CN107434837B - 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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- CN107434837B CN107434837B CN201710803254.0A CN201710803254A CN107434837B CN 107434837 B CN107434837 B CN 107434837B CN 201710803254 A CN201710803254 A CN 201710803254A CN 107434837 B CN107434837 B CN 107434837B
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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 fields, specifically, it is related to a kind of priming paint acrylic resin and preparation method thereof, the priming paint is mainly formed by adhesive force function monomer, (methyl) acrylic ester monomer and hydroxyl esters monomer polymerization with acrylic resin；Preferably, the priming paint is mainly polymerized by following components by mass percentage with acrylic resin: 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 fields, in particular to a kind of priming paint acrylic resin and preparation method thereof.
Background technique
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
Its with no or low volatile organic constituents (VOC) discharge, energy saving, curing rate is fast, it is wear-resisting it is scratch-resistant, decorative effect is good,
The advantages that suitable for heat-sensitive material, 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, for the requirement for meeting global environmental protection, the discharge of VOC is limited in coating, solidifies UV
There is the more preferably impetus in the research and development and application of coating.So far from the 1970s, the coating material solidified technology of UV has 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 especially swift and violent, has become one of leading green coating product of 21 century.
Before the coating material solidified coating of UV, it usually needs precoating layer priming paint, for guaranteeing the quality and decoration of coating
Performance is of great significance.In order to improve priming paint to the adhesive force of ground, the dicoration and anti-corrosion, antiultraviolet of coating are improved
Etc. performances prepare priming paint using various pigment such as acrylic resin wetting and dispersing silver powder, toners, it is then preferable with photostability
UV finishing coat 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 are also gradually increased, various novel grounds, composite material etc.
It comes into being, and for these special substrates, such as nylon, nylon+glass, PC+ glass, alloy, metal plastic composite material,
In the prior art bottom can only be solved by ground processing, bottoming water, addition the methods of adhesive force auxiliary agent or multiple tracks spraying process
The performances such as paint and the ply adhesion problem of UV finishing coat and water boiling resistance.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
It is not contained in molecular structure or containing hydrophilic radicals such as few carboxyls and hydroxyl, by the existing acrylic acid tree for being used for UV priming paint
Priming paint made of rouge is used for special substrate, will lead to poor adhesive force of the priming paint on special substrate.And in the prior art yet
The acrylic resin of the preferable priming paint of adhesive force on special substrate can not developed.
In view of this, the present invention is specifically proposed.
Summary 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 free radical polymerization
It obtains, 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, the method by point
Adhesive force function monomer is introduced 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 progress friendship when later period film toasts and covers UV finishing coat
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 above-mentioned purpose of the invention, the following technical scheme is adopted:
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 polymerization form；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 of the present invention, by introducing adhesive force function monomer, effectively improves priming paint propylene with acrylic resin
Adhesive force, ply adhesion and water boiling resistance performance of the acid resin on special substrate.
Preferably, the adhesive force function monomer is mainly by following components preparation: 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
: 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, introduce hydroxyl esters on phosphorus acrylic monomer
On the one hand monomer improves the compatibility of phosphorus acrylic monomer and resin, on the other hand increases 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 value, 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 finally obtained adhesive force function monomer is the molecular structure with polyfunctionality.Also, it is multifunctional
The molecular structure of degree is capable of forming the microgel that part has intramolecular crosslinking structure in the course of the polymerization process, can significantly improve
The rheological property of coating enhances the mechanical property and durability of coating；It can be further when later period film toasts and covers UV finishing coat
Cross-linking reaction is carried out, adhesive force of the priming paint acrylic resin on special substrate is improved.
Through each starting monomer of regulation adhesive force function monomer in the range of above-mentioned amount, during the reaction, phosphorus
After acrylic monomer and hydroxyl esters monomer reaction, also retaining has the unreacted carboxylic group in part, enable carboxylic group with
PART EPOXY base monomer reaction, in finally obtained adhesive force function monomer, comprising multiple degrees of functionality such as carboxyl, epoxy group with
And double bond etc., and part microgel is formed, facilitate the further crosslinking in later period, improves adhesive force.
Preferably, the phosphorus acrylic monomer includes one of phosphoric acid, phosphorus pentoxide, polyphosphoric acids or a variety of.
