CN109369842B - Preparation method of composite acrylate emulsion - Google Patents

Preparation method of composite acrylate emulsion Download PDF

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CN109369842B
CN109369842B CN201811156419.0A CN201811156419A CN109369842B CN 109369842 B CN109369842 B CN 109369842B CN 201811156419 A CN201811156419 A CN 201811156419A CN 109369842 B CN109369842 B CN 109369842B
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kettle
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CN109369842A (en
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邵亚
王琳
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Jiangsu Normal University
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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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a preparation method of composite acrylic ester emulsion, adding polyoxyethylene octyl phenol ether-10, sodium dodecyl sulfate, ammonium persulfate into an emulsifying kettle, then adding deionized water, stirring and dissolving, sequentially adding butyl acrylate, methyl methacrylate and methacrylic acid into the pre-emulsifying kettle, stirring and emulsifying to obtain monomer pre-emulsion, sequentially adding sodium bicarbonate and deionized water into a polymerization kettle, starting stirring to dissolve the monomer pre-emulsion, placing the monomer pre-emulsion into a 50 ℃ water bath, then installing a constant-pressure dropping funnel, weighing 5 parts of the prepared monomer pre-emulsion, adding the monomer pre-emulsion into the polymerization kettle, adding modified nano hydroxyapatite material, weighing ammonium persulfate, dissolving the ammonium persulfate into water, slowly adding the monomer pre-emulsion into the polymerization kettle, adjusting the water bath temperature to 82 ℃ to slowly rise the temperature, slowly dropping the monomer pre-emulsion after the temperature rises to 82 ℃, washing the pre-emulsifying kettle with water after dropping and dropping the polymerization kettle, adjusting the pH value to 8 by ammonia water to obtain the composite nano acrylate emulsion.

