CN110551252A - preparation method of flame-retardant ASA resin for building materials - Google Patents
preparation method of flame-retardant ASA resin for building materials Download PDFInfo
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- CN110551252A CN110551252A CN201910966962.5A CN201910966962A CN110551252A CN 110551252 A CN110551252 A CN 110551252A CN 201910966962 A CN201910966962 A CN 201910966962A CN 110551252 A CN110551252 A CN 110551252A
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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
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
Abstract
The invention relates to a preparation method of flame-retardant ASA resin for building materials, in particular to a preparation technology of a flame-retardant agglomerating agent, and a method for preparing the flame-retardant ASA resin by regulating and controlling the particle size of acrylate rubber through the agglomerating agent. The technical principle of the invention is to realize the following two functions in the preparation process of the agglomerating agent, wherein firstly, carboxylic acid groups are ensured on the surface of the agglomerating agent particles as much as possible, thus being beneficial to the fusion between the interfaces of the agglomerating agent particles and the agglomerated particles; secondly, reactive flame retardant monomers are introduced into the agglomerant, so that the agglomerant latex particles have better flame retardant grade after subsequent fusion. The flame-retardant agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, the agglomerated latex is grafted with styrene and acrylonitrile to obtain flame-retardant ASA resin, and the flame-retardant grade of the ASA resin in the technical scheme is better than that of the ASA resin prepared in a conventional mode.
Description
Technical Field
The invention relates to a preparation method of ASA resin, in particular to a preparation technology of a flame-retardant agglomerating agent, and a method for preparing the flame-retardant ASA resin by regulating and controlling the particle size of acrylate rubber through the agglomerating agent.
background
ASA resin is a ternary graft copolymer consisting of acryiate styrene acrylonitrile, invented by BASF corporation, germany, and was commercialized in 1968. The ASA resin adopts polyacrylate without a double-bond structure to replace polybutadiene rubber in ABS, and only light waves with the wavelength of below 300nm can age the ASA resin; the weather resistance of the ASA resin is about 10 times higher than that of ABS; meanwhile, ASA resin has high impact resistance, high mechanical strength, good heat resistance and chemical resistance, so the ASA resin is widely applied to the fields of building materials, automobiles, electronic and electric appliances, outdoor equipment and the like.
The ASA resin is prepared into butyl acrylate emulsion by adopting an emulsion polymerization method conventionally, then the emulsion is subjected to a grafting reaction of styrene and acrylonitrile to obtain the ASA resin, and the physical and mechanical properties of the ASA resin are regulated and controlled by controlling factors such as the particle size, the crosslinking degree and the grafting degree of the acrylate rubber emulsion. Similar to ABS resin, ASA resin is also an engineering resin material with an excellent comprehensive performance, wherein a resin shell layer is grafted on the surface of the ASA resin, and a rubber phase is arranged inside the ASA resin. The UL flame retardant rating for typical ASA resins is HB, which is the lowest flame retardant rating. The ASA resin needs to introduce an agglomeration technology in the preparation process, an agglomerating agent is also a rubber emulsion with a structure similar to that of polybutyl acrylate rubber, and the flame retardant grade of the ASA resin is also HB.
The common method for improving the flame-retardant grade of the ASA resin adopts a mode of adding the flame retardant, the flame retardant is relatively difficult to disperse and easy to agglomerate in the adding mode, and the flame retardant is easy to decompose and separate out in the post-processing process, so that loss is caused, and the flame-retardant effect is reduced. The patent CN CN102002203B applied by Shanghai Jinfa science and technology development Limited company is a flame-retardant asa modified resin and a preparation method thereof, wherein the flame-retardant asa modified resin comprises 20-55 parts of acrylate-styrene-acrylonitrile ternary graft copolymer and 25-55 parts of styrene-acrylonitrile resin; 12-20 parts of a brominated flame retardant; 3-7 parts of antimony flame retardant; 0.1-1.5 parts of an anti-dripping additive; 0.2-1 part of antioxidant; 0.3-1 part of ultraviolet absorbent; 0.2-1 part of processing aid. The preparation method comprises the following steps: accurately weighing each component, and placing the components into a high-speed mixer for uniform mixing. Shenzhen Shanke polymer new material Limited, and a flame-retardant ASA material and a preparation method thereof, and discloses a flame-retardant ASA material and a preparation method thereof. The flame-retardant ASA material is prepared from the following components in percentage by weight: 72-82% of a ternary graft copolymer consisting of acrylonitrile, styrene and acrylate; 2-7% of a toughening agent; 12-18% of tetrabromobisphenol A; 3.0-7.0% of antimony trioxide; 0.3-0.5% of ultraviolet absorbent; 0.1-1.0% of antioxidant; 0.3-0.7% of lubricant. The flame-retardant ASA material has flame-retardant property.