Phosphate in the phosphorus acrylic monomer can form firm chemical bond with polar substrates surface；Phosphate and gold
Belonging to ground can promote to adhere to by hydrogen bond action, and similar phosphatic chemical bond can be formed with part metals, have simultaneously
There is phosphorization, improves coating adhesion；Also, the phosphorus acrylic monomer and the hydroxyl esters monomer can carry out esterification
Di Ester 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 ensured 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, guarantees dispersion
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 and resin have preferable compatibility, and certain chemistry can be formed with ground
In conjunction with, form chemical binding force between film and ground, and from film by the effects of dissolving each other, wind and film knot
It is combined, to further increase adhesive force.
Preferably, the epoxy based monomers include glycidyl methacrylate, tertiary carbonic acid glycidyl ester, adjacent toluene
One of glycidol ether, benzyl glycidyl ether are a variety of.
The epoxy based monomers and resin have preferable compatibility, and certain chemical bonding, In can be formed with ground
Chemical binding force is formed between film and ground, and is incorporated in one by the effects of dissolving each other, winding and film certainly in film
It rises, to further increase adhesive force.
Preferably, described (methyl) the acrylics monomer includes methyl methacrylate, butyl methacrylate, methyl
One of isobutyl acrylate, butyl acrylate are a variety of.
Preferably, the initiator includes one or both of benzoyl peroxide and peroxidized t-butyl perbenzoate.
Preferably, the solvent includes one of toluene, isobutanol, butyl acetate, ethyl acetate or a variety of.
A kind of preparation method of priming paint acrylic resin, comprising the following steps:
1) phosphorus acrylic monomer is added portionwise in hydroxyl esters monomer, after reacting 1-5h, polymerization inhibitor and epoxy group list is added
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 reaction kettle, stirring is simultaneously
It is warming up to reflux temperature reaction 1-2h, obtains mixture A；
3) (methyl) acrylic ester monomer is added dropwise into mixture A obtained in step 2), hydroxyl esters monomer, causes
The mixture of agent and solvent, the reaction was continued after completion of dropwise addition 1-2h obtain mixture B；
4) (methyl) acrylic ester monomer, hydroxyl esters monomer, attachment are added dropwise into mixture B obtained in step 3)
Power function monomer, initiator and solvent, the reaction was continued after completion of dropwise addition 1-2h obtain mixture C；
5) initiator and solvent are added into mixture C obtained in step 4), the reaction was continued 3-5h；
6) cool down, solvent is added and obtains priming paint acrylic resin after mixing evenly.
The method is easy 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 part polyfunctionality molecular structure and microgel molecular structure is formed, rear
Meeting further progress cross-linking reaction when the baking of phase film and cover UV finishing coat, improves the priming paint acrylic resin at special bottom
Adhesive force on material.And by segmented polymerization technique, after other monomers polymerization is first added, it is eventually adding adhesive force function list
Body makes adhesive force function monomer be located at molecular chain-end；Since the amount of adhesive force function monomer is less, it can guarantee it positioned at the end of the chain
Active group exposure, avoids its active group and is wrapped by, can effectively contact with ground, improves adhesive force.If be first added
Adhesive force function monomer, the polyfunctionality that will lead in adhesive force function monomer are excessively 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 made effectively to be introduced the end of the chain in molecule, guarantees its activity
Group exposure, avoids its active group and is wrapped by, can effectively contact 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 the mixture of benzoyl peroxide and peroxidized t-butyl perbenzoate.
Preferably, the polymerization inhibitor is hydroquinone.The polymerization inhibitor can effectively avoid preparing adhesive force function list
When body, the polymerization of double bond therein guarantees the activity of the double bond degree of functionality in adhesive force function monomer in the follow-up process.
Preferably, in the step 1), under conditions of 30-40 DEG C, hydroxyl esters are added in phosphorus acrylic monomer in batches
In monomer.
Compared with prior art, the invention has the benefit that
1) the more existing priming paint on special substrate of the priming paint that acrylic resin of the invention is prepared is compared, layer
Between adhesive force it is good and have 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 regulating and controlling the ratio of each monomer, so that formation polyfunctionality molecular structure and part are micro- solidifying in adhesive force function monomer
Xanthan molecule structure, when later period film toasts and covers UV finishing coat, meeting further progress cross-linking reaction, improves the priming paint with third
Adhesive force of the olefin(e) acid resin on special substrate；
3) preparation method of the invention is easy to operate, and stability and reproducibility are good, will be attached by segmented polymerization technique
Put forth effort function monomer and be introduced into molecular chain-end, guarantees the exposure of its active group, avoid its active group and be wrapped by, it can be the bottom of with
Material effectively contacts, and improves adhesive force.
