CN108912261B - Flame-retardant acrylate miniemulsion and preparation method thereof - Google Patents

Flame-retardant acrylate miniemulsion and preparation method thereof Download PDF

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CN108912261B
CN108912261B CN201810504530.8A CN201810504530A CN108912261B CN 108912261 B CN108912261 B CN 108912261B CN 201810504530 A CN201810504530 A CN 201810504530A CN 108912261 B CN108912261 B CN 108912261B
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acrylate
flame
miniemulsion
retardant
preparation
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CN108912261A (en
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敬小波
王小君
陈八斤
包界杰
江小平
付海宏
汪小燕
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Zhejiang ChuanHua functional new material Co.,Ltd.
Transfar Zhilian Co Ltd
Hangzhou Transfar Fine Chemicals Co Ltd
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Hangzhou Transfar Fine Chemicals Co Ltd
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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
    • C08F220/16—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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08K3/38—Boron-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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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

Abstract

The invention discloses a flame-retardant acrylate miniemulsion and a preparation method thereof. The flame-retardant acrylate miniemulsion disclosed by the invention consists of a nano zinc borate nuclear layer and a polyacrylate shell layer, and the preparation method comprises the following steps of: adding an acrylate monomer into a reaction container, sequentially adding a co-stabilizer, nano zinc borate, di (methacryloyloxyethyl) hydrogen phosphate and N-trimethylol methacrylamide, and stirring until the mixture is uniformly mixed; adding phosphate ester anionic non-ionic emulsifier and sodium carbonate into deionized water for full dissolution, then dripping into the obtained mixed solution, and performing ultrasonic treatment for 10-20 minutes; introducing nitrogen, adding a redox initiator at 20-30 ℃ to initiate polymerization, adding an after-treatment agent to perform after-treatment, keeping the temperature for 0.3-0.8 h, then cooling to below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion. The emulsion disclosed by the invention is halogen-free and aldehyde-free, safe and environment-friendly, has a remarkable flame retardant effect after film formation, and has good mechanical properties and water resistance.