The flame-retardant ASA resin is prepared by adding the comonomer of a reactive flame retardant into the agglomerating agent latex during the synthesis stage, so that the flame retardant is uniformly dispersed, is in the rubber phase easy to burn, is chemically bonded with the agglomerating agent, is not easy to run off, and ensures the long-acting flame-retardant effect. The common reactive flame retardant is added into a reaction system during the polymerization reaction of macromolecules, participates in the reaction in a monomer form, and becomes a part of polymers through chemical bonding, such as 2, 3-dibromopropanol, dibromophenol, tetrabromophthalic anhydride and the like. Such flame retardants are generally used for thermosetting resins such as polyurethanes, epoxy resins, unsaturated polyesters, and phenol resins. The reactive flame retardant in the ASA resin agglomerating agent process is a flame retardant monomer containing olefinic double bonds and capable of participating in free radical polymerization, so that the flame retardance of the ASA resin is improved.
Disclosure of Invention
the invention aims to provide a preparation method of a flame-retardant ASA resin, in particular to a flame-retardant agglomerating agent designed to achieve the purpose of flame-retarding the ASA resin, and a specific implementation principle schematic diagram is shown in figure 1 in the attached drawing of the specification.
The technical principle of the invention is to realize two functional adjustments in the preparation process of the agglomerating agent, wherein firstly, carboxylic acid groups are ensured on the surface of the agglomerating agent particles as much as possible, thus being beneficial to the fusion between the interfaces of the agglomerating agent particles and the agglomerated particles; and secondly, a flame retardant group monomer is introduced into the agglomerating agent, so that the agglomerating agent latex particles have better flame retardance after subsequent fusion. In the invention, halogen flame-retardant groups are introduced on side groups by the agglomeration agent for ASA; the combustion of ASA resins in the presence of oxygen is a very vigorous oxidation reaction, also a chain chemical reaction, which generates reactive HO-free radicals when burned, and hydrocarbons and water when the HO-free radicals encounter rubber molecules. Under aerobic conditions, the hydrocarbon can continue to decompose and generate HO-free radicals, thereby forming chain reactions and continuing the combustion. To prevent the ASA resin from burning or to extinguish it requires either oxygen blocking or a reduction in the concentration of HO-radicals. The flame-retardant agglomerating agent is heated and decomposed to release halogen gas and hydrogen halide, and the halogen can play a certain role in blocking oxygen; the hydrogen halide can react with HO-free radicals to generate water and halogen ions, the halogen ions can react with hydrocarbons to generate hydrogen halide, and the hydrogen halide can further eliminate the HO-free radicals, thereby reducing the concentration of the HO-free radicals and slowing the combustion speed until the HO-free radicals are extinguished. It is also emphasized that the agglomeration agent is encapsulated in the internal rubber phase of the ASA resin to provide the ASA resin with an increased flame retardant rating.
