CN108192016A - Acrylic emulsion and preparation method thereof and acrylate structural adhesive comprising it and preparation method and application - Google Patents
Acrylic emulsion and preparation method thereof and acrylate structural adhesive comprising it and preparation method and application Download PDFInfo
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- CN108192016A CN108192016A CN201810126950.7A CN201810126950A CN108192016A CN 108192016 A CN108192016 A CN 108192016A CN 201810126950 A CN201810126950 A CN 201810126950A CN 108192016 A CN108192016 A CN 108192016A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- 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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- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- 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
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- Health & Medical Sciences (AREA)
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Abstract
Acrylate structural adhesive the present invention provides acrylic emulsion and preparation method thereof and comprising it and preparation method and application.Acrylic emulsion of the present invention be by first under the conditions of high shear dispersion, by raw material of acrylic monomers, epoxy resin, emulsifier and crosslinking agent carry out pre-emulsification, then again using reaction kettle be added dropwise method it is obtained.In the present invention, by for preparation process, the adjustment of the raw materials such as emulsifier used, crosslinking agent, so that prepared acrylic emulsion is with good stability and caking property, it and can be with external wall, particularly alkaline stronger new wall has good adhesion, and will not generate phenomena such as fracturing and flaking off；Meanwhile can also be used to the top sizing of paper by the further prepared acrylate structural adhesive of the acrylic emulsion, so as to play the role of improving paper strength, tear-proof, and resistance denaturation.
Description
Technical field
The present invention relates to lotion field, in particular to acrylic emulsion and preparation method thereof and its third is included
Olefin(e) acid ester structure glue and preparation method and application.
Background technology
Present building trade selects acrylic acid ordinary emulsion (such as phenylpropyl alcohol, the pure third gradegrade C) as base-material to match producing building envelope mostly
Close priming paint.However, these base-materials are mostly without by modification or using simple two dimension crosslinking or only with list
One grafting is handled, thus its water resistance, chemical-resistant stability and caking property intensity are generally poor, adhesion strength with base material,
The technical indicators such as strong degree are also all relatively more general, so that it cannot realize really excellent back cover effect.Simultaneously as new wall
Materials for wall alkalinity is stronger, thus also can generate destruction to base-material coating and influence paint vehicle film forming, and cause what is formed
Paint film is unable to reach quality requirement.
Thus, a kind of new acrylic emulsion is developed, is ten either for coating industry or building trade
Divide necessary.
In view of this, it is special to propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of acrylic emulsion, in preparation method of the present invention, leads to
The adjustment for preparing raw material and technique is crossed, so as to be effectively improved the performance of obtained acrylic emulsion.
The second object of the present invention is to provide a kind of acrylic emulsion as prepared by the method for the present invention.
The third object of the present invention is to provide a kind of acrylate structural adhesive using acrylic emulsion of the present invention as raw material,
And the preparation method and application of the acrylate structural adhesive.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of acrylic emulsion, the preparation method include the following steps：Under the conditions of high shear dispersion,
By acrylic monomers, epoxy resin, emulsifier and crosslinking agent hybrid reaction, acrylic emulsion is obtained.
Preferably, in the preparation method of acrylic emulsion of the present invention, the acrylic monomers includes acrylic acid, third
Acrylamide, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid hydroxyl second
One or more of ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl styrene and styrene；
And/or the epoxy resin includes：One or more of glycidyl methacrylate, aqueous epoxy resins.
Preferably, in the preparation method of acrylic emulsion of the present invention, the crosslinking agent includes：Triallyl different three
Polycyanate ester.
Preferably, in the preparation method of acrylic emulsion of the present invention, the emulsifier includes：Alkyl alcohol ether/phenol
One or more of ether surfactant and sulfosuccinate sodium/ammonium salt.
Meanwhile the present invention also provides the acrylic emulsions that the preparation method by acrylic emulsion of the present invention obtains.
Further, the present invention also provides a kind of acrylate structural adhesive, the raw material packets of the acrylate structural adhesive
Include acrylic emulsion of the present invention.
Meanwhile the present invention also provides the preparation method of the water-and acrylate structure glue, the method includes such as
Lower step：
Acrylic emulsion of the present invention is mixed with auxiliary material to get to the acrylate structural adhesive；
Preferably, in the preparation method of water-and acrylate structure glue of the present invention, the auxiliary material includes ethylene glycol,
And one or both of alcohol ester 12.
