CN106699957A - Preparation method of hydroxy acrylic acid emulsion - Google Patents
Preparation method of hydroxy acrylic acid emulsion Download PDFInfo
- Publication number
- CN106699957A CN106699957A CN201611120628.0A CN201611120628A CN106699957A CN 106699957 A CN106699957 A CN 106699957A CN 201611120628 A CN201611120628 A CN 201611120628A CN 106699957 A CN106699957 A CN 106699957A
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- Prior art keywords
- emulsion
- preparation
- initiator
- acrylic emulsion
- hydroxyl acrylic
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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
-
- 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
-
- 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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a hydroxy acrylic acid emulsion and belongs to the field of material preparation. The method is characterized by comprising steps as follows: (1) an emulsifier and all monomers are stirred and mixed, and a pre-emulsion is obtained; (2) the remaining emulsifier, sodium bicarbonate and deionized water are put in a four-neck bottle, stirred, subjected to reflux treatment and heated, and the pre-emulsion and an initiator are added after the emulsifier is dissolved; (3) the remaining pre-emulsion and initiator are added dropwise after the reaction ends, the mixture is cooled to the room temperature, the emulsion is poured out, and the hydroxy acrylic acid emulsion is prepared. The hydroxy acrylic acid emulsion used for a glass coating is prepared by taking methyl methacrylate, butyl acrylate, methacrylic acid, styrene and hydroxyethyl methacrylate as comonomers with a semi-continuous seed emulsion polymerization method. The prepared hydroxy acrylic acid emulsion has good viscosity, molecular weight and stability. The preparation method adopts a simple process and is easy to operate and suitable for popularization and application.
Description
Technical field
The invention belongs to field of material preparation, more particularly to a kind of preparation method of hydroxyl acrylic emulsion.
Background technology
Traditionally, the decoration of glass is by adding pigment during founding glass, or with carving after glass is cast
Carve, the technique such as frosted reaches the effect of art, and process is time-consuming to take a lot of work.With the development of coating technology, directly applied in glass surface
The trend for being filled with increase properties of product or reaching expected decorative effect increasingly increases.Wherein, the related exploitation of waterborne glass coatings is former
Reason can also directly apply to other such as ceramics, plated item, cold aluminium materials, as most fast field of growing up in glass coating.
In water paint, aqueous polyurethane coating, curing rate is good but high cost；Water-borne Alkyd Coatings have dryness poor, protect
The more shortcoming such as photosensitiveness is bad；Water-based hydroxyl acrylic coating development prospect is wide.
Acrylic emulsion have low cost, good weatherability, gloss it is high, it is environmentally friendly the characteristics of, be with fastest developing speed, kind in coating
Most environment-friendly type coatings.Study the profit to base material such as hydroxyl value, glass transition temperature, curing rate of acrylic coating
The influence of wet, paint film strength, the construction technology of coating, the gloss saturation degree of coating etc., is conducive to expanding its application field, replaces
For environmental pollution product.
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of preparation method of hydroxyl acrylic emulsion.
The technical scheme is that：
A kind of preparation method of hydroxyl acrylic emulsion, it is characterised in that comprise the following steps：
（1）By the emulsifying agent of mass fraction 20% and base methyl acrylate, butyl acrylate, hydroxyethyl methacrylate, benzene second
Alkene, methacrylic acid, potassium peroxydisulfate, amino resins, lauryl mercaptan whole monomer stirring mix to obtain pre-emulsion；
（2）Residual emulsifier, sodium acid carbonate and deionized water are put into four-necked bottle, are stirred, backflow, heating, after emulsifying agent dissolving,
Add the pre-emulsion of mass fraction 20% and the initiator of mass fraction 50%；
（3）After reaction 2-3h, remaining pre-emulsion and initiator are added dropwise respectively, 2 h are dripped off, are incubated 1 h, ammonification water adjusts pH value,
Cooling down pours out the preparation that emulsion completes hydroxyl acrylic emulsion to room temperature.
The preparation method of hydroxyl acrylic emulsion of the present invention, the emulsifying agent mass fraction 2.0%.
