CN109535583A - The preparation method of titania modified epoxy styrene-acrylic resin composite material - Google Patents

The preparation method of titania modified epoxy styrene-acrylic resin composite material Download PDF

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Publication number
CN109535583A
CN109535583A CN201710861144.XA CN201710861144A CN109535583A CN 109535583 A CN109535583 A CN 109535583A CN 201710861144 A CN201710861144 A CN 201710861144A CN 109535583 A CN109535583 A CN 109535583A
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acrylic resin
modified epoxy
composite material
styrene
epoxy styrene
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CN201710861144.XA
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Chinese (zh)
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黄�俊
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Zhangjiagang New Material Technology Development Co Ltd
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Zhangjiagang New Material Technology Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/108—Hydrocarbon resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This application discloses a kind of preparation methods of titania modified epoxy styrene-acrylic resin composite material, it include: (1), using ethylene glycol monomethyl ether as solvent, azodiisobutyronitrile is initiator, N hydroxymethyl acrylamide is crosslinking agent, it is passed through nitrogen under agitation 20~30 minutes, 85~90 DEG C are then heated to, mixed solution is obtained；In 30~45 minutes progress polymerization reactions of mixed solution and dripping monomer, the reaction time 3~4 hours, it is cooled to 35~50 DEG C after polymerization reaction, water management pH value is then ammoniated in reaction system to 8~9, obtains epoxy styrene-acrylic resin；(2), using Hydrolyze method synthesis of titanium dioxide colloidal sol, curing agent diethylenetriamine is added, solidifies 20~40 minutes at 100~120 DEG C, obtains titania modified epoxy styrene-acrylic resin film.The present invention is by introducing titanium dioxide in modified epoxy styrene-acrylic resin, so that the thermal stability and adhesive force of composite material greatly improve.

Description

The preparation method of titania modified epoxy styrene-acrylic resin composite material
Technical field
The application belongs to water-based ink technical field, multiple more particularly to a kind of titania modified epoxy styrene-acrylic resin The preparation method of condensation material.
Background technique
Styrene-acrylic resin has the characteristics that excellent: resin transparency is good, and glossiness is high, good film-forming property, and adhesive force is strong；With it is other The common binder resins such as acrylic resin, chlorine wax tree rouge have good intermiscibility；It is the basis third for producing ink, coating, paint Olefin(e) acid resin, therefore be research field more active at present.
But existing styrene-acrylic resin still has the problem that poor adhesive force, stability are poor and smell is big.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of titania modified epoxy styrene-acrylic resin composite material, To overcome deficiency in the prior art.
To achieve the above object, the invention provides the following technical scheme:
The embodiment of the present application discloses a kind of preparation method of titania modified epoxy styrene-acrylic resin composite material, packet It includes:
(1), using ethylene glycol monomethyl ether as solvent, azodiisobutyronitrile is initiator, and N hydroxymethyl acrylamide is crosslinking Agent is passed through nitrogen 20~30 minutes under agitation, is then heated to 85~90 DEG C, obtains mixed solution；In mixed solution 30~45 minutes progress polymerization reactions of middle dropwise addition monomer, the reaction time 3~4 hours, are cooled to 35~50 after polymerization reaction DEG C, water management pH value is then ammoniated in reaction system to 8~9, obtains epoxy styrene-acrylic resin；
(2), using Hydrolyze method synthesis of titanium dioxide colloidal sol, curing agent diethylenetriamine is added, solidifies at 100~120 DEG C 20~40 minutes, obtain titania modified epoxy styrene-acrylic resin film.
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, monomer is Styrene, ethyl acrylate, methacrylic acid and glycidyl methacrylate mixture.
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, styrene, The weight ratio of ethyl acrylate, methacrylic acid and glycidyl methacrylate is (45~55): (3~4): (17~ 30): (4~5).
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, azo two The weight of isobutyronitrile and monomer is (8~10): 100.
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, N- hydroxyl first The weight ratio of base acrylamide and monomer is (0.8~1.2): 100.
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, titanium dioxide The synthetic method of titanium colloidal sol includes: that tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are dissolved in the aqueous solution of ethyl alcohol, and control pH=1~ 2, it 30~45 DEG C of hydrolysis temperature, is stirred 2~4 hours.
Preferably, in the preparation method of above-mentioned titania modified epoxy styrene-acrylic resin composite material, metatitanic acid four The mass ratio of N-butyl and acetylacetone,2,4-pentanedione is 1:(1.2~1.8).
Compared with the prior art, the advantages of the present invention are as follows: the present invention in modified epoxy styrene-acrylic resin by introducing Titanium dioxide, so that the thermal stability and adhesive force of composite material greatly improve.
Specific embodiment
The present invention is described further by the following example: according to following embodiments, the present invention may be better understood. However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
Embodiment 1
Using ethylene glycol monomethyl ether as solvent, azodiisobutyronitrile is initiator, and N hydroxymethyl acrylamide is crosslinking agent, It is passed through nitrogen under stirring condition 20 minutes, is then heated to 85 DEG C, obtains mixed solution.
In 45 minutes progress polymerization reactions of mixed solution and dripping monomer, the reaction time 4 hours, monomer was styrene, third The mixture of olefin(e) acid ethyl ester, methacrylic acid and glycidyl methacrylate, wherein styrene, ethyl acrylate, methyl The weight ratio of acrylic acid and glycidyl methacrylate is 55:3:30:5, and the weight of azodiisobutyronitrile and monomer is 10: 100, the weight ratio of N hydroxymethyl acrylamide and monomer is 1.2:100.
It is cooled to 50 DEG C after polymerization reaction, water management pH value is then ammoniated in reaction system to 8, obtains epoxy phenylpropyl alcohol Resin；
Using Hydrolyze method synthesis of titanium dioxide colloidal sol: tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are dissolved in the aqueous solution of ethyl alcohol In, wherein the mass ratio of tetra-n-butyl titanate and acetylacetone,2,4-pentanedione is 1:1.8, controls pH=2,45 DEG C of hydrolysis temperature, is stirred 4 Hour.Curing agent diethylenetriamine is added, solidifies 40 minutes at 120 DEG C, it is thin to obtain titania modified epoxy styrene-acrylic resin Film.
All-round property testing is carried out to film, smooth surface, glossiness be good, it is not blistering, do not fall off, adhesive force is 1 grade, pencil hardness reaches 6H.
Embodiment 2
Using ethylene glycol monomethyl ether as solvent, azodiisobutyronitrile is initiator, and N hydroxymethyl acrylamide is crosslinking agent, It is passed through nitrogen under stirring condition 30 minutes, is then heated to 90 DEG C, obtains mixed solution.
In 45 minutes progress polymerization reactions of mixed solution and dripping monomer, the reaction time 4 hours, monomer was styrene, third The mixture of olefin(e) acid ethyl ester, methacrylic acid and glycidyl methacrylate, wherein styrene, ethyl acrylate, methyl The weight ratio of acrylic acid and glycidyl methacrylate is 55:3:20:4, and the weight of azodiisobutyronitrile and monomer is 10: 100, the weight ratio of N hydroxymethyl acrylamide and monomer is 0.8:100.
It is cooled to 50 DEG C after polymerization reaction, water management pH value is then ammoniated in reaction system to 9, obtains epoxy phenylpropyl alcohol Resin；
Using Hydrolyze method synthesis of titanium dioxide colloidal sol: tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are dissolved in the aqueous solution of ethyl alcohol In, wherein the mass ratio of tetra-n-butyl titanate and acetylacetone,2,4-pentanedione is 1:1.2, controls pH=2,45 DEG C of hydrolysis temperature, is stirred 4 Hour.Curing agent diethylenetriamine is added, solidifies 40 minutes at 100 DEG C, it is thin to obtain titania modified epoxy styrene-acrylic resin Film.
All-round property testing is carried out to film, smooth surface, glossiness be good, it is not blistering, do not fall off, adhesive force is 1 grade, pencil hardness reaches 6H.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive Property include so that include a series of elements process, method, article or equipment not only include those elements, but also Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic Element.