Likewise, the application the present invention also provides water-and acrylate structure glue of the present invention in papermaking；
And/or application of the water-and acrylate structure glue of the present invention in external wall processing.
Further, present invention provides the paper surfaces comprising water-and acrylate structure glue of the present invention to apply
Jelly；
And/or the external wall processing coating comprising water-and acrylate structure glue of the present invention.
Meanwhile the present invention also provides a kind of paper, the paper is through paper surface of the present invention by raw material paper
It is obtained after sizing agent processing.
Compared with prior art, beneficial effects of the present invention are：
In the present invention, by for preparation process, the adjustment of the raw materials such as emulsifier used, crosslinking agent so that prepared
Acrylic emulsion is with good stability and caking property, can be with external wall, particularly alkaline stronger new wall tool
There is good adhesion, and phenomena such as fracturing and flaking off will not be generated；
Meanwhile it is applied by the surface that the further prepared acrylate structural adhesive of the acrylic emulsion can also be used to paper
Glue, so as to play the role of improving paper strength, tear-proof, and resist faint-hearted denaturation.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
It can not meet reality in view of the acrylic resin high molecular material currently as external wall closed material base-material
Border use demand, especially for the actual techniques problem such as the tolerance of the stronger new wall of alkalinity is poor, the present invention provides
A kind of novel acrylic lotion, by for raw materials used and technique adjustment, so that prepared acrylic emulsion
It disclosure satisfy that the use technology of external wall closing requires.
Specifically, acrylic emulsion provided by the present invention, is with acrylic monomers, epoxy resin, emulsifier, Yi Jijiao
It is obtained by the reaction for raw material to join agent；
Wherein, in above-mentioned raw materials, the acrylic monomers is：Acrylic acid, acrylamide, methacrylic acid, acrylic acid first
Ester, ethyl acrylate, butyl acrylate, methyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid
One or more of hydroxypropyl acrylate, methyl styrene and styrene；
The epoxy resin is：One or more of glycidyl methacrylate, aqueous epoxy resins；
The crosslinking agent is：Iso-cyanuric acid triallyl ester.
The emulsifier is：One in alkyl alcohol ether/phenol ether surfactant and sulfosuccinate sodium/ammonium salt
Kind is several.
Further, in addition to as above raw material, the raw material of acrylic emulsion provided by the present invention can also include initiator,
The auxiliary materials such as neutralizer and preservative；
Wherein, the initiator includes the initiation of the persulfuric acid salts such as tert-butyl hydroperoxide, ammonium persulfate, potassium peroxydisulfate
Agent；
The neutralizer includes：Triethylamine, isopropylamine, trimethyl ethamine, ammonium hydroxide and APM-95 etc.；
The preservative includes：Kathon CG etc..
The monomer of conventional styrene-acrylic emulsion is generally with styrene, acrylamide, acrylic acid, acrylic resin, molecular weight
Conditioning agent and initiator are raw material, and using prepared by seed emulsion polymerization pre-emulsification.
And in the present invention, by the raw material prepared for conventional acrylic lotion and the adjustment of technique, so as to effectively change
The performance of prepared acrylic emulsion has been apt to it, in terms of raw material adjustment：
First, in the present invention, triallyl ester isocyanates (TAIC) is increased as crosslinking agent, since TAIC has three
A active group, thus during reaction, three groups are carried out at the same time reaction, can form space multistory crosslinking, so as to
It can realize the stereoeffect at microcosmic seat, increase structural stress, the variation for having matter with the material in existing market,
With structural stress, tensile strength is considerably increased, and becomes a kind of structural material.
Secondly, it is used as raw material by increasing acrylic acid epoxy base monomer, so that being grafted in product propylene yogurt liquid
Epoxy group can also greatly increase adhesive force；Meanwhile in acrylic emulsion building-up process, can with epoxy group occur and
It is grafted, changes the adhesion strength of product；Further, by with the crosslinked effects of TAIC so that obtained product
Material is provided with 3 D cross-linked structure on microcosmic, considerably increases the structural mechanics characteristic of material.
In general, traditional water-based acrylic resin material, if in the case that glass transition temperature is more than 10 DEG C, often shape
It is poor with the cohesive force of priming paint into the film of one layer of hard, and in the present invention, by increasing the parallel epoxy group of epoxy resin
The defects of rolling into a ball graft modification, this respect can be substantially improved
Finally, our technology is in this materials synthesis, employs that stability is good, has good hydrophily, simultaneously
Structure and one kind or several in the close alkyl polyethylene of acrylate, alkanolamide or sulfosuccinate sodium/ammonium salt
The compound of kind is as emulsifier, so that obtained pre-emulsion has good chemical stability, even if (big for a long time
In for 24 hours) place the phenomenon that will not being layered；Meanwhile even if directly by highly basic, CaCl2Or prepared by cement addition
In acrylic emulsion, the stability of acrylic acid solution will not be influenced；
The dosage of emulsifier is preferably controlled the 0.5~2% of raw material gross mass.