Description

Preparation method of composite acrylate emulsion
Technical Field
The invention relates to a preparation method of a composite acrylate emulsion.
Background
The polyacrylate emulsion has excellent performance and may be used widely in paint, adhesive, fabric finishing agent, leather finishing, ink and other fields. However, most of the polyacrylate emulsions are ordinary emulsions, and have large particle diameters, and most of them are white opaque low-viscosity colloidal dispersions having particle diameters of 0.1 to 1 μm.
Due to the properties of the nano material such as surface effect, small-size effect, quantum size effect and the like, the nano polymer particles have high surface energy and low film forming temperature of nano particles, and can obtain a paint film with higher glass transition temperature at the same film forming temperature, thereby having better weather resistance and pollution resistance. The diameter of the colloidal particle of the general polymer emulsion is more than 100nm, and the microemulsion polymerization started in the early 80 s can directly prepare the nano polymer colloidal particle with the particle size of 10-50nm, and the nano latex can effectively improve the properties of the emulsion, such as film forming performance, film density, smoothness and the like. With the perfection of microemulsion polymerization preparation technology, it has become possible to prepare water paint by using the nano polymer latex.
Disclosure of Invention
The invention discloses a preparation method of a composite acrylate emulsion, and the prepared acrylate emulsion has excellent physical properties.
A process for preparing composite acrylate emulsion includes such steps as adding polyoxyvinyl octylphenol ether-10 (0.30 wt. portions), sodium laurylsulfate (0.3), ammonium persulfate (0.15), deionized water (20), stirring for dissolving, sequentially adding butyl acrylate, methyl methacrylate and methacrylic acid, stirring for emulsifying for 15min to obtain monomer pre-emulsion, sequentially adding sodium bicarbonate (0.2) and deionized water (30), stirring for dissolving, putting in 50 deg.C water bath,
then a constant pressure dropping funnel is arranged, 5 parts of prepared monomer pre-emulsion is weighed and added into a polymerization kettle, 0.3 part of modified nano-hydroxyapatite material is added, 0.3 part of ammonium persulfate is weighed and dissolved in 5 parts of water, the mixture is slowly added into the polymerization kettle, the water bath temperature is adjusted to 82 ℃ at the same time, the temperature is slowly raised, after the temperature is raised to 82 ℃, the monomer pre-emulsion is slowly dropped for 2 hours or so,
then 5 parts of water is taken to flush the pre-emulsification kettle and added into the polymerization kettle dropwise, and the pH value is adjusted to 8 by ammonia water, so as to obtain the composite nano acrylate emulsion.
The modified nano hydroxyapatite material is prepared as follows: dispersing 20 parts of nano hydroxyapatite powder with the diameter of 40nm into 200 parts of water, regulating the pH value to 5 by using hydrochloric acid, then dropwise adding 5 parts of epichlorohydrin (the mass concentration is 99%, and the purity is analyzed and sold in the market) into the solution, reacting for 6 hours at 25 ℃, filtering to remove the epichlorohydrin which does not participate in the reaction, and obtaining the epichlorohydrin modified nano hydroxyapatite; adding 4 wt% of hyperbranched polyamidoamine (2 parts) acid solution into epoxy chloropropane modified nano-hydroxyapatite (20 parts), then adding 4 wt% of NaOH solution (200 parts), stirring for 2 hours at 40 ℃, then carrying out suction filtration on the nano-hydroxyapatite, washing to be neutral, and putting into an oven for drying to obtain the modified hyperbranched polyamide nano-hydroxyapatite.
Has the advantages that: the oxygen atoms on the carbonyl group on the surface of the nano-hydroxyapatite can be combined with the carboxyl or hydroxyl of the monomer pre-emulsion to form hydrogen bonds, and a polymer layer is formed on the surface of the microsphere, so that the agglomeration phenomenon of nano-substances is reduced, the emulsion rheology is enhanced, the nano-hydroxyapatite after the modified hyperbranched polyamide has a small-size effect, can be filled into an emulsion coating, and effectively enhances the physical isolation effect of the emulsion coating. In addition, the nano hydroxyapatite is subjected to in-situ polymerization on the surface to generate polyamide, the polyamide is added into the emulsion, the mechanical property of the coating is improved, the hyperbranched polyamide in the pore channel extends to the pore opening to generate new bonds with the matrix latex, the crosslinking density of the system is increased, and the tensile strength and the elongation at break of the coating are further multiplied.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of composite acrylic ester emulsion comprises the steps of adding 0.30 part of polyoxyethylene octyl phenol ether-10, 0.3 part of lauryl sodium sulfate and 0.15 part of ammonium persulfate into an emulsifying kettle, then adding 20 parts of deionized water, starting stirring to completely dissolve the polyoxyethylene octyl phenol ether-10, the lauryl sodium sulfate and the ammonium persulfate, sequentially adding 15 parts of butyl acrylate, 20 parts of methyl methacrylate and 2 parts of methacrylic acid into a pre-emulsifying kettle, stirring and emulsifying for 15min to obtain a monomer pre-emulsion, sequentially adding 0.2 part of sodium bicarbonate and 30 parts of deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, starting stirring to dissolve the sodium bicarbonate and the deionized water, placing the mixture into a water bath at 50 ℃,
then a constant-pressure dropping funnel is arranged, 5 parts of prepared monomer pre-emulsion is weighed and added into a polymerization kettle, 0.3 part of modified nano-hydroxyapatite material is added, 0.3 part of ammonium persulfate is weighed and dissolved in 5 parts of water, the mixture is slowly added into the polymerization kettle, the water bath temperature is adjusted to 82 ℃ at the same time, the temperature is slowly raised, after the temperature is raised to 82 ℃, the monomer pre-emulsion is slowly dropped, 5m parts of water is taken after the dropping is finished, the pre-emulsion kettle is washed and added into the polymerization kettle, and the pH value is adjusted to be 8 by ammonia water, so that the composite nano-acrylate emulsion is obtained.
The modified nano hydroxyapatite material is prepared as follows: dispersing 20 parts of nano hydroxyapatite powder with the diameter of 40nm into 200 parts of water, regulating the pH value to 5 by using hydrochloric acid, then dropwise adding 5 parts of epichlorohydrin (the mass concentration is 99%, and the purity is analyzed and sold in the market) into the solution, reacting for 6 hours at 25 ℃, filtering to remove the epichlorohydrin which does not participate in the reaction, and obtaining the epichlorohydrin modified nano hydroxyapatite; adding 4 wt% of hyperbranched polyamidoamine (2 parts) acid solution into epoxy chloropropane modified nano-hydroxyapatite (20 parts), then adding 4 wt% of NaOH solution (200 parts), stirring for 2 hours at 40 ℃, then carrying out suction filtration on the nano-hydroxyapatite, washing to be neutral, and putting into an oven for drying to obtain the modified hyperbranched polyamide nano-hydroxyapatite.
Example 2
The difference from the embodiment 1 is that,
20 parts of butyl acrylate, 15 parts of methyl methacrylate and 2 parts of methacrylic acid, the rest being the same.
Example 3
The difference from the embodiment 1 is that,
15 parts of butyl acrylate, 15 parts of methyl methacrylate and 1 part of methacrylic acid, the remainder being identical.
Comparative example 1
The difference from the embodiment 1 is that,
no modified nano hydroxyapatite material is added.
Comparative example 2
The difference from the embodiment 1 is that,
the nano hydroxyapatite powder is not modified and is a common hydroxyapatite material.
Comparative example 3
The difference from the embodiment 1 is that,
the modified nano hydroxyapatite material is epoxy chloropropane modified nano hydroxyapatite instead of modified hyperbranched polyamide nano hydroxyapatite.
The following table shows the mechanical properties and water resistance of the emulsions of the examples and comparative examples after film formation
Figure 551735DEST_PATH_IMAGE002
Tests show that the embodiment of the invention has excellent mechanical property and water resistance.