The preparation method of hydroxyl acrylic emulsion of the present invention, the initiator quality fraction 0.7%.
The preparation method of hydroxyl acrylic emulsion of the present invention, the butyl acrylate and methyl methacrylate
Ratio is 0.77.
The rate of addition of the preparation method of hydroxyl acrylic emulsion of the present invention, the emulsion and initiator is 0.50
mL/min。
The technical effects of the invention are that：
The preparation method of hydroxyl acrylic emulsion of the present invention, by using semi-continuous seed emulsion polymerization method, with methyl
Methyl acrylate (MMA), butyl acrylate (BA), methacrylic acid (AC), styrene (St), hydroxyethyl methacrylate
(HEMA) as comonomer, be prepared for the hydroxyl acrylic emulsion for glass lacquer, the hydroxyl acrylic emulsion of preparation it is viscous
Degree degree, molecular weight, good stability, and preparation method process is simple of the present invention, it is easy to operate, be suitable to popularization and application.
Specific embodiment
Embodiment 1
A kind of preparation method of hydroxyl acrylic emulsion, it is characterised in that comprise the following steps：
（1）By the emulsifying agent of mass fraction 20% and base methyl acrylate (MMA), butyl acrylate (BA), hydroxyethyl methacrylate
Ethyl ester (HEMA), styrene (St), methacrylic acid (AC), potassium peroxydisulfate (KPS), amino resins, lauryl mercaptan whole
Monomer stirring mixes to obtain pre-emulsion；
（2）Residual emulsifier, sodium acid carbonate and deionized water are put into four-necked bottle, are stirred, backflow, heating, after emulsifying agent dissolving,
Add the pre-emulsion of mass fraction 20% and the initiator of mass fraction 50%；
（3）After reaction 2-3h, remaining pre-emulsion and initiator are added dropwise respectively, 2h is dripped off, are incubated 1h, ammonification water regulation pH value, drop
Temperature is cooled to room temperature, pours out the preparation that emulsion completes hydroxyl acrylic emulsion.
The preparation method of hydroxyl acrylic emulsion of the present invention, the emulsifying agent mass fraction 2.0%.
The preparation method of hydroxyl acrylic emulsion of the present invention, the initiator quality fraction 0.7%.
The preparation method of hydroxyl acrylic emulsion of the present invention, the butyl acrylate and methyl methacrylate
Ratio is 0.77.
The rate of addition of the preparation method of hydroxyl acrylic emulsion of the present invention, the emulsion and initiator is 0.50
mL/min。
According to waterborne glass coatings industry use requirement, waterborne glass coatings sufficiently flexible must be provided and adhere to help, while needing
More than 2H hardness is kept with anti-scratch scuffing.Before solidification, the glass transition temperature of paint film is in 30-40 DEG C, number-average molecular weight point
Cloth can provide the hardness and adhesive force for using between 2-4 ten thousand.After solidification, the adhesive force of paint film reaches 0 grade, and hardness reaches
3H, physical and chemical performance requirement normal temperature 15d are without turning white, without bubbling, without the water resistance for coming off, and require the property of ethanol-tolerant having had
Energy.
Mass fraction with emulsifying agent increases, molecular weight and molecular weight distribution, glass transition temperature, hydroxyl value changes
Less, viscosity increased, the increase of emulsion colloidal particle diameter.Synthetic emulsion is characterized by particle size analyzer, when emulsifying agent mass fraction point
Not Wei 1.5%, 2.0%, 2.5% when, emulsion particle diameter volume mean diameter is followed successively by 0.5,0.62,2.09 μm.As emulsifying agent is used
The increase of amount, the micella number that emulsifier molecules are formed increases, the probability increase that micelle collision is combined, and increases micelle granularity,
Emulsion particle size distribution broadens.Emulsifying agent mass fraction increases simultaneously, and the collision of micelle also results in stability of emulsion variation, easily
Gel.