And in terms of preparation process, the present invention in abandoned traditional stirring pre-emulsification technology, but take high shear into
Row pre-emulsification.
Further, used process of preparing using the present invention, it is not only more efficient, but also can reduce for breast
The use of agent, while prepared stability of emulsion is more excellent.
The technique of the above-mentioned preparation method of the present invention, mainly first will under high shear conditions, by acrylic monomers, epoxy
Resin, partial emulsifier (preferably 40% emulsifier) and crosslinking agent are mixed to get pre-emulsion；
Then, then by part pre-emulsion and residual emulsifier being mixed to get seed emulsion, (this step is preferably in reaction kettle
Middle progress)；Finally, then by remaining pre-emulsion it is added dropwise in seed emulsion, and add in initiator, then cools down, add in adjuvant, into
And obtain acrylic emulsion.
As above specific steps can refer to as follows：
In high-shear emulsion machine, add in portions of de-ionized water, partial emulsifier (preferably 40% emulsifier) and
Then crosslinking agent adds in acrylic monomers, epoxy resin, and mixes under high shear conditions, obtain acrylic acid pre-emulsion；
Then, the emulsifier of surplus and the deionized water of surplus, heating stirring, heating are added in a kettle
To 60~65 DEG C, the pre-emulsion of formula ratio 10% or so is added in, as seed emulsion, carries out seed reaction；
79 DEG C are continuously heating to, rapid reaction occurs, 86 DEG C of controlling reaction temperature ＜, is added dropwise in 2~2.5h remaining pre-
Lotion then heats to 90 DEG C；The state that period is kept stirring, and gradually add initiator so that reaction is completed, and is cooled to ＜
45 DEG C, neutralizer, preservative are added in, adjusts pH to 7 or so, blowing, packaging.
Further, ethylene glycol and alcohol ester ten can also be coordinated second-class auxiliary using acrylic emulsion of the present invention as raw material
Material, obtains acrylate structural adhesive；
And the preparation method of acrylate structural adhesive as described above is more convenient, by prepared acrylic emulsion with it is auxiliary
Material mixing.
As the not only stable structure, but also can also be used to papermaking and build of the acrylate structural adhesive prepared by as above method
It builds in industry.
Specifically, in paper industry, can using acrylate structural adhesive of the present invention as paper surface sizing agent or
Functional component in paper surface sizing agent and use.
And by applying acrylate structural adhesive of the present invention in paper outer surface, it can cause paper that there is special work(
Can, and the intensity of paper can be increased, obtain having good tear-proof, anti-deformation behavior specialties；
Further, since the presence of paper own wt (is particularly in the production process of actual paper, the length of paper
Degree may be up to hundreds of meters or several kilometers), in conventional production technology, even if having used conventional surface in paper surface
Sizing agent also results in paper and the problem of lack of homogeneity that both ends width is wide, intermediate width is narrow occurs, and with prepared by the present invention
Acrylate construction glue as Cypres, then can cause paper that there is better intensity, into without prepared by generation
Paper the wide unevenness of different parts situation.
And in building trade, then acrylate structural adhesive of the present invention as external wall seal coat or can be built
The function raw material for building exterior wall seal coat uses；
For common coating, acrylate structural adhesive permeability and caking property higher of the present invention, and penetrate into
The structure glue of wall can play the role of rivet, so as to increase the globality with the binding force of wall and painting structure, prevent
Priming paint and the finishing coat on upper strata come off.
Embodiment 1
Using methyl methacrylate, acrylamide, acrylic acid and methyl acrylate as raw material propylene acid monomers；Methyl
Glycidyl Acrylate is raw material epoxy resin；Iso-cyanuric acid triallyl ester is crosslinking agent；Alkyl alcohol ether and alkanolamide
For emulsifier；Triethylamine is neutralizer；Kathon CG is preservative, prepares the acrylic emulsion of embodiment 1.