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 carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
Priming paint acrylic resin provided in this embodiment, the mass percent of each raw material are as shown in table 1.
Priming paint acrylic resin step 2) -6 in 1 embodiment 1 of table) 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 mass percentage of each raw material is respectively 30%, 55% and 15%.
The preparation method of the priming paint acrylic resin, comprising the following steps:
1) adhesive force function monomer is prepared: with ice water temperature control under the conditions of 40 DEG C of temperature, in batches by phosphorus pentoxide
It is added in hydroxyethyl methacrylate, after reacting 3h, hydroquinone and glycidyl methacrylate is added, is warming up to 90-
After 95 DEG C of reaction 3h, cooling obtains adhesive force function monomer；Wherein, the hydroquinone presses matter as polymerization inhibitor, additional amount
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 reaction kettle, stirs and is warming up to reflux temperature reaction 1h, obtain mixture A；
3) methyl methacrylate, butyl methacrylate, metering system are added dropwise into mixture A obtained in step 2)
Sour hydroxyl ethyl ester, benzoyl peroxide, peroxidized t-butyl perbenzoate, butyl acetate mixture, time for adding 3h, be added dropwise knot
1h is reacted after beam at a reflux temperature, obtains mixture B；
4) methyl methacrylate, butyl methacrylate, metering system are added dropwise into mixture B obtained in 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 into mixture C obtained in step 4), the reaction was continued 3h；
6) cool down, ethyl acetate is added, stop reaction after mixing evenly, obtain the priming paint acrylic resin.
Embodiment 2
Priming paint acrylic resin provided in this embodiment, the mass percent of each raw material are as shown in table 2.
Priming paint acrylic resin step 2) -6 in 2 embodiment 2 of table) each raw material proportioning
Wherein, the adhesive force function monomer is by phosphoric acid, hydroxyethyl methacrylate and adjacent toluene glycidol ether system
Made of standby, the mass percentage of each raw material is respectively 35%, 52% and 13%.
The preparation method of the priming paint acrylic resin, comprising the following steps:
1) it prepares adhesive force function monomer: with ice water temperature control under the conditions of 30 DEG C of temperature, first is added in phosphoric acid in batches
In base hydroxy-ethyl acrylate, after reacting 3h, hydroquinone and adjacent toluene glycidol ether is added, is warming up to 90-95 DEG C of reaction 3h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinone as polymerization inhibitor, additional amount 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 reaction kettle, stirs and is warming up to reflux temperature reaction
1h obtains mixture A；
3) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise into mixture A obtained in step 2)
Olefin(e) acid butyl ester, hydroxyethyl methacrylate, benzoyl peroxide, peroxidized t-butyl perbenzoate, butyl acetate mixture, drop
It is 3h between added-time, reacts 1h after completion of dropwise addition at a reflux temperature, obtain mixture B；
4) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise into mixture B obtained in 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 into mixture C obtained in step 4), the reaction was continued 3h；
6) cool down, ethyl acetate is added, stop reaction after mixing evenly, obtain the priming paint acrylic resin.
Embodiment 3
Priming paint acrylic resin provided in this embodiment, the mass percent of each raw material are as shown in table 3.
Priming paint acrylic resin step 2) -6 in 3 embodiment 3 of table) each raw material proportioning
Wherein, the adhesive force function monomer is by polyphosphoric acids, hydroxy-ethyl acrylate and tertiary carbonic acid glycidyl ester system
Made of standby, the mass percentage of each raw material is respectively 35%, 55% and 10%.