Specifically, the preparation method of the flame-retardant ASA resin mainly comprises the following steps of:
1. The agglomerant is synthesized by mixing 30-80 parts by mass of mono alkenyl carboxylic acid ester monomer, 15-35 parts by mass of mono alkenyl carboxylic acid monomer and 5-35 parts by mass of mono alkenyl flame retardant monomer according to a formula, wherein the total mass of the mixed monomers is 100 parts by mass, the addition amount of the emulsifier is 0.1-10 parts by mass, the addition amount of the molecular weight regulator is 0.01-0.5 part by mass, the addition amount of the initiator is 0.1-1 part by mass, and the deionized water is 100 parts by mass and 200 parts by mass. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 2/3 mass monoalkenyl carboxylic acid monomers, reserving 1/2 mass monoalkenyl flame retardant monomers, reserving 1/2 mass emulsifier and reserving 1/2 mass initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed and the reaction temperature, adding 1/2 mass initiator, reacting for a period of time, dropwise adding the rest mixed monomers and the rest emulsifier, adding the initiator with the reserved 1/2 mass when dropwise adding the mixed monomers 1/3, and obtaining the agglomerant emulsion after the reaction is finished.
2. The agglomerating agent emulsion and the butyl acrylate emulsion are metered according to the mass ratio of 1: 4-10, the agglomerating agent emulsion is added into the stirred butyl acrylate emulsion, the temperature and the stirring speed are controlled, and the average particle size of the agglomerating agent emulsion is about 350-550nm after a period of time;
3. The preparation of butyl acrylate emulsion is that 100 mass portions of butyl acrylate, 0.1 to 2.0 mass portions of cross-linking agent and 0.01 to 0.8 mass portion of emulsifying agent are mixed and dispersed into 150 mass portions of deionized water, initiator is added, reaction temperature and stirring speed are controlled, and emulsion is obtained after reaction for a period of time;
4. Calculating the mass of a grafting monomer according to the dry basis weight of the agglomerated mixed emulsion, wherein the mass of a conventional grafting monomer is 20-80% of the dry glue weight, weighing styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1) after calculation, adding 0.2-2 parts by mass of an emulsifier, 0.01-0.8 part by mass of a molecular weight regulator and 200 parts by mass of deionized water, adding an organic peroxide initiator to control the reaction temperature and the stirring speed, reacting for a period of time to obtain ASA resin, and carrying out the working procedures of coagulation, washing, drying, blending granulation and the like to obtain a product, and testing the mechanical property of the ASA resin according to the standard.
The agglomerant is prepared by copolymerizing monoalkenyl carboxylic acid ester monomers, monoalkenyl carboxylic acid monomers and monoalkenyl flame retardant monomers through emulsion free radical copolymerization;
Wherein the carboxylic ester monomer can be methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate and other monomers with similar structures, and butyl acrylate is preferred;
The monoene carboxylic acid monomer can be acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, isocrotonic acid, vinyl benzoic acid, hexenoic acid and other monomers containing monoene and carboxylic acid groups, and is preferably methacrylic acid;
The mono-alkenyl flame retardant monomer is an organic halide monomer containing mono-alkenyl substituent groups, and the structural formula of the mono-alkenyl flame retardant monomer is as follows: RX; wherein: r is an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, which can be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, tetramethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably vinyl; x is F, Cl, Br, I a halogen or a halogen-containing derivative, preferably Br;
The emulsifier can be anionic emulsifiers such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, saturated sodium aliphatate, potassium dodecyl sulfonate, potassium dodecyl sulfate, saturated rosin potassium and the like, and the sodium dodecyl benzene sulfonate and the sodium dodecyl sulfate are preferred;
The initiator can be potassium persulfate, sodium persulfate, ammonium persulfate and the like, preferably potassium persulfate;
The molecular weight regulator can be an auxiliary agent suitable for the chain transfer action of an emulsion free radical polymerization system, such as tert-dodecyl mercaptan, dodecyl mercaptan and the like, and preferably tert-dodecyl mercaptan;
The preparation process of the agglomerating agent of the invention requires 30 to 80 parts by mass of mono-alkenyl carboxylic ester monomer, preferably 70 parts; 15-35 parts by mass, preferably 20 parts by mass, of a monoalkenyl carboxylic acid monomer; 5-35 parts by mass of mono-alkenyl flame retardant monomer, preferably 10 parts; according to the formula, the addition amount of the emulsifier is 0.1-10 parts by mass and preferably 0.8 part by mass, the addition amount of the molecular weight regulator is 0.01-0.5 part by mass and preferably 0.05 part by mass, the addition amount of the initiator is 0.1-1 part by mass and preferably 0.5 part by mass, and the addition amount of the deionized water is 100-200 parts by mass and preferably 150 parts by mass, calculated by taking the total mass of the mixed monomers as 100 parts by mass. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 2/3 mass of mono-alkenyl carboxylic acid monomers, reserving 1/2 mass of mono-alkenyl flame retardant monomers, reserving 1/2 mass of the emulsifier and reserving 1/2 mass of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 500rpm and the reaction temperature at 45-80 ℃, adding 1/2 mass of the initiator, reacting for 20-50min, dropwise adding the rest mixed monomers and the emulsifier, adding the initiator with reserved 1/2 mass when dropwise adding the mixed monomers 1/3, and obtaining the agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, and styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin.