Preparation process is with reference to as follows：
In high-shear emulsion machine, portions of de-ionized water, partial emulsifier and crosslinking agent are added in, then acrylic acid list
Body, epoxy resin, and mix under high shear conditions, obtain acrylic acid pre-emulsion；
Then, the emulsifier of surplus and the deionized water of surplus, heating stirring, heating are added in a kettle
To 60~65 DEG C, the pre-emulsion of formula ratio 10% or so is added in, as seed emulsion, carries out seed reaction；
79 DEG C are continuously heating to, rapid reaction occurs, 86 DEG C of controlling reaction temperature ＜, is added dropwise in 2~2.5h remaining pre-
Lotion then heats to 90 DEG C；The state that period is kept stirring, and gradually add initiator so that reaction is completed, and is cooled to ＜
45 DEG C, neutralizer, preservative are added in, adjusts pH to 7 or so, blowing, packaging.
Then, 1 gained acrylic emulsion of embodiment with alcohol ester 12 is mixed, obtains the acrylate structural of embodiment 1
Glue.
Embodiment 2
By raw material propylene of ethyl acrylate, hydroxy-ethyl acrylate, methyl methacrylate and methacrylic acid, acid is single
Body；Aqueous epoxy resins are raw material epoxy resin；Iso-cyanuric acid triallyl ester is crosslinking agent；Alkyl phenol ether and sulfosuccinic
Sodium salt is emulsifier；Ammonium hydroxide is neutralizer；Kathon CG is preservative, prepares the acrylic emulsion of embodiment 2.
Preparation process reference implementation example 1.
Then, 2 gained acrylic emulsion of embodiment with ethylene glycol is mixed, obtains the acrylate structural adhesive of embodiment 2.
Embodiment 3
By raw material propylene of hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl styrene and styrene, acid is single
Body；Glycidyl methacrylate, aqueous epoxy resins are raw material epoxy resin；Iso-cyanuric acid triallyl ester is crosslinking
Agent；Alkyl alcohol ether and sulfosuccinic acid ester ammonium salt are emulsifier；Trimethyl ethamine is neutralizer；Kathon CG is preservative, is prepared
The acrylic emulsion of embodiment 3.
Preparation process reference implementation example 1.
Then, 3 gained acrylic emulsion of embodiment with ethylene glycol and alcohol ester 12 is mixed, obtains the propylene of embodiment 3
Acrylate structure glue.
Embodiment 4
With acrylic acid, acrylamide, methacrylic acid, methyl acrylate and methyl methacrylate and acrylic acid hydroxyl
Propyl ester is raw material propylene acid monomers；Aqueous epoxy resins are raw material epoxy resin；Iso-cyanuric acid triallyl ester is crosslinking agent；
Alkyl alcohol ether and sulfosuccinic acid ester sodium salt are emulsifier；Isopropylamine is neutralizer；Kathon CG is preservative, prepares embodiment 4
Acrylic emulsion.
Preparation process reference implementation example 1.
Then, 4 gained acrylic emulsion of embodiment with ethylene glycol and alcohol ester 12 is mixed, obtains the propylene of embodiment 4
Acrylate structure glue.
Embodiment 5
With acrylamide, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl acrylate and methyl styrene are
Raw material propylene acid monomers；Aqueous epoxy resins are raw material epoxy resin；Iso-cyanuric acid triallyl ester is crosslinking agent；Alkylol
Ether and sulfosuccinic acid ester ammonium salt are emulsifier；APM-95 is neutralizer；Kathon CG is preservative, prepares the propylene of embodiment 5
Yogurt liquid.
Preparation process reference implementation example 1.
Then, 5 gained acrylic emulsion of embodiment with alcohol ester 12 is mixed, obtains the acrylate structural of embodiment 5
Glue.
Experimental example 1
(1) acrylic emulsion stability test
(i) 12h will be placed under normal temperature condition as the acrylic emulsion prepared by 1 method of embodiment, then observes its shape
State；
As a result, it has been found that the acrylic emulsion of embodiment 1 is not demulsified after long-time is placed.
(ii) CaCl is added in as the acrylic emulsion prepared by 2 method of embodiment2After stir evenly, and cause CaCl2
Concentration reach 1M, then stand 6h, be observed；
As a result, it has been found that the acrylic emulsion of embodiment 2 is not demulsified under the conditions of high salt, stability keeps good
It is good.
(iii) to as being stirred evenly, and make after adding in No. 400 cement in the acrylic emulsion prepared by 3 method of embodiment
The pH for obtaining lotion reaches 13 or so, then stands 6h, is observed；
As a result, it has been found that the acrylic emulsion of embodiment 3 is not demulsified, slagging, after 6h, cement normally lumps, intensity, toughness
It increased.
