CN107434837A - A kind of priming paint acrylic resin and preparation method thereof - Google Patents
A kind of priming paint acrylic resin and preparation method thereof Download PDFInfo
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- CN107434837A CN107434837A CN201710803254.0A CN201710803254A CN107434837A CN 107434837 A CN107434837 A CN 107434837A CN 201710803254 A CN201710803254 A CN 201710803254A CN 107434837 A CN107434837 A CN 107434837A
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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
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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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Abstract
The present invention relates to painting field, specifically, it is related to a kind of priming paint acrylic resin and preparation method thereof, the priming paint is mainly polymerized with acrylic resin by adhesive force function monomer, (methyl) acrylic ester monomer and hydroxyl esters monomer；Preferably, the priming paint is mainly polymerized with acrylic resin by following components by mass percentage：Adhesive force function monomer 0.02% 0.1%, (methyl) acrylic ester monomer 43% 48%, hydroxyl esters monomer 1% 7%, initiator 0.3% 0.8% and solvent 45% 55%；Wherein, the adhesive force function monomer is prepared by following components：Phosphorus acrylic monomer, hydroxyl esters monomer and epoxy based monomers.The priming paint acrylic resin of the application can effectively improve its adhesive force on special substrate, ply adhesion and water boiling resistance performance.
Description
Technical field
The present invention relates to painting field, in particular to a kind of priming paint acrylic resin and preparation method thereof.
Background technology
Coating material solidified ultraviolet light (UV) is a kind of environment-friendly type energy-saving coating developed by Bayer A.G nineteen sixty-eight, due to
It has no or low volatile organic constituents (VOC) discharge, save the energy, curing rate it is fast, it is wear-resisting it is scratch-resistant, decorative effect is good,
The advantages that suitable for heat-sensitive material, it is widely used in the Material Fields such as timber, plastics, optical fiber, paper.Also, with existing
The high speed development of generation science and technology, to meet the requirement of global environmental protection, in coating VOC discharge limited, solidify UV
There is the more preferably impetus in the research and development and application of coating.From the 1970s so far, the coating material solidified technologies of UV have obtained prominent fly
The development pushed ahead vigorously, the market share increase sharply.Wherein, the UV of the developed countries and regions such as North America, Europe and Japan is coating material solidified
Development is particularly swift and violent, has become one of leading green coating product of 21 century.
Before the coating material solidified applications of UV, it usually needs precoating layer priming paint, its quality and decoration for ensureing application
Performance, it is significant.In order to improve adhesive force of the priming paint to ground, the dicoration and anti-corrosion, antiultraviolet of coating are improved
Etc. performance, using various pigment such as acrylic resin wetting and dispersing silver powder, toners, priming paint is prepared, it is then preferable with photostability
UV finish paints carry out Lacquer finish be the more common method of manufacturer.
With the development of science and technology, the appreciation level of people and requirement also gradually step up, various new grounds, composite etc.
Arise at the historic moment, and for these special substrates, such as nylon, nylon+glass, PC+ glasses, alloy, metal plastic composite,
It can only be handled in the prior art by ground, bottoming water, addition adhesive force auxiliary agent or solve bottom the methods of multiple tracks spraying coating process
The performances such as the ply adhesion problem and water boiling resistance of paint and UV finish paints.And the existing acrylic resin for UV priming paint, mainly
It is the ground relatively easily adhered to for ABS and PC etc., in order to meet the requirement of water boiling resistance, these existing acrylic resins
Do not contained in molecular structure or containing hydrophilic radicals such as few carboxyls and hydroxyl, by the existing acrylic acid tree for UV priming paint
Priming paint made of fat is used for special substrate, can cause poor adhesive force of the priming paint on special substrate.And in the prior art yet
Without the acrylic resin that can develop the preferable priming paint of adhesive force on special substrate.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of priming paint acrylic resin, and the priming paint is phosphorus with acrylic resin
The polymer-modified adhesive force function monomer of acid esters, (methyl) acrylic ester monomer and hydroxyl esters monomer pass through radical polymerization
Obtain, its adhesive force on special substrate, ply adhesion and water boiling resistance performance can be effectively improved.
