that the function
Monomer is using vinyltrimethoxysilane, methacryloxypropyl trimethoxy silane, (the 'beta '-methoxy second of vinyl three
Oxygroup) silane, allyl methacrylate silicon polymers in one kind or mentioned component mixed with arbitrary proportion.
4. a kind of acrylic acid ester emulsion for plastic basis material according to claim 1, which is characterized in that live on the surface
Property agent be anion emulsifier and nonionic emulsifier (1-10) in mass ratio：The combined emulsifier formed after (1-5) mixing.
5. a kind of acrylic acid ester emulsion for plastic basis material according to claim 4, which is characterized in that the anion
Emulsifier is using lauryl sulfate, dialkyl group -2- sodium sulfosuccinates, succinic acid sodium sulfonate, dodecyl sodium sulfate, ten
One kind or mentioned component in dialkyl benzene sulfonic acids sodium mix in any proportion.
6. a kind of acrylic acid ester emulsion for plastic basis material according to claim 4 or 5, which is characterized in that described non-
Ionic emulsifying agent is using in octadecanoic acid ester of polyethylene glycol, alkyl phenol polyoxyethylene ether, alkyl alcohol ethoxylates class
A kind of or mentioned component mixes in any proportion.
7. a kind of acrylic acid ester emulsion for plastic basis material according to claim 1, which is characterized in that the initiator
For in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate one kind or mentioned component mixed with arbitrary proportion.
8. a kind of acrylic acid ester emulsion for plastic basis material according to claim 1, which is characterized in that the pH is adjusted
Agent is ammonium hydroxide.
9. the preparation method described in a kind of any one of claim 1-8 for the acrylic acid ester emulsion of plastic basis material, feature exist
In specifically including following steps：
A) preparation of bottom material liquid A：To equipped with blender, condenser, constant flow pump feeding device reaction kettle in, be added 10-30 parts
0.5-1 parts of deionized water, surfactant, 80-85 DEG C is raised to by temperature in the kettle；
B) preparation of monomer solution B：At normal temperatures and pressures by the Butyl acrylate of formula ratio, methyl methacrylate, styrene,
Function monomer and residual surface activating agent, 0.5-2 parts of hydrophily unsaturated organic acid, 5-10 parts of deionized water are mixed into uniformly
Solution, and stir 20-30 minutes it is spare；
C) preparation of initiator solution C：The initiator of formula ratio is added in remaining deionized water, stirring and dissolving is spare；
D) it waits for that temperature in the kettle reaches 80-85 DEG C, 1-5 parts of monomer solution B made in step b), stirring is added into reaction kettle
After 1min, start the made initiator solution C of a dropping step c), after reacting 15-40min, maintain temperature in the kettle at 80-85 DEG C,
And residual monomer solution B is added dropwise into reaction kettle, time for adding is 3-5 hours, and control initiator solution C time for adding compares monomer
The time for adding of solution B is 5-10 minutes more；
E) when monomer solution B is added dropwise to residue 1/3, while remaining hydrophily unsaturated organic acid is added dropwise, controls hydrophily
Unsaturated organic acid drips off simultaneously with monomer solution B；
F) after agent solution C to be triggered is added dropwise to complete, reaction kettle is warming up to 83-87 DEG C, keeps the temperature 1-3 hours；
G) to the end of heat preservation, temperature of reaction kettle is down to 45-50 DEG C, and pH adjusting agent is added and adjusts pH to 7-9, stirs 20-30
Minute, filtering and discharging is to get required acrylic acid ester emulsion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625532A (en) * | 2021-01-21 | 2021-04-09 | 山东益利油漆有限公司 | Efficient anticorrosive water-based acrylic coating and preparation method thereof |
| WO2021197055A1 (en) * | 2020-04-01 | 2021-10-07 | 上海保立佳新材料有限公司 | Acrylate emulsion with high water whitening resistance and preparation method therefor |
| 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 |
| CN114805666A (en) * | 2022-05-13 | 2022-07-29 | 泰兴盛嘉树脂有限公司 | Waterborne itaconic acid modified acrylic resin and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418824A (en) * | 2015-11-12 | 2016-03-23 | 佛山市顺德区巴德富实业有限公司 | Reaction-activity-controllable acrylate emulsion and preparation method thereof |
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2018
- 2018-02-28 CN CN201810168150.1A patent/CN108570123A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418824A (en) * | 2015-11-12 | 2016-03-23 | 佛山市顺德区巴德富实业有限公司 | Reaction-activity-controllable acrylate emulsion and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021197055A1 (en) * | 2020-04-01 | 2021-10-07 | 上海保立佳新材料有限公司 | Acrylate emulsion with high water whitening resistance and preparation method therefor |
| CN112625532A (en) * | 2021-01-21 | 2021-04-09 | 山东益利油漆有限公司 | Efficient anticorrosive water-based acrylic coating 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 |
| CN114805666A (en) * | 2022-05-13 | 2022-07-29 | 泰兴盛嘉树脂有限公司 | Waterborne itaconic acid modified acrylic resin and preparation method and application thereof |
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Application publication date: 20180925 |