And as above-mentioned experimental result it is found that had good stability as the acrylic emulsion prepared by the method for the present invention, Er Qienai
Saline alkali is strong, even if under the conditions of high concentration is saline and alkaline, remaining on can keep stable for a long time, will not be demulsified.
(2) acrylate structural adhesive performance test
(i) using the acrylate structural adhesive of embodiment 4 as experiment coating, meanwhile, using commercial coating as comparison coating；
Southern somewhere is coated on using experiment coating and comparison coating as back cover coating respectively and creates wall light brick
Surface, surface of wall is in alkalinity；
It after coating 2h, splits, comparison coating can only cover the surface of brick, and the acrylic acid structure prepared by the present invention
The permeability of glue is substantially better than control group；
Meanwhile carry out peel test, it is found that the stripping difficulty of structure glue of the present invention is higher than control group.
(2) using the acrylate structural adhesive of embodiment 5 as experiment paper surface sizing agent, with commercially available for control paper surface
Sizing agent；
Then, technique is wallpaper paper-dope spreading technique, original pure acrylic latex produced using Zhengzhou, henan factory,
After use instead acrylic acid structure glue of the present invention as paper surface sizing agent carry out check experiment；
As a result, it has been found that after using acrylic acid structure glue of the present invention, the tearing toughness of paper improves 12%；
Meanwhile to compare pure acrylic latex as paper surface sizing agent, the shape of 300m running water line paper becomes
5.6%, and the shape of structure glue of the present invention becomes 1.2%, while water resistance increases by 20%.
It can be seen that acrylate structural adhesive of the present invention for external wall have good adhesion, and even if
For a long time, it more under the conditions of harsh environment, will not fall off；
Meanwhile acrylate structural adhesive of the present invention can be used as a Cypres and use, and compared to commercially available
Cypres for, acrylate structural adhesive of the present invention is for anti-deformation nature, intensity and the resistance to tearing of paper
The raising of energy becomes apparent, and can obtain the uniformity and performance more preferably paper, reduces the waste of paper.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of acrylic emulsion, which is characterized in that the preparation method includes the following steps：
Under the conditions of high shear dispersion, by acrylic monomers, epoxy resin, emulsifier and crosslinking agent hybrid reaction, third is obtained
Olefin(e) acid lotion.
2. the preparation method of acrylic emulsion according to claim 1, which is characterized in that the acrylic monomers includes：
Acrylic acid, acrylamide, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, third
One or more of olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl styrene and styrene；
And/or the epoxy resin includes one or more of glycidyl methacrylate, aqueous epoxy resins.
3. the preparation method of acrylic emulsion according to claim 1, which is characterized in that the crosslinking agent includes：Triolefin
Propyl fulminuric acid ester.
4. the preparation method of acrylic emulsion according to claim 1, which is characterized in that the emulsifier includes：Alkyl
One or more of alcohol ether/phenol ether surfactant and sulfosuccinate sodium/ammonium salt.
5. the acrylic emulsion obtained as the preparation method described in any one of claim 1-4.
6. a kind of acrylate structural adhesive, which is characterized in that the raw material of the acrylate structural adhesive is included described in claim 5
Acrylic emulsion.
7. the preparation method of the acrylate structural adhesive described in claim 6, which is characterized in that the method includes walking as follows
Suddenly：
Acrylic emulsion described in claim 5 is mixed with auxiliary material to get to the acrylate structural adhesive；
Preferably, the auxiliary material includes one or both of ethylene glycol and alcohol ester 12.
8. application of the acrylate structural adhesive described in claim 7 in papermaking；
And/or application of the acrylate structural adhesive described in claim 7 in external wall processing.
9. include the paper surface sizing agent of the acrylate structural adhesive described in claim 7；
And/or the external wall processing coating comprising the acrylate structural adhesive described in claim 7.
10. a kind of paper, which is characterized in that the paper is through the paper surface sizing agent described in claim 9 as raw material paper
It is obtained after processing.
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| CN201810126950.7A CN108192016A (en) | 2018-02-08 | 2018-02-08 | Acrylic emulsion and preparation method thereof and acrylate structural adhesive comprising it and preparation method and application |
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| CN111253527A (en) * | 2020-01-15 | 2020-06-09 | 深圳市瑞成科讯实业有限公司 | Water-resistant moisture-proof sizing agent, preparation method and water-resistant moisture-proof paper |
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