The second object of the present invention is to provide a kind of preparation method of priming paint acrylic resin, methods described by point
Adhesive force function monomer is incorporated into molecular chain-end by segmentation polymerization technique, and passes through the control to function monomer content, forming portion
Divide polyfunctionality molecular structure and microgel molecular structure, it can further be handed over when later stage film toasts and covers UV finish paints
Connection reaction, improves adhesive force of the priming paint acrylic resin on special substrate.The preparation method process conditions are bright
Really, stability and reproducibility are good.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of priming paint acrylic resin, the priming paint is with acrylic resin mainly by adhesive force function monomer, (first
Base) acrylic ester monomer and hydroxyl esters monomer be polymerized；Preferably, the priming paint with acrylic resin mainly by
Following components by mass percentage is polymerized：
Adhesive force function monomer 0.02%-0.1%, (methyl) acrylic ester monomer 43%-48%, hydroxyl esters monomer
1%-7%, initiator 0.3%-0.8% and solvent 45%-55%.
Priming paint acrylic resin of the present invention effectively improves priming paint propylene by introducing adhesive force function monomer
Adhesive force, ply adhesion and water boiling resistance performance of the acid resin on special substrate.
Preferably, the adhesive force function monomer is mainly prepared by following components：Phosphorus acrylic monomer, hydroxyl esters monomer
And epoxy based monomers.It is furthermore preferred that the adhesive force function monomer is mainly prepared by following components by mass percentage
's：Phosphorus acrylic monomer 25%-35%, hydroxyl esters monomer 50%-60% and epoxy based monomers 10%-15%.
The adhesive force function monomer is prepared by phosphorus acrylic monomer, hydroxyl esters monomer and epoxy based monomers
, wherein, esterification can be carried out between phosphorus acrylic monomer and hydroxyl esters monomer, hydroxyl esters are introduced on phosphorus acrylic monomer
Monomer, the compatibility of phosphorus acrylic monomer and resin is on the one hand improved, on the other hand adds degree of functionality；Phosphorus acrylic monomer and hydroxyl
The reactant of esterification of base esters monomer further can react to form adhesive force function monomer with epoxy based monomers again, on the one hand reduce
Acid number, improves stability, has on the other hand been further introduced into epoxy functionality in adhesive force function monomer, has improved
Can reactive functional group degree so that the adhesive force function monomer finally given is the molecular structure for having polyfunctionality.It is also, multifunctional
The molecular structure of degree can form part in the course of the polymerization process has the microgel of intramolecular crosslinking structure, can significantly improve
The rheological property of coating, strengthen the mechanical property and durability of coating；Can be further when later stage film toasts and covers UV finish paints
Cross-linking reaction is carried out, improves adhesive force of the priming paint acrylic resin on special substrate.
By regulating and controlling each starting monomer of adhesive force function monomer in the range of above-mentioned amount, during the course of the reaction, phosphorus
After acrylic monomer and hydroxyl esters monomer reaction, also retaining has the unreacted carboxylic group in part so that carboxylic group can be with
PART EPOXY base monomer reaction, in the adhesive force function monomer finally given, comprising multiple degrees of functionality such as carboxyl, epoxy radicals with
And double bond etc., and part microgel is formed, contribute to the further crosslinking in later stage, improve adhesive force.
Preferably, the phosphorus acrylic monomer includes the one or more in phosphoric acid, phosphorus pentoxide, polyphosphoric acids.