The preparation method of the flame-retardant ASA resin comprises the steps of preparing a flame-retardant agglomerating agent, agglomerating butyl acrylate rubber and grafting to prepare the ASA resin in the following way. The preparation of the butyl acrylate emulsion is that 100 parts by mass of butyl acrylate, 1.0 part by mass of cross-linking agent diallyl phthalate and 0.3 part by mass of emulsifying agent are mixed and dispersed into 150 parts by mass of deionized water, initiator potassium persulfate is added, the temperature is controlled to be 45-80 ℃, the stirring speed is controlled to be 100-500rpm, and the emulsion is obtained after reaction is carried out for 50-150min, wherein the reaction raw materials can adopt different modes such as segmented replenishment and the like; the flame-retardant agglomerating agent emulsion and the butyl acrylate emulsion are measured according to the mass ratio of 1: 4, the agglomerating agent emulsion is added into the stirred butyl acrylate emulsion, the temperature is controlled to be 45-80 ℃, the stirring speed is 100-; calculating the mass of a grafting monomer according to the dry basis of the agglomerated mixed emulsion, wherein the mass of a conventional grafting monomer accounts for 60 percent of the dry glue amount, weighing styrene and acrylonitrile monomers (the ratio of the styrene monomer to the acrylonitrile monomer is 3: 1) after calculation, adding 1.5 parts by mass of an emulsifier, 0.06 part by mass of a molecular weight regulator and 200 parts by mass of deionized water, adding 0.3 part by mass of lauroyl peroxide as an organic peroxide initiator, controlling the reaction temperature to be 50 ℃ and the stirring speed to be 400rpm, reacting for 30-80min to obtain ASA resin, and carrying out the working procedures of coagulation, washing, drying, blending granulation and the like to obtain a product, and testing the mechanical property and the flame retardant grade of the ASA resin according to the standard.
Drawings
FIG. 1 is a schematic diagram of the agglomeration principle of flame retardant ASA resin.
Detailed Description
The raw material auxiliaries required for the specific implementation of the invention are as follows:
(1) Methacrylic acid, butyl acrylate, reagent grade, commercially available; vinyl chloride, dichloroethylene, vinyl bromide, ethylene dibromide, reagent grade, commercially available;
(2) Acrylonitrile, styrene, sodium dodecyl sulfate, tert-dodecyl mercaptan, potassium persulfate, deionized water, industrial grade, commercially available;
(3) other reagents not mentioned were reagent grade and commercially available.
The mechanical property test is carried out according to the corresponding national standard.
Example 1:
73g of butyl acrylate monomer and 12g of methacrylic acid monomer; 15g of ethylene dibromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 0.2g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.03g, the addition amount of initiator potassium persulfate is 0.5g, and the addition amount of deionized water is 150 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 8g of methacrylic acid monomers, reserving 7.5g of vinyl trimethoxy silane, reserving 0.1g of the emulsifier and reserving 0.25g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 500rpm and the reaction temperature at 60 ℃, adding 0.25g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 20min, adding the initiator with the reserved mass of 1/2 once when dropwise adding 1/3 of the reserved mixed monomers, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Comparative example 1: without adding flame retardant
73g of butyl acrylate monomer and 12g of methacrylic acid monomer; 0g of ethylene dibromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 0.2g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.03g, the addition amount of initiator potassium persulfate is 0.5g, and the addition amount of deionized water is 150 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 8g of methacrylic acid monomers, reserving 0g of vinyltrimethoxysilane, reserving 0.1g of the emulsifier and reserving 0.25g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 500rpm and the reaction temperature to be 60 ℃, adding 0.25g of the initiator, reacting for 20min, dropwise adding the reserved mixed monomers and the emulsifier, adding the initiator with the reserved mass of 1/2 once when the amount of the reserved mixed monomers 1/3 is added, and obtaining an agglomerant emulsion after the reaction is finished.
the agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Example 2: the flame retardant rating is slightly lower than 1
75g of butyl acrylate monomer and 15g of ethyl acrylic acid monomer; 10g of vinyl chloride monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 2g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.1g, the addition amount of initiator potassium persulfate is 0.7g, and the addition amount of deionized water is 160 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 10g of ethacrylic acid monomer, reserving 5g of chloroethylene, reserving 1g of the emulsifier and reserving 0.35g of an initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 300rpm and the reaction temperature to be 60 ℃, adding 0.35g of the initiator, dropwise adding the reserved mixed monomer and the emulsifier after reacting for 30min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomer 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant of the ASA resin are tested according to the standard.
Comparative example 2: the acrylate emulsion is directly agglomerated, then the agglomerated emulsion is subjected to grafting reaction, and chloroethylene is added in the reaction process, so that the flame retardant level is low;
75g of butyl acrylate monomer and 15g of ethyl acrylic acid monomer; vinyl chloride monomer 0 g; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 2g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.1g, the addition amount of initiator potassium persulfate is 0.7g, and the addition amount of deionized water is 160 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 10g of ethyl acrylic monomer, reserving 0g of chloroethylene, reserving 1g of the emulsifier and reserving 0.35g of an initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 300rpm and the reaction temperature to be 60 ℃, adding 0.35g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 30min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomers 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex, vinyl chloride is grafted on the agglomerated latex, ASA resin is obtained, the ASA resin is obtained through the processes of agglomeration, washing, drying, blending granulation and the like, and the mechanical property of the ASA resin is tested according to the standard.
example 3: strong agglomeration effect, strong reinforcing effect, high flame-retardant grade
30g of butyl acrylate monomer and 35g of methacrylic acid monomer; 35g of vinyl bromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 6g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.31g, the addition amount of initiator potassium persulfate is 0.9g, and the addition amount of deionized water is 190 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 25g of methacrylic acid monomers, reserving 18g of vinyl bromide, reserving 3g of the emulsifier and reserving 0.45g of an initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 500rpm and the reaction temperature at 65 ℃, adding 0.45g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 50min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomers 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
the agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Comparative example 3: no methacrylic acid monomer is added, the part is complemented by butyl acrylate, no agglomeration effect is generated, the mechanical property is poorer than that of the proportion 2, and the flame retardant effect is not changed
65g of butyl acrylate monomer and 0g of methacrylic acid monomer; 35g of vinyl bromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 6g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.31g, the addition amount of initiator potassium persulfate is 0.9g, and the addition amount of deionized water is 190 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 0g of methacrylic acid monomer, reserving 18g of vinyl bromide, reserving 3g of the emulsifier and reserving 0.45g of an initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 500rpm and the reaction temperature at 65 ℃, adding 0.45g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 50min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomers 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Example 4: the flame retardant effect is stronger than 1
45g of butyl acrylate monomer and 25g of methacrylic acid monomer; 30g of ethylene dibromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl benzene sulfonate is 10g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.25g, the addition amount of initiator potassium persulfate is 0.6g, and the addition amount of deionized water is 120 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 16g of methacrylic acid monomers, reserving 13g of ethylene dibromide, reserving 5g of the emulsifier and reserving 0.3g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 400rpm and the reaction temperature at 58 ℃, adding 0.3g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 45min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomers 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Comparative example 4: no polymerization of dibromoethane monomer
45g of butyl acrylate monomer and 25g of methacrylic acid monomer; 30g of dibromoethane monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl benzene sulfonate is 10g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.25g, the addition amount of initiator potassium persulfate is 0.6g, and the addition amount of deionized water is 120 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 16g of methacrylic acid monomers, reserving 13g of dibromoethane, reserving 5g of the emulsifier and reserving 0.3g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed at 400rpm and the reaction temperature at 58 ℃, adding 0.3g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 45min, adding the initiator with the reserved mass of 1/2 once when dropwise adding the reserved mixed monomers 1/3, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Example 5:
50g of butyl methacrylate monomer and 35g of methacrylic acid monomer; 15g of dichloroethylene monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl benzene sulfonate is 0.1g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.01g, the addition amount of initiator potassium persulfate is 0.1g, and the addition amount of deionized water is 100 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 24g of methacrylic acid monomers, reserving 8g of dichloroethylene, reserving 0.05g of the emulsifier and reserving 0.05g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 100rpm and the reaction temperature to be 55 ℃, adding 0.05g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 50min, adding the initiator with the reserved mass of 1/2 once when dropwise adding 1/3 of the reserved mixed monomers, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Comparative example 5: butyl prenate polymerization and poor weather resistance
50g of butyl prenoate monomer and 35g of methacrylic acid monomer; 15g of dichloroethylene monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl benzene sulfonate is 0.1g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.01g, the addition amount of initiator potassium persulfate is 0.1g, and the addition amount of deionized water is 100 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 24g of methacrylic acid monomers, reserving 8g of dichloroethylene, reserving 0.05g of the emulsifier and reserving 0.05g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 100rpm and the reaction temperature to be 55 ℃, adding 0.05g of the initiator, dropwise adding the reserved mixed monomers and the emulsifier after reacting for 50min, adding the initiator with the reserved mass of 1/2 once when dropwise adding 1/3 of the reserved mixed monomers, and obtaining an agglomerant emulsion after the reaction is finished.
The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
example 6:
70g of butyl acrylate monomer and 20g of methacrylic acid monomer; 10g of vinyl bromide monomer; mixing according to the formula, wherein the addition amount of emulsifier sodium dodecyl sulfate is 0.2g, the addition amount of molecular weight regulator tert-dodecyl mercaptan is 0.03g, the addition amount of initiator potassium persulfate is 0.5g, and the addition amount of deionized water is 150 g. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 14g of methacrylic acid monomers, reserving 5g of vinyl bromide, reserving 0.1g of the emulsifier and reserving 0.25g of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed to be 500rpm and the reaction temperature to be 60 ℃, adding 0.25g of the initiator, reacting for 20min, dropwise adding the reserved mixed monomers and the emulsifier, adding the initiator with the reserved mass of 1/2 once when the amount of the reserved mixed monomers 1/3 is added, and obtaining an agglomerant emulsion after the reaction is finished.
the agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, styrene and acrylonitrile are grafted on the agglomerated latex to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
Comparative example 6: acetic acid is used as an agglomerating agent, the mechanical property is poor, and the flame retardant level is low
Acetic acid is used as an agglomerating agent for agglomerating butyl acrylate emulsion, the agglomerated latex is grafted with styrene and acrylonitrile to obtain ASA resin, the ASA resin is subjected to the processes of agglomeration, washing, drying, blending granulation and the like to obtain a product, and the mechanical property and the flame retardant grade of the ASA resin are tested according to the standard.
TABLE 1 mechanical Properties of ASA resins in examples and comparative examples
Claims (21)
1. The invention relates to a preparation method of a flame-retardant ASA resin, which mainly relates to a preparation and use method of a flame-retardant agglomerating agent, and comprises the following steps: the agglomerant is synthesized by mixing 30-80 parts by mass of mono alkenyl carboxylic acid ester monomer, 15-35 parts by mass of mono alkenyl carboxylic acid monomer and 5-35 parts by mass of mono alkenyl flame retardant monomer according to a formula, wherein the total mass of the mixed monomers is 100 parts by mass, the addition amount of the emulsifier is 1-10 parts by mass, the addition amount of the molecular weight regulator is 0.01-0.5 part by mass, the addition amount of the initiator is 0.1-1 part by mass, and the deionized water is 100 parts by mass and 200 parts by mass. Weighing monomers, an emulsifier, a molecular weight regulator and deionized water, reserving 2/3 mass of mono-alkenyl carboxylic acid monomers, reserving 1/2 mass of mono-alkene flame retardant monomers, reserving 1/2 mass of the emulsifier and reserving 1/2 mass of the initiator, mixing the rest materials in a reactor, starting stirring, controlling the rotating speed and the reaction temperature, adding 1/2 mass of the initiator, dropwise adding the rest mixed monomers and the emulsifier after reacting for a period of time, supplementing the initiator with the reserved 1/2 mass when dropwise adding the mixed monomers 1/3, and obtaining the agglomerant emulsion after the reaction is finished. The agglomerating agent emulsion is used for agglomerating butyl acrylate emulsion, and the agglomerated latex is grafted with styrene and acrylonitrile to obtain the high-strength ASA resin.