Description

Flame-retardant acrylate miniemulsion and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a flame-retardant acrylate miniemulsion and a preparation method thereof.
Background
With the improvement of environmental protection and safety protection consciousness, halogen-free flame retardance has become a research hotspot of polyacrylate materials. Most of flame-retardant acrylate emulsion is prepared by adding a flame retardant later at present, the addition amount is usually high, and the mechanical stability of the emulsion and the water resistance of an emulsion film are often influenced due to poor compatibility and easy migration of the external flame retardant and a polymer. In recent years, methods such as physically coating inorganic nanoparticles and copolymerizing a flame-retardant monomer and acrylate are used, so that the method is an effective method for improving the utilization rate of a flame retardant and improving the application performance of an emulsion film.
N-methylol acrylamide is a common cross-linking agent for acrylate emulsion, is low in price and remarkable in effect, but formaldehyde is released in the cross-linking process to limit the application of the N-methylol acrylamide. The crosslinking degree is improved by using the matching of various aldehyde-free crosslinking agents, the mechanical property and the water resistance of the emulsion film can be greatly improved, and the stable carbon skeleton can be constructed by the aid of a system under the action of high temperature or flame.
Patent CN105085790B obtains stable bulk flame retardant acrylate emulsion by copolymerizing vinyl silane grafted metal hydroxide functional monomer and acrylic monomer, but the flame retardant effect of metal hydroxide used alone is limited. Patent CN105111358A synthesizes organic phosphorus and magnesium hydroxide synergistic acrylate composite emulsion, has durable, low-smoke, nontoxic and environment-friendly flame retardant performance, uses fluorine-containing monomer to improve water resistance, but polymer is not fully crosslinked to improve mechanical strength, and does not mention the construction of a flame retardant carbon forming system.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the flame-retardant acrylate miniemulsion, which effectively combines a nano inorganic substance and a flame-retardant monomer, so that the flame-retardant acrylate miniemulsion has good stability, and the mechanical property and the flame-retardant effect are improved.
Therefore, the invention adopts the following technical scheme: the flame-retardant acrylate miniemulsion consists of a nano zinc borate nuclear layer and a polyacrylate shell layer.
In addition to the technical scheme, the flame-retardant acrylate miniemulsion is prepared from the following raw materials in parts by weight by a miniemulsion polymerization method:
Figure GDA0002739975260000011
Figure GDA0002739975260000021
the invention adopts another technical scheme that: the preparation method of the flame-retardant acrylate miniemulsion comprises the following steps:
1) adding an acrylate monomer into a reaction container, starting stirring, sequentially adding a co-stabilizer, nano zinc borate, di (methacryloyloxyethyl) hydrogen phosphate and N-trimethylolpropane methacrylamide, and stirring until the mixture is uniformly mixed;
2) adding a phosphate ester anionic nonionic emulsifier and sodium carbonate into deionized water, stirring for dissolving, then dripping into the mixed solution obtained in the step 1), and performing ultrasonic treatment for 10-20 minutes;
3) introducing nitrogen, adding a redox initiator at 20-30 ℃ to initiate polymerization reaction, continuing to react for 2-4 hours at 60-80 ℃, adding an after-treatment agent to perform after-treatment and keeping the temperature for 0.3-0.8 hour, then cooling to below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion;
the dosage of the raw materials is as follows by weight:
Figure GDA0002739975260000022
as a supplement to the above technical scheme, the acrylate monomer is one or a mixture of more than two of acrylonitrile, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate.
As a supplement to the technical scheme, the co-stabilizer is one of hexadecane and dodecyl acrylate.
In addition to the above technical scheme, the phosphate anionic nonionic emulsifier has the following structural formula:
Figure GDA0002739975260000031
wherein R is C12～C14N is 4 to 6.
As a supplement to the above technical scheme, the redox initiator is one of sodium persulfate/sodium bisulfite and ammonium persulfate/sodium hydrosulfite.
In addition to the above technical solution, the post-treatment agent is tert-butyl hydroperoxide/ascorbic acid.
The invention has the following beneficial effects: according to the invention, by adopting a miniemulsion polymerization technology, zinc borate and a flame-retardant monomer are effectively combined to obtain a halogen-free formaldehyde-free and high-stability body flame-retardant emulsion; the nano zinc borate, the di (methacryloyloxyethyl) hydrogen phosphate and the N-trihydroxymethyl methacrylamide simultaneously play a flame retardant role and a crosslinking role, and the emulsion is crosslinked through ionic crosslinking and chemical bonds after being formed into a film, so that the emulsion has good mechanical properties and water resistance, and helps to construct a stable carbon skeleton under the action of high temperature and flame.
Detailed Description
The present invention is described below by way of specific examples, but the present invention is not limited to these examples.
Example 1
30.5 g of tert-butyl acrylate and 9.5g of methyl acrylate were placed in a reaction vessel, stirred, and 1.5g of dodecyl acrylate, 2.2g of nano zinc borate, 5.0g of di (methacryloyloxyethyl) hydrogen phosphate and 10.0g of 10.0g N-trimethylolmethacrylamide were added in this order and stirred until mixed uniformly. Then a mixed solution of 5.4g of phosphate anionic nonionic emulsifier and 2.0g of sodium carbonate in 110g of deionized water is slowly dropped in, and then ultrasonic treatment is carried out for 15 minutes. Introducing nitrogen, adding 3.0g of sodium persulfate/3.0 g of sodium bisulfite at the temperature of 20-30 ℃ to initiate polymerization reaction, continuing to react for 3 hours at the temperature of 70-80 ℃, adding 2.0g of tert-butyl hydroperoxide/2.0 g of ascorbic acid for post-treatment, preserving heat for 0.5 hour, then cooling to the temperature below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion.
Example 2
32.5g of butyl acrylate, 25.2 g of methylstyrene and 22.3g of tert-butyl methacrylate are placed in a reaction vessel, stirred, 1.5g of hexadecane, 4.5g of nano-zinc borate, 12.0g of di (methacryloyloxyethyl) hydrogen phosphate and 3.4g N-trimethylolmethacrylamide are added in this order and stirred until a homogeneous mixture is obtained. Then a mixed solution of 5.0g of phosphate anionic nonionic emulsifier and 1.4g of sodium carbonate in 150g of deionized water is slowly dropped in, and then ultrasonic treatment is carried out for 10 minutes. Introducing nitrogen, adding 4.0g of sodium persulfate/4.0 g of sodium bisulfite at the temperature of 20-30 ℃ to initiate polymerization reaction, continuing to react for 3 hours at the temperature of 60-70 ℃, adding 3.0g of tert-butyl hydroperoxide/3.0 g of ascorbic acid for post-treatment, preserving heat for 0.3 hour, then cooling to the temperature below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion.
Example 3
34.0g of butyl acrylate, 20.5 g of styrene and 25.5g of methyl methacrylate are added to a reaction vessel, stirring is started, 4.0g of dodecyl acrylate, 5.0g of nano zinc borate, 8.0g of di (methacryloyloxyethyl) hydrogen phosphate and 5.0g of 5.0g N-trimethylolmethacrylamide are added in this order, and stirring is carried out until uniform mixing is achieved. Then a mixed solution of 6.5g of phosphate anionic nonionic emulsifier and 3.0g of sodium carbonate in 150g of deionized water is slowly dropped in, and then ultrasonic treatment is carried out for 20 minutes. Introducing nitrogen, adding 4.0g of ammonium persulfate/4.0 g of sodium hydrosulfite at the temperature of 20-30 ℃ to initiate polymerization reaction, continuing to react for 3 hours at the temperature of 65-75 ℃, adding 1.0g of tert-butyl hydroperoxide/1.0 g of ascorbic acid for post-treatment, preserving heat for 0.8 hour, cooling to the temperature below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion.
Example 4
8.0g of acrylonitrile, 22.5 g of styrene and 24.8g of ethyl acrylate were added to a reaction vessel, and stirring was started, 4.0g of hexadecane, 3.1g of nano zinc borate, 5.8g of di (methacryloyloxyethyl) hydrogen phosphate and 5.0g of 5.0g N-trimethylolmethacrylamide were added in this order, and stirring was carried out until uniform mixing was achieved. Then, a mixed solution of 3.0g of phosphate anionic nonionic emulsifier and 1.4g of sodium carbonate in 120g of deionized water was slowly dropped, followed by sonication for 15 minutes. Introducing nitrogen, adding 2.0g of sodium persulfate/2.0 g of sodium bisulfite at the temperature of 20-30 ℃ to initiate polymerization reaction, continuing to react for 3 hours at the temperature of 60-70 ℃, adding 1.5g of tert-butyl hydroperoxide/1.5 g of ascorbic acid for post-treatment, preserving heat for 0.5 hour, then cooling to the temperature below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion.
Comparative example 1
The only difference from example 4 is that N-trimethylolmethacrylamide was not present.
Comparative example 2
The only difference from example 4 is that the di (methacryloyloxyethyl) hydrogen phosphate is replaced by a non-crosslinking reactive phosphorus-containing monomer, methacrylic ether phosphate, in the same amount.
Comparative example 3
The difference from example 4 is only that the nano zinc borate is changed into nano magnesium hydroxide, and the amount is not changed.
The flame retardant acrylate miniemulsions provided in examples 1 to 4 and comparative examples 1 to 3, respectively, were dried in a mold to form films, and were sufficiently dried and crosslinked by baking at 100 c for 10 minutes, and then subjected to mechanical property testing and thermal property (TGA) analysis, as shown in table 1 below. Comparing example 4 with comparative examples 1 to 3, it can be seen that nano zinc borate, di (methacryloyloxyethyl) hydrogen phosphate and N-trimethylol methacrylamide effectively enhance the mechanical properties of the resin and synergistically exert the flame retardant and carbon forming effects.
TABLE 1
Figure GDA0002739975260000041
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Any simple modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.