Phosphate in the phosphorus acrylic monomer can form firm chemical bond with polar substrates surface；Phosphate and gold
Belong to ground to promote to adhere to by hydrogen bond action, and similar phosphatic chemical bond can be formed with part metals, have simultaneously
There is phosphorization, improve coating adhesion；Also, the phosphorus acrylic monomer can carry out esterification with the hydroxyl esters monomer
Di esters material is formed, the phosphate with certain long-chain can be permeated by phosphate-based stronger penetrating power
To the superficial layer of ground, certain holdfast effect is formed, the stability and water boiling resistance performance of phosphorus acrylic monomer is improved, was both protecting
Water boiling resistance performance etc. is also ensure that while demonstrate,proving adhesive force.
Preferably, the hydroxyl esters monomer is selected from dihydroxypropyl esters monomer.
Double bond group is contained in the dihydroxypropyl esters monomer, increases the degree of functionality in adhesive force function monomer,
And promote the formation of part microgel；Also, compatibility of the dihydroxypropyl esters monomer in resin is more preferably, ensure scattered
Stability.
Preferably, the dihydroxypropyl esters monomer includes hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid
Hydroxyl ethyl ester and hydroxy propyl methacrylate.
The dihydroxypropyl esters monomer has preferable compatibility with resin, can form certain chemistry with ground again
With reference to, form chemical binding force between film and ground, and from film by effect and the film knot such as dissolving each other, winding
It is combined, so as to further improve adhesive force.
Preferably, the epoxy based monomers include GMA, tertiary carbonic acid glycidyl ester, adjacent toluene
One or more in glycidol ether, benzyl glycidyl ether.
The epoxy based monomers have preferable compatibility with resin, can form certain chemical bond with ground again,
Form chemical binding force between film and ground, and one is incorporated in by the effect and film such as dissolving each other, winding from film
Rise, so as to further improve adhesive force.
Preferably, described (methyl) acrylics monomer includes methyl methacrylate, butyl methacrylate, methyl
One or more in isobutyl acrylate, butyl acrylate.
Preferably, the initiator includes one or both of benzoyl peroxide and peroxidized t-butyl perbenzoate.
Preferably, the solvent includes the one or more in toluene, isobutanol, butyl acetate, ethyl acetate.
A kind of preparation method of priming paint acrylic resin, comprises the following steps：
1) phosphorus acrylic monomer is added portionwise in hydroxyl esters monomer, after reacting 1-5h, adds polymerization inhibitor and epoxy radicals list
Body, after being warming up to 90-95 DEG C of reaction 1-5h, cooling obtains adhesive force function monomer；
2) (methyl) acrylic ester monomer, hydroxyl esters monomer, initiator and solvent are added in reactor, stirring is simultaneously
Reflux temperature reaction 1-2h is warming up to, obtains mixture A；
3) (methyl) acrylic ester monomer, hydroxyl esters monomer are added dropwise in the mixture A obtained into step 2), triggers
Agent and the mixture of solvent, continue to react 1-2h after completion of dropwise addition, obtain mixture B；
4) (methyl) acrylic ester monomer, hydroxyl esters monomer, attachment are added dropwise in the mixture B obtained into step 3)
Power function monomer, initiator and solvent, continue to react 1-2h after completion of dropwise addition, obtain mixture C；
5) initiator and solvent are added in the mixture C obtained into step 4), continues to react 3-5h；
6) cool, add solvent, after stirring, obtain priming paint acrylic resin.
Methods described is simple to operate, and stability and reproducibility are good.In the preparation method, by adhesive force function list
Each starting monomer content of body is controlled, and forms part polyfunctionality molecular structure and microgel molecular structure, it is rear
Phase film toasts and can further carry out cross-linking reaction when covering UV finish paints, improves the priming paint acrylic resin at special bottom
Adhesive force on material.And by segmented polymerization technique, after first adding other monomers polymerization, it is eventually adding adhesive force function list
Body, adhesive force function monomer is set to be located at molecular chain-end；Because the amount of adhesive force function monomer is less, it can be ensured positioned at the end of the chain
Active group exposes, and avoids its active group and is wrapped by, can effectively be contacted with ground, improves adhesive force.If first add
Adhesive force function monomer, the polyfunctionality in adhesive force function monomer can be caused excessively to be crosslinked.