The preparation method of the priming paint acrylic resin, comprising the following steps:
1) it prepares adhesive force function monomer: with ice water temperature control under the conditions of 35 DEG C of temperature, polyphosphoric acids being added in batches
Enter in hydroxy-ethyl acrylate, after reacting 5h, hydroquinone and tertiary carbonic acid glycidyl ester is added, is warming up to 90-95 DEG C of reaction 5h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinone as polymerization inhibitor, additional amount is propylene by mass
The 3% of sour hydroxyl ethyl ester；
2) by methyl methacrylate, Isobutyl methacrylate, butyl methacrylate, hydroxy-ethyl acrylate, peroxide
The mixed solvent for changing benzoyl and toluene and isobutanol is added in reaction kettle, stirs and is warming up to reflux temperature reaction 2h, obtain
To mixture A；
3) methyl methacrylate, Isobutyl methacrylate, methyl-prop are added dropwise into mixture A obtained in step 2)
Olefin(e) acid butyl ester, hydroxy-ethyl acrylate, benzoyl peroxide, peroxidized t-butyl perbenzoate, butyl acetate mixture, when 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 into mixture B obtained in 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 into mixture C obtained in step 4), the reaction was continued 5h；
6) cool down, ethyl acetate is added, stop reaction after mixing evenly, obtain the priming paint acrylic resin.
Embodiment 4
Priming paint acrylic resin provided in this embodiment, the mass percent of each raw material are as shown in table 4.
Priming paint acrylic resin step 2) -6 in 4 embodiment 4 of table) each raw material proportioning
Wherein, the adhesive force function monomer is by phosphorus pentoxide, hydroxypropyl acrylate and benzyl glycidyl ether system
Made of standby, the mass percentage of each raw material is respectively 25%, 60% and 15%.
The preparation method of the priming paint acrylic resin, comprising the following steps:
1) adhesive force function monomer is prepared: with ice water temperature control under the conditions of 40 DEG C of temperature, in batches by phosphorus pentoxide
It is added in hydroxypropyl acrylate, after reacting 1h, hydroquinone and benzyl glycidyl ether is added, is warming up to 90-95 DEG C of reaction 1h
Afterwards, cooling obtains adhesive force function monomer；Wherein, for the hydroquinone as polymerization inhibitor, additional amount 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 reaction kettle, stirs and is warming up to reflux temperature reaction 1.5h, obtain mixture A；
3) methyl methacrylate, butyl methacrylate, metering system are added dropwise into mixture A obtained in step 2)
Sour hydroxyl ethyl ester, benzoyl peroxide, peroxidized t-butyl perbenzoate, butyl acetate mixture, time for adding 3h, be added dropwise knot
1.5h is reacted after beam at a reflux temperature, obtains mixture B；
4) methyl methacrylate, butyl methacrylate, metering system are added dropwise into mixture B obtained in 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 into mixture C obtained in step 4), the reaction was continued 4h；
6) cool down, ethyl acetate is added, stop reaction after mixing evenly, obtain the priming paint acrylic resin.
Experimental example 1
In order to clearer the advantages of showing environment-friendly type coating provided herein, following experimental example is provided for saying
It is bright.The acrylic resin of following comparative example 1 and comparative example 2 is compared as a comparison case, is formulated as follows:
Comparative example 1: adhesive force function monomer is not added in comparative example 1
Priming paint acrylic resin step 2) -6 in 5 comparative example 1 of table) each raw material proportioning
Comparative example 2: it joined a certain amount of adhesive force function monomer in comparative example 2
Priming paint acrylic resin step 2) -6 in 6 comparative example 2 of table) each raw material proportioning
The performance of the priming paint acrylic resin of embodiments herein 1-4 and comparative example 1-2 is measured and is compared:
Measurement method: painting according to professional standard configuration white paint and silver, and paint film adhesion is followed successively by 0 to poor evaluation criterion from good
Grade, 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.
7 paint film adhesion test result of table
8 paint film of table is 100 DEG C resistance to, adhesive force test result after boiling in 1 hour
Table 9 is with paint application property and storage stability test result
By above-mentioned measurement of comparison result table 7- table 9 it is found that priming paint acrylic resin of the invention, according to professional standard
White paint and silver paint are prepared, preferable paint film adhesion and water boiling resistance performance are all had on different grounds, and it matches paint construction
Phenomena such as performance is excellent, is not in wire drawing, and there is excellent storge quality.And for adhesive force is not added 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, the paint film adhesion on special substrate is very poor, and water boiling resistance performance is poor.It is a certain amount of for joined in comparative example 2
Adhesive force function monomer, the paint film adhesion and water boiling resistance performance on different grounds are more excellent, but its with paint application property
Difference, it may appear that the case where spraying wire drawing, and be not easy to store, be stored 30 days under the conditions of 50 DEG C, it may appear that the phenomenon that gel.