With the increase of initiator quality fraction, acrylic resin hydroxyl value increases, and glass transition temperature change is not clear
Aobvious, molecular weight and molecualr weight distribution change is little.When initiator concentration increases, generation free radical number increases, monomer reaction
Speed increases, and the speed that free radical spreads from the opposite micella of water increases, and generation latex number increases, and viscosity increases.Meanwhile, make
With hydrophilic ionic type initiator, due to having taken ionic group-SO on macromolecular chain4-, the enhancing of macromolecular chain hydrophily,
Play similar assistant for emulsifying agent effect so that micelle number increases, and system viscosity increases.
Potassium peroxydisulfate KPS belongs to inorganic peroxy class initiator, and effective decomposition temperature scope is in 60-80 DEG C and initiator activity
It is very high.It is different in different temperatures efficiency of initiation with reference to monomer reactivity.Acrylic monomer is active in the course of the polymerization process, due to list
The reactivity ratio of body is different, and the big monomer of activity is first polymerized, and is polymerized after the small monomer of activity.Temperature is polymerized suitable at 60-75 DEG C
Sequence：Methyl methacrylate is more than butyl acrylate more than acrylic acid more than styrene.
In course of reaction, heating or cooling need slowly to carry out, and otherwise cause hot-spot, and initiator molecule has little time to expand
Shedding can not trigger the monomer polymerization of outside and decompose generation side reaction rapidly, form stable molecule, and molecule is used as nucleus, crystal
Slowly grow up, monomer concentration is big,
And a large amount of reunions are produced, while largely consuming initiator, reduce initiator efficiency of initiation and polymer conversion.Finally
Big to product particle, emulsion dispersibility is bad.Temperature is too high, the stability reduction of dispersed phase, can also produce gel effect, occurs
Agglomeration, emulsion is unstable, and settles.
Monomer and initiator are added dropwise simultaneously, monomer is almost balanced with the relative quantity of initiator, monomer is aggregated in stabilization
Carried out in system, form micella uniform, it is to avoid local concentration is excessive.When monomer dropping is too fast, local concentration is excessive, local poly-
Close speed fast, initiator has little time dispersion and goes out just to decompose, and consumes a large amount of initiators, makes reaction insufficient.Disperse uneven, glue
Grain is unable to homogeneous nucleation, and micelle is big, is agglomerated into macromolecular sedimentation.
With the increase of hydroxy-ethyl acrylate mass fraction, the hydroxyl value of Hydroxylated acrylic resin first increases, after slightly drop
It is low.The change of hydroxyl value is primarily due to hydroxy acrylic acid hydroxyl ethyl ester in copolymerization, when its mass fraction is less than 10%, insatiable hunger
And double-bond polymerization, hydroxyl little on end group participates in polymerization, when hydroxy-ethyl acrylate mass fraction is more than 10%, hydroxyl value
Greatly, it is easy to which intramolecular polycondensation occurs, hydroxyl value is reduced.At this moment, hydroxyl value can only by other means be increased.From experimental data
Confirm, when increase HEMA mass fraction, hydroxyl value increase, HEMA from 7.5% to 11% hydroxyl value increase quickly, from 11% to
11.4%, hydroxyl value increases slow trend, so as to find the mass fraction of optimal HEMA.
Gather because glass surface has hydroxyl to form hydrogen bond or be shunk with hydroxyl with the hydroxyl of water-based hydroxyl acrylic emulsion
Close and form-Si-O-C- chemical bond rock-steady structures, make film adhesive good.Hydroxyethyl acrylate monomers belong to hard monomer, increase hydroxyl
Base value also increases the hardness of film simultaneously.Hydroxylated acrylic resin is applied on the glass substrate, the adhesive force of paint film reach 4 grades with
On, hardness reaches more than H grades.To Hydroxylated acrylic resin that HEMA mass fractions are 10% on glass curing of coating, paint film
Acidproof alkali salt and resistance to wine ability reach the requirement of glass lacquer.Hydroxyl third for glass lacquer is prepared for using emulsion polymerization technique
Olefin(e) acid resin, in acrylic acid copolymer system, by initiator, emulsifying agent mass fraction, and polymerizing condition, by the present invention
Described method is prepared for the preferable hydroxyl acrylic emulsion of viscosity, molecular weight, emulsion intercalation method.Increase the quality point of HEMA
Number, emulsion hydroxyl value first increases to be reduced afterwards.According to hardness and adhesive force requirement, regulation HE-MA mass fractions are 11% or so, hydroxyl
Base value reaches the solidifying requirements for doing glass lacquer in 5%-6%.