Preferably, the quality of (methyl) acrylic ester monomer being separately added into the step 2) to the step 4)
Than for (20-25) ﹕ (45-55) ﹕ (20-35)；
And/or the mass ratio for the hydroxyl esters monomer being separately added into the step 2) to the step 4) is (20-
25) ﹕ (45-55) ﹕ (20-35)；
And/or the mass ratio for the initiator being separately added into the step 2) to the step 5) is (10-15) ﹕ (30-
60) ﹕ (10-15) ﹕ (10-60)；
And/or the mass ratio for the solvent being separately added into the step 2) to the step 6) is (45-55) ﹕ (8-
15) ﹕ (5-10) ﹕ (2-4) ﹕ (16-40).
Regulated and controled by above-mentioned ratio, adhesive force function monomer is effectively introduced the end of the chain in molecule, ensure its activity
Group exposes, and avoids its active group and is wrapped by, can effectively be contacted with ground, improves adhesive force.
Preferably, the solvent in the step 2) is the mixture of toluene and isobutanol, and the step 3) is into step 5)
Solvent be butyl acetate, the solvent in the step 6) is ethyl acetate.
Preferably, the step 2), 4) and 5) in initiator be benzoyl peroxide, the initiator in the step 3)
For benzoyl peroxide and the mixture of peroxidized t-butyl perbenzoate.
Preferably, the polymerization inhibitor is hydroquinones.The polymerization inhibitor can effectively avoid preparing adhesive force function list
During body, the polymerization of double bond therein, ensure the activity of the double bond degree of functionality in subsequent process in adhesive force function monomer.
Preferably, in the step 1), under conditions of 30-40 DEG C, phosphorus acrylic monomer is added into hydroxyl esters in batches
In monomer.
Compared with prior art, beneficial effects of the present invention are：
1) the more existing priming paint on special substrate of priming paint that acrylic resin of the invention is prepared is compared, layer
Between adhesive force it is good and there is good water boiling resistance performance；
2) adhesive force function monomer of the invention, in advance by phosphorus acrylic monomer, hydroxyl esters monomer and epoxy based monomers
Mixing, by the ratio for regulating and controlling each monomer so that polyfunctionality molecular structure is formed in adhesive force function monomer and part is micro- solidifying
Xanthan molecule structure, cross-linking reaction can be further carried out when later stage film toasts and covers UV finish paints, improves the priming paint with third
Adhesive force of the olefin(e) acid resin on special substrate；
3) preparation method of the invention is simple to operate, and stability and reproducibility are good, will be attached by segmented polymerization technique
Put forth effort function monomer and be incorporated into molecular chain-end, ensure that its active group exposes, avoid its active group and be wrapped by, can be the bottom of with
Material effectively contacts, and improves adhesive force.
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 present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The priming paint acrylic resin that the present embodiment provides, the mass percent of its each raw material are as shown in table 1.
Priming paint acrylic resin step 2) -6 in the embodiment 1 of table 1) each raw material proportioning
Wherein, the adhesive force function monomer is contracted by phosphorus pentoxide, hydroxyethyl methacrylate and methacrylic acid
Water glyceride is prepared, and the weight/mass percentage composition of each raw material is respectively 30%, 55% and 15%.