Claims (1)

1. A preparation method of composite acrylic ester emulsion comprises the steps of adding 0.30 part of polyoxyethylene octyl phenol ether-10, 0.3 part of lauryl sodium sulfate and 0.15 part of ammonium persulfate into an emulsifying kettle, then adding 20 parts of deionized water, starting stirring to completely dissolve the polyoxyethylene octyl phenol ether-10, the lauryl sodium sulfate and the ammonium persulfate, sequentially adding 15 parts of butyl acrylate, 20 parts of methyl methacrylate and 2 parts of methacrylic acid into a pre-emulsifying kettle, stirring and emulsifying for 15min to obtain a monomer pre-emulsion, sequentially adding 0.2 part of sodium bicarbonate and 30 parts of deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, starting stirring to dissolve the sodium bicarbonate and the deionized water, placing the mixture into a water bath at 50 ℃,
then a constant-pressure dropping funnel is arranged, 5 parts of prepared monomer pre-emulsion is weighed and added into a polymerization kettle, 0.3 part of modified hyperbranched polyamide nano-hydroxyapatite is added, 0.3 part of ammonium persulfate is weighed and dissolved in 5 parts of water, the mixture is slowly added into the polymerization kettle, the water bath temperature is adjusted to 82 ℃ at the same time, the temperature is slowly increased, after the temperature is increased to 82 ℃, the monomer pre-emulsion is slowly dropped, 5 parts of water is taken after dropping, the pre-emulsion kettle is washed and dropped into the polymerization kettle, and the pH value is adjusted to 8 by ammonia water, so that the composite nano-acrylate emulsion is obtained;
the modified nano hydroxyapatite material is prepared as follows: dispersing 20 parts of nano hydroxyapatite powder with the diameter of 40nm into 200 parts of water, regulating the pH value to 5 by using hydrochloric acid, then dropwise adding 5 parts of epichlorohydrin with the mass concentration of 99% and the commercial analytical purity into the solution, reacting for 6 hours at 25 ℃, filtering to remove the epichlorohydrin which does not participate in the reaction, and obtaining the epichlorohydrin modified nano hydroxyapatite; adding 2 parts of acid solution of 4 wt% of hyperbranched polyamide into 20 parts of epoxy chloropropane modified nano-hydroxyapatite, then adding 200 parts of 4 wt% NaOH solution, stirring for 2 hours at 40 ℃, then carrying out suction filtration on the nano-hydroxyapatite, washing to be neutral, and placing into an oven for drying to obtain the modified hyperbranched polyamide nano-hydroxyapatite.
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CN111663327A (en) * 2020-06-05 2020-09-15 西安工程大学 Preparation method of polyacrylic acid based graphene core-shell structure composite fiber
CN112251097A (en) * 2020-10-20 2021-01-22 汤普勒新材料嘉兴有限公司 Multifunctional polyacrylate nano composite coating agent and preparation method thereof
CN115926566A (en) * 2022-11-21 2023-04-07 南昌大学 Temporary protective coating for surface of nuclear fuel rod and preparation method thereof

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JPH0632809A (en) * 1992-05-18 1994-02-08 Hitachi Chem Co Ltd Three-dimensional polymer fine particle, its production, shrink-controlling agent and unsaturated polyester resin composition
DE69329259T2 (en) * 1992-05-27 2001-02-22 Mitsui Chemicals Inc Use of an emulsion of a polymer containing (meth) acrylate units as a dental adhesive
CN102030873B (en) * 2010-10-27 2012-09-05 华南理工大学 Method for preparing nano silicon dioxide/polyacrylate composite emulsion
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