Claims (5)
1. a kind of preparation method of hydroxyl acrylic emulsion, it is characterised in that comprise the following steps：
（1）By the emulsifying agent of mass fraction 20% and base methyl acrylate, butyl acrylate, hydroxyethyl methacrylate, benzene second
Alkene, methacrylic acid, potassium peroxydisulfate, amino resins, lauryl mercaptan whole monomer stirring mix to obtain pre-emulsion；
（2）Residual emulsifier, sodium acid carbonate and deionized water are put into four-necked bottle, are stirred, backflow, heating, after emulsifying agent dissolving,
Add the pre-emulsion of mass fraction 20% and the initiator of mass fraction 50%；
（3）After reaction 2-3h, remaining pre-emulsion and initiator are added dropwise respectively, 2 h are dripped off, are incubated 1 h, ammonification water adjusts pH value,
Cooling down pours out the preparation that emulsion completes hydroxyl acrylic emulsion to room temperature.
2. the preparation method of hydroxyl acrylic emulsion according to claim 1, it is characterised in that：The emulsifying agent quality point
Number 2.0%.
3. the preparation method of hydroxyl acrylic emulsion according to claim 1, it is characterised in that：The initiator quality point
Number 0.7%.
4. the preparation method of hydroxyl acrylic emulsion according to claim 1, it is characterised in that：The butyl acrylate with
The ratio of methyl methacrylate is 0.77.
5. the preparation method of hydroxyl acrylic emulsion according to claim 1, it is characterised in that：The emulsion and initiator
Rate of addition be 0.50 mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611120628.0A CN106699957A (en) | 2016-12-08 | 2016-12-08 | Preparation method of hydroxy acrylic acid emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611120628.0A CN106699957A (en) | 2016-12-08 | 2016-12-08 | Preparation method of hydroxy acrylic acid emulsion |
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| Publication Number | Publication Date |
|---|---|
| CN106699957A true CN106699957A (en) | 2017-05-24 |
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ID=58936136
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611120628.0A Pending CN106699957A (en) | 2016-12-08 | 2016-12-08 | Preparation method of hydroxy acrylic acid emulsion |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554040A (en) * | 2018-12-20 | 2019-04-02 | 惠州市银海涂料有限公司 | A kind of self-drying aqueous dumb light glass lacquer and preparation method thereof |
| CN109810219A (en) * | 2019-01-28 | 2019-05-28 | 宝骏新兴建材（天津）有限公司 | Lotion and preparation method thereof based on hydroxy acrylate |
| CN110172119A (en) * | 2019-04-24 | 2019-08-27 | 武汉双虎涂料有限公司 | A kind of water-based hydroxyl acrylic emulsion and preparation method thereof |
| CN111138932A (en) * | 2019-12-19 | 2020-05-12 | 湖南太子化工涂料有限公司 | High-wear-resistance water-based paint for agricultural machinery and preparation method thereof |
-
2016
- 2016-12-08 CN CN201611120628.0A patent/CN106699957A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554040A (en) * | 2018-12-20 | 2019-04-02 | 惠州市银海涂料有限公司 | A kind of self-drying aqueous dumb light glass lacquer and preparation method thereof |
| CN109810219A (en) * | 2019-01-28 | 2019-05-28 | 宝骏新兴建材（天津）有限公司 | Lotion and preparation method thereof based on hydroxy acrylate |
| CN110172119A (en) * | 2019-04-24 | 2019-08-27 | 武汉双虎涂料有限公司 | A kind of water-based hydroxyl acrylic emulsion and preparation method thereof |
| CN111138932A (en) * | 2019-12-19 | 2020-05-12 | 湖南太子化工涂料有限公司 | High-wear-resistance water-based paint for agricultural machinery and preparation method thereof |
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Application publication date: 20170524 |