The preparation method of the priming paint acrylic resin, comprises the following steps：
1) adhesive force function monomer is prepared：With frozen water temperature control under 40 DEG C of temperature conditionss, by phosphorus pentoxide in batches
Add in hydroxyethyl methacrylate, after reacting 3h, add hydroquinones and GMA, be warming up to 90-
After 95 DEG C of reaction 3h, cooling obtains adhesive force function monomer；Wherein, the hydroquinones presses matter as polymerization inhibitor, its addition
Amount is calculated as the 1% of hydroxyethyl methacrylate；
2) by methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, benzoyl peroxide and
The mixed solvent of toluene and isobutanol is added in reactor, is stirred and is warming up to reflux temperature reaction 1h, obtains mixture A；
3) methyl methacrylate, butyl methacrylate, metering system are added dropwise in the mixture A obtained into step 2)
Sour hydroxyl ethyl ester, benzoyl peroxide, peroxidized t-butyl perbenzoate, the mixture of butyl acetate, time for adding 3h, knot is added dropwise
1h is reacted after beam at a reflux temperature, obtains mixture B；
4) methyl methacrylate, butyl methacrylate, metering system are added dropwise in the mixture B obtained into step 3)
Sour hydroxyl ethyl ester, adhesive force function monomer, benzoyl peroxide, butyl acetate, time for adding 1.5h, are flowing back after completion of dropwise addition
At a temperature of insulation reaction 1h, obtain mixture C；
5) benzoyl peroxide and butyl acetate are added in the mixture C obtained into step 4), continues to react 3h；
6) cool, add ethyl acetate, stop reaction after stirring, obtain the priming paint acrylic resin.
Embodiment 2
The priming paint acrylic resin that the present embodiment provides, the mass percent of its each raw material are as shown in table 2.
Priming paint acrylic resin step 2) -6 in the embodiment 2 of table 2) each raw material proportioning
Wherein, the adhesive force function monomer is by phosphoric acid, hydroxyethyl methacrylate and adjacent toluene glycidol ether system
For what is formed, the weight/mass percentage composition of each raw material is respectively 35%, 52% and 13%.
The preparation method of the priming paint acrylic resin, comprises the following steps：
1) adhesive force function monomer is prepared：With frozen water temperature control under 30 DEG C of temperature conditionss, phosphoric acid is added into first in batches
In base hydroxy-ethyl acrylate, after reacting 3h, hydroquinones and adjacent toluene glycidol ether are added, is warming up to 90-95 DEG C of reaction 3h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinones as polymerization inhibitor, its addition is methyl by mass
The 1% of hydroxy-ethyl acrylate；
2) by methyl methacrylate, Isobutyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate,
The mixed solvent of benzoyl peroxide and toluene and isobutanol is added in reactor, is stirred and is warming up to reflux temperature reaction
1h, obtain mixture A；
3) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise in the mixture A obtained into step 2)
Olefin(e) acid butyl ester, hydroxyethyl methacrylate, benzoyl peroxide, peroxidized t-butyl perbenzoate, the mixture of butyl acetate, drop
It is 3h between added-time, reacts 1h after completion of dropwise addition at a reflux temperature, obtains mixture B；
4) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise in the mixture B obtained into step 3)
Adhesive force function monomer that olefin(e) acid butyl ester, hydroxyethyl methacrylate, step 1) are prepared, benzoyl peroxide, acetic acid fourth
Ester, time for adding 1.5h, after completion of dropwise addition, insulation reaction 1h, obtains mixture C at a reflux temperature；
5) benzoyl peroxide and butyl acetate are added in the mixture C obtained into step 4), continues to react 3h；
6) cool, add ethyl acetate, stop reaction after stirring, obtain the priming paint acrylic resin.
Embodiment 3
The priming paint acrylic resin that the present embodiment provides, the mass percent of its each raw material are as shown in table 3.
Priming paint acrylic resin step 2) -6 in the embodiment 3 of table 3) each raw material proportioning
Wherein, the adhesive force function monomer is by polyphosphoric acids, hydroxy-ethyl acrylate and tertiary carbonic acid glycidyl ester system
For what is formed, the weight/mass percentage composition of each raw material is respectively 35%, 55% and 10%.