Claims (6)

1. The preparation method of the flame-retardant acrylate miniemulsion is characterized in that the flame-retardant acrylate miniemulsion consists of a nano zinc borate nuclear layer and a polyacrylate shell layer,
the preparation method of the flame-retardant acrylate miniemulsion comprises the following steps:
1) adding an acrylate monomer into a reaction container, starting stirring, sequentially adding a co-stabilizer, nano zinc borate, di (methacryloyloxyethyl) hydrogen phosphate and N-trimethylolpropane methacrylamide, and stirring until the mixture is uniformly mixed;
2) adding a phosphate ester anionic nonionic emulsifier and sodium carbonate into deionized water, stirring for dissolving, then dripping into the mixed solution obtained in the step 1), and performing ultrasonic treatment for 10-20 minutes;
3) introducing nitrogen, adding a redox initiator at 20-30 ℃ to initiate polymerization reaction, continuing to react for 2-4 hours at 60-80 ℃, adding an after-treatment agent to perform after-treatment and keeping the temperature for 0.3-0.8 hour, then cooling to below 45 ℃, filtering and discharging to obtain the flame-retardant acrylate miniemulsion;
the dosage of the raw materials is as follows by weight:
Figure FDA0002739975250000011
2. the method according to claim 1, wherein the acrylate monomer is one or a mixture of two or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, t-butyl acrylate and t-butyl methacrylate.
3. The method according to claim 1, wherein the co-stabilizer is one of hexadecane and dodecyl acrylate.
4. The method of claim 1, wherein the phosphate anionic nonionic emulsifier has the following structural formula:
Figure FDA0002739975250000012
wherein R is C12～C14N is 4 to 6.
5. The method according to claim 1, wherein the redox initiator is one of sodium persulfate/sodium bisulfite and ammonium persulfate/sodium hydrosulfite.
6. The method of claim 1, wherein the post-treatment agent is t-butyl hydroperoxide/ascorbic acid.
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KR101191114B1 (en) * 2008-01-18 2012-11-15 주식회사에이엔지랩 Aqueous pressure-sensitive adhesive composition, process for preparing thereof and pressure-sensitive adhesive film comprising the same
CN103225215B (en) * 2013-04-28 2015-02-04 百利合化工（中山）有限公司 Environmental protection fire retardation type textile printing coating material and preparation method thereof
CN105111358B (en) * 2015-08-07 2017-09-22 陕西科技大学 A kind of phosphorous polyacrylate/nanometer Mg (OH)2The preparation method of complex emulsions

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