Thus, priming paint acrylic resin of the invention effectively improves priming paint propylene by introducing adhesive force function monomer appropriate
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, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where 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 (9)
1. a kind of priming paint acrylic resin, which is characterized in that the priming paint is with acrylic resin mainly by pressing quality percentage
Following components than meter 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%；
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%；
The phosphorus acrylic monomer includes one of phosphoric acid, phosphorus pentoxide, polyphosphoric acids or a variety of；
The hydroxyl esters monomer is selected from dihydroxypropyl esters monomer, and the dihydroxypropyl esters monomer includes acrylic acid hydroxyl
Ethyl ester, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxy propyl methacrylate；
The epoxy based monomers include glycidyl methacrylate, tertiary carbonic acid glycidyl ester, adjacent toluene glycidol ether,
One of benzyl glycidyl ether is a variety of；
The preparation method of the priming paint acrylic resin, comprising the following steps:
1) phosphorus acrylic monomer is added portionwise in hydroxyl esters monomer, after reacting 1-5h, polymerization inhibitor and epoxy based monomers is added, rise
After temperature 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 reaction kettle, stir and heats up
1-2h is reacted to reflux temperature, obtains mixture A；
3) into mixture A obtained in step 2) be added dropwise (methyl) acrylic ester monomer, hydroxyl esters monomer, initiator and
The mixture of solvent, the reaction was continued after completion of dropwise addition 1-2h obtain mixture B；
4) (methyl) acrylic ester monomer, hydroxyl esters monomer, adhesive force function are added dropwise into mixture B obtained in step 3)
Can monomer, initiator and solvent, the reaction was continued after completion of dropwise addition 1-2h obtains mixture C；
5) initiator and solvent are added into mixture C obtained in step 4), the reaction was continued 3-5h；
6) cool down, solvent is added and obtains priming paint acrylic resin after mixing evenly.
2. priming paint acrylic resin according to claim 1, which is characterized in that the epoxy based monomers include methyl-prop
One of olefin(e) acid ethylene oxidic ester, tertiary carbonic acid glycidyl ester, adjacent toluene glycidol ether, benzyl glycidyl ether are more
Kind.
3. priming paint acrylic resin according to claim 1, which is characterized in that (methyl) acrylic ester monomer
Including one of methyl methacrylate, butyl methacrylate, Isobutyl methacrylate, butyl acrylate or a variety of.
4. priming paint acrylic resin according to claim 1, which is characterized in that the initiator includes benzoyl peroxide first
One or both of acyl and peroxidized t-butyl perbenzoate.
5. priming paint acrylic resin according to claim 1, which is characterized in that the solvent include toluene, isobutanol,
One of butyl acetate, ethyl acetate are a variety of.
6. priming paint acrylic resin according to claim 1, which is characterized in that in the step 2) to the step 4)
In the mass ratio of (methyl) acrylic ester monomer that is separately added into be (20-25) ﹕ (45-55) ﹕ (20-35).
7. priming paint acrylic resin according to claim 1, which is characterized in that in the step 2) to the step 4)
In the mass ratio of hydroxyl esters monomer that is separately added into be (20-25) ﹕ (45-55) ﹕ (20-35).
8. priming paint acrylic resin according to claim 1, which is characterized in that in the step 2) to the step 5)
In the mass ratio of initiator that is separately added into be (10-15) ﹕ (30-60) ﹕ (10-15) ﹕ (10-60).
9. priming paint acrylic resin according to claim 1, which is characterized in that in the step 2) to the step 6)
In the mass ratio of solvent that is separately added into be (45-55) ﹕ (8-15) ﹕ (5-10) ﹕ (2-4) ﹕ (16-40).
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| CN201710803254.0A CN107434837B (en) | 2017-09-08 | 2017-09-08 | A kind of priming paint acrylic resin and preparation method thereof |
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| CN201710803254.0A CN107434837B (en) | 2017-09-08 | 2017-09-08 | A kind of priming paint acrylic resin and preparation method thereof |
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| CN107434837B true CN107434837B (en) | 2019-10-29 |
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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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| CN107434837A (en) | 2017-12-05 |
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