The preparation method of the priming paint acrylic resin, comprises the following steps：
1) adhesive force function monomer is prepared：With frozen water temperature control under 35 DEG C of temperature conditionss, polyphosphoric acids is added in batches
Enter in hydroxy-ethyl acrylate, after reacting 5h, add hydroquinones and tertiary carbonic acid glycidyl ester, be warming up to 90-95 DEG C of reaction 5h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinones as polymerization inhibitor, its addition is propylene by mass
The 3% of sour hydroxyl ethyl ester；
2) by methyl methacrylate, Isobutyl methacrylate, butyl methacrylate, hydroxy-ethyl acrylate, peroxide
Change benzoyl and the mixed solvent of toluene and isobutanol is added in reactor, stir and be warming up to reflux temperature reaction 2h, obtain
To mixture A；
3) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise in the mixture A obtained into step 2)
Olefin(e) acid butyl ester, hydroxy-ethyl acrylate, benzoyl peroxide, peroxidized t-butyl perbenzoate, the mixture of butyl acetate, during dropwise addition
Between be 3h, 2h is reacted after completion of dropwise addition at a reflux temperature, obtains mixture B；
4) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise in the mixture B obtained into step 3)
Adhesive force function monomer that olefin(e) acid butyl ester, hydroxy propyl methacrylate, step 1) are prepared, benzoyl peroxide, acetic acid fourth
Ester, time for adding 1.5h, after completion of dropwise addition, insulation reaction 2h, obtains mixture C at a reflux temperature；
5) benzoyl peroxide and butyl acetate are added in the mixture C obtained into step 4), continues to react 5h；
6) cool, add ethyl acetate, stop reaction after stirring, obtain the priming paint acrylic resin.
Embodiment 4
The priming paint acrylic resin that the present embodiment provides, the mass percent of its each raw material are as shown in table 4.
Priming paint acrylic resin step 2) -6 in the embodiment 4 of table 4) each raw material proportioning
Wherein, the adhesive force function monomer is by phosphorus pentoxide, hydroxypropyl acrylate and benzyl glycidyl ether system
For what is formed, the weight/mass percentage composition of each raw material is respectively 25%, 60% and 15%.
The preparation method of the priming paint acrylic resin, comprises the following steps：
1) adhesive force function monomer is prepared：With frozen water temperature control under 40 DEG C of temperature conditionss, by phosphorus pentoxide in batches
Add in hydroxypropyl acrylate, after reacting 1h, add hydroquinones and benzyl glycidyl ether, be warming up to 90-95 DEG C of reaction 1h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinones as polymerization inhibitor, its addition is propylene by mass
The 2% of sour hydroxypropyl acrylate；
2) by methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, benzoyl peroxide and
The mixed solvent of toluene and isobutanol is added in reactor, is stirred and is warming up to reflux temperature reaction 1.5h, obtains mixture A；
3) methyl methacrylate, butyl methacrylate, metering system are added dropwise in the mixture A obtained into step 2)
Sour hydroxyl ethyl ester, benzoyl peroxide, peroxidized t-butyl perbenzoate, the mixture of butyl acetate, time for adding 3h, knot is added dropwise
1.5h is reacted after beam at a reflux temperature, obtains mixture B；
4) methyl methacrylate, butyl methacrylate, metering system are added dropwise in the mixture B obtained into step 3)
Sour hydroxyl ethyl ester, adhesive force function monomer, benzoyl peroxide, butyl acetate, time for adding 1.5h, are flowing back after completion of dropwise addition
At a temperature of insulation reaction 1.5h, obtain mixture C；
5) benzoyl peroxide and butyl acetate are added in the mixture C obtained into step 4), continues to react 4h；
6) cool, add ethyl acetate, stop reaction after stirring, obtain the priming paint acrylic resin.
Experimental example 1
The advantages of in order to clearer displaying environment-friendly type coating provided herein, there is provided following experimental example is used to say
It is bright.The acrylic resin of following comparative example 1 and comparative example 2 is compared as a comparison case, its formula is as follows：
Comparative example 1：Adhesive force function monomer is not added in comparative example 1
Priming paint acrylic resin step 2) -6 in the comparative example 1 of table 5) each raw material proportioning
Comparative example 2：A certain amount of adhesive force function monomer is added in comparative example 2
Priming paint acrylic resin step 2) -6 in the comparative example 2 of table 6) each raw material proportioning
Embodiments herein 1-4 and comparative example 1-2 priming paint are measured with the performance of acrylic resin and compared：
Measuring method：Painted according to professional standard configuration white paint and silver, paint film adhesion is followed successively by 0 from good to poor evaluation criterion
Level, 1 grade, 2 grades, 3 grades, 4 grades, 5 grades；Unchanged, thickening, gel are followed successively by poor evaluation criterion from good with paint storage stability.