Claims (7)

1. a kind of preparation method of titania modified epoxy styrene-acrylic resin composite material characterized by comprising
(1), using ethylene glycol monomethyl ether as solvent, azodiisobutyronitrile is initiator, and N hydroxymethyl acrylamide is crosslinking agent, It is passed through nitrogen under stirring condition 20~30 minutes, is then heated to 85~90 DEG C, obtains mixed solution；In mixed solution and dripping 30~45 minutes progress polymerization reactions of monomer, the reaction time 3~4 hours, are cooled to 35~50 DEG C, then after polymerization reaction Water management pH value is ammoniated in reaction system to 8~9, obtains epoxy styrene-acrylic resin；
(2), using Hydrolyze method synthesis of titanium dioxide colloidal sol, curing agent diethylenetriamine is added, solidify 20 at 100~120 DEG C~ 40 minutes, obtain titania modified epoxy styrene-acrylic resin film.
2. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 1, feature Be: monomer is the mixture of styrene, ethyl acrylate, methacrylic acid and glycidyl methacrylate.
3. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 2, feature Be: styrene, ethyl acrylate, methacrylic acid and glycidyl methacrylate weight ratio be (45~55): (3 ~4): (17~30): (4~5).
4. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 2, feature Be: the weight of azodiisobutyronitrile and monomer is (8~10): 100.
5. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 2, feature Be: the weight ratio of N hydroxymethyl acrylamide and monomer is (0.8~1.2): 100.
6. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 1, feature Be: the synthetic method of TiO 2 sol includes: that tetra-n-butyl titanate and acetylacetone,2,4-pentanedione are dissolved in the aqueous solution of ethyl alcohol, PH=1~2 are controlled, 30~45 DEG C of hydrolysis temperature, are stirred 2~4 hours.
7. the preparation method of titania modified epoxy styrene-acrylic resin composite material according to claim 6, feature Be: the mass ratio of tetra-n-butyl titanate and acetylacetone,2,4-pentanedione is 1:(1.2~1.8).
CN201710861144.XA 2017-09-21 2017-09-21 The preparation method of titania modified epoxy styrene-acrylic resin composite material Withdrawn CN109535583A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057039A (en) * 1996-04-26 2000-05-02 Seiko Epson Corporation Coating composition
CN102585083A (en) * 2012-01-10 2012-07-18 江苏科技大学 Nano TiO2 modified styrene-acrylic emulsion and preparation method thereof
CN103289002A (en) * 2013-06-09 2013-09-11 昆山嘉力普制版胶粘剂油墨有限公司 Connecting resin for water paint and preparation method of connecting resin
CN104151998A (en) * 2014-08-21 2014-11-19 灵汇技术股份有限公司 Anti-scrubbing composite antibacterial metal paint and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057039A (en) * 1996-04-26 2000-05-02 Seiko Epson Corporation Coating composition
CN102585083A (en) * 2012-01-10 2012-07-18 江苏科技大学 Nano TiO2 modified styrene-acrylic emulsion and preparation method thereof
CN103289002A (en) * 2013-06-09 2013-09-11 昆山嘉力普制版胶粘剂油墨有限公司 Connecting resin for water paint and preparation method of connecting resin
CN104151998A (en) * 2014-08-21 2014-11-19 灵汇技术股份有限公司 Anti-scrubbing composite antibacterial metal paint and preparation method thereof

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Application publication date: 20190329