Measurement result is as shown in table 7, table 8 and table 9.
The paint film adhesion test result of table 7
The paint film of table 8 is resistance to 100 DEG C, adhesive force test result after boiling in 1 hour
Table 9 is with paint application property and storage stability test result
Pass through above-mentioned measurement of comparison result table 7- tables 9, priming paint acrylic resin of the invention, according to professional standard
Prepare white paint and silver paints, preferable paint film adhesion and water boiling resistance performance is respectively provided with different grounds, and it constructs with paint
Performance is excellent, phenomena such as being not in wire drawing, and has excellent storge quality.And for not adding adhesive force in comparative example 1
Function monomer, although it is more excellent with paint workability and stability, its paint film adhesion performance on different grounds is not
Together, its paint film adhesion on special substrate is very poor, and water boiling resistance poor performance.It is a certain amount of for being added in comparative example 2
Adhesive force function monomer, its paint film adhesion and water boiling resistance performance on different grounds is more excellent, but its with paint application property
Difference, it may appear that spray the situation of wire drawing, and be not easy to store, stored 30 days under the conditions of 50 DEG C, it may appear that the phenomenon of gel.
Thus, priming paint acrylic resin of the invention, by introducing appropriate adhesive force function monomer, effectively improve priming paint propylene
Adhesive force, ply adhesion and water boiling resistance performance of the acid resin on special substrate, and with excellent with paint application property
Energy and storage characteristics.
Although illustrate and describing the present invention with specific embodiment, but 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 priming paint acrylic resin, it is characterised in that the priming paint is with acrylic resin mainly by adhesive force function
Monomer, (methyl) acrylic ester monomer and hydroxyl esters monomer are polymerized；Preferably, the priming paint acrylic resin
Mainly it is polymerized by following components by mass percentage：
Adhesive force function monomer 0.02%-0.1%, (methyl) acrylic ester monomer 43%-48%, hydroxyl esters monomer 1%-
7%th, initiator 0.3%-0.8% and solvent 45%-55%.
2. priming paint acrylic resin according to claim 1, it is characterised in that the adhesive force function monomer mainly by
Prepared by following components：Phosphorus acrylic monomer, hydroxyl esters monomer and epoxy based monomers；
Preferably, the adhesive force function monomer is mainly prepared by following components by mass percentage：Phosphorus acrylic monomer
25%-35%, hydroxyl esters monomer 50%-60% and epoxy based monomers 10%-15%.
3. priming paint acrylic resin according to claim 1 or 2, it is characterised in that the phosphorus acrylic monomer includes phosphorus
One or more in acid, phosphorus pentoxide, polyphosphoric acids.
4. priming paint acrylic resin according to claim 1 or 2, it is characterised in that the hydroxyl esters monomer is selected from
Dihydroxypropyl esters monomer.
5. priming paint acrylic resin according to claim 4, it is characterised in that the dihydroxypropyl esters monomer bag
Include hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxy propyl methacrylate.
6. priming paint acrylic resin according to claim 1 or 2, it is characterised in that the epoxy based monomers include first
Base glycidyl acrylate, tertiary carbonic acid glycidyl ester, adjacent toluene glycidol ether, one kind in benzyl glycidyl ether or
It is a variety of.
7. priming paint acrylic resin according to claim 1 or 2, it is characterised in that (methyl) acrylics
Monomer includes methyl methacrylate, butyl methacrylate, Isobutyl methacrylate, one kind in butyl acrylate or more
Kind.
8. priming paint acrylic resin according to claim 1 or 2, it is characterised in that the initiator includes peroxidating
One or both of benzoyl and peroxidized t-butyl perbenzoate；And/or the solvent includes toluene, isobutanol, acetic acid fourth
One or more in ester, ethyl acetate.
9. a kind of preparation method of priming paint acrylic resin, it is characterised in that comprise the following steps：
1) phosphorus acrylic monomer is added portionwise in hydroxyl esters monomer, after reacting 1-5h, adds polymerization inhibitor and epoxy based monomers, rise
After temperature reacts 1-5h to 90-95 DEG C, cooling obtains adhesive force function monomer；
2) (methyl) acrylic ester monomer, hydroxyl esters monomer, initiator and solvent are added in reactor, stirs and heat up
1-2h is reacted to reflux temperature, obtains mixture A；
3) in the mixture A obtained into step 2) be added dropwise (methyl) acrylic ester monomer, hydroxyl esters monomer, initiator and
The mixture of solvent, continue to react 1-2h after completion of dropwise addition, obtain mixture B；
4) (methyl) acrylic ester monomer, hydroxyl esters monomer, adhesive force work(are added dropwise in the mixture B obtained into step 3)
Energy monomer, initiator and solvent, continue to react 1-2h after completion of dropwise addition, obtain mixture C；
5) initiator and solvent are added in the mixture C obtained into step 4), continues to react 3-5h；
6) cool, add solvent, after stirring, obtain priming paint acrylic resin.
10. the preparation method of priming paint acrylic resin according to claim 9, it is characterised in that in the step 2)
The mass ratio of (methyl) acrylic ester monomer being separately added into the step 4) is (20-25) ﹕ (45-55) ﹕ (20-
35)；
And/or the mass ratio for the hydroxyl esters monomer being separately added into the step 2) to the step 4) is (20-25) ﹕
(45-55) ﹕ (20-35)；
And/or the mass ratio for the initiator being separately added into the step 2) to the step 5) is (10-15) ﹕ (30-60) ﹕
(10-15) ﹕ (10-60)；
And/or the mass ratio for the solvent being separately added into the step 2) to the step 6) is (45-55) ﹕ (8-15) ﹕ (5-
10) ﹕ (2-4) ﹕ (16-40).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117798A (en) * | 2004-10-21 | 2006-05-11 | Kansai Paint Co Ltd | Water-based coating composition |
| CN102167771A (en) * | 2010-11-26 | 2011-08-31 | 湖南晟通科技集团有限公司 | Anti-corrosion primer emulsion and preparation method thereof |
| CN102199240A (en) * | 2011-03-17 | 2011-09-28 | 北京化工大学 | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint |
| CN102757523A (en) * | 2011-04-25 | 2012-10-31 | 北京化工大学 | Preparation method of core-shell acrylic acid elastic emulsion containing phosphate group |
| CN103525235A (en) * | 2013-09-24 | 2014-01-22 | 淮南师范学院 | Aqueous rust-removal and rustproof nano coating and preparation method thereof |
-
2017
- 2017-09-08 CN CN201710803254.0A patent/CN107434837B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117798A (en) * | 2004-10-21 | 2006-05-11 | Kansai Paint Co Ltd | Water-based coating composition |
| CN102167771A (en) * | 2010-11-26 | 2011-08-31 | 湖南晟通科技集团有限公司 | Anti-corrosion primer emulsion and preparation method thereof |
| CN102199240A (en) * | 2011-03-17 | 2011-09-28 | 北京化工大学 | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint |
| CN102757523A (en) * | 2011-04-25 | 2012-10-31 | 北京化工大学 | Preparation method of core-shell acrylic acid elastic emulsion containing phosphate group |
| CN103525235A (en) * | 2013-09-24 | 2014-01-22 | 淮南师范学院 | Aqueous rust-removal and rustproof nano coating and preparation method thereof |
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