2. The agglomerant of claim 1 is prepared from the emulsion free radical copolymerization of monoalkenyl carboxylic ester monomers, monoalkenyl carboxylic acid monomers, monoalkenyl flame retardant monomers.
3. The carboxylate monomer according to claim 1 or 2, wherein the carboxylate monomer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, amyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, and the like, preferably butyl acrylate.
4. The mono-olefin carboxylic acid monomer as claimed in claim 1 or 2, which is a mono-olefin and carboxylic acid group-containing monomer such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, isocrotonic acid, vinylbenzoic acid, hexenoic acid, etc., preferably methacrylic acid.
5. The mono-alkenyl flame retardant monomer of claims 1 and 2, which is a mono-alkenyl substituent-containing organic halide monomer having the formula: RX; wherein: r-an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, which can be vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, tetramethylvinyl, 1-heptenyl, methacryloxypropyl, methacryloxy, preferably vinyl; x is F, Cl, Br, I halogen or a halogen-containing derivative, preferably Br.
6. The emulsifier of claim 1 can be anionic emulsifier such as sodium dodecylbenzene sulfonate, sodium dodecylsulfate, saturated sodium fatty acid, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, saturated potassium rosinate, etc., preferably sodium dodecylbenzene sulfonate and sodium dodecylsulfate.
7. The initiator according to claim 1 may be potassium persulfate, sodium persulfate, ammonium persulfate, etc., preferably potassium persulfate.
8. The molecular weight regulator according to claim 1, wherein the molecular weight regulator is tertiary dodecanethiol, dodecanethiol or a chain transfer aid suitable for emulsion radical polymerization, preferably tertiary dodecanethiol.
9. The monoalkenyl carboxylate monomer according to claim 1, wherein the amount of the monoalkenyl carboxylate monomer is 30 to 80 parts by mass, preferably 70 parts by mass.
10. The monoalkenyl carboxylic acid monomer according to claim 1, in an amount of 15 to 35 parts by mass, preferably 20 parts.
11. The mono alkenyl flame retardant monomer according to claim 1, which is 5 to 35 parts by mass, preferably 10 parts.
12. The composition according to claim 1, wherein the emulsifier is added in an amount of 0.1 to 10 parts by mass, preferably 0.8 part by mass, based on 100 parts by mass of the total mixed monomers.
13. The composition according to claim 1, wherein the molecular weight modifier is 0.01 to 0.5 part by mass, preferably 0.05 part by mass, based on 100 parts by mass of the total mixed monomers.
14. the initiator as claimed in claim 1, is added in an amount of 0.1 to 1 part by mass, preferably 0.5 part by mass, based on 100 parts by mass of the total mixed monomers.
15. the process according to claim 1, wherein the amount of the deionized water is preferably 150 parts by mass per 100 parts by mass of the total mixed monomers and 200 parts by mass of the deionized water.
16. Weighing the reagent of claim 1, wherein 2/3 mass of vinyl carboxylic acid monomer, 1/2 mass of mono-alkenyl flame retardant monomer, 1/2 mass of emulsifier and 1/2 mass of initiator are reserved.
17. The process as claimed in claim 1, wherein the rotation speed is controlled at 100-500rpm and the reaction temperature is controlled at 45-80 ℃.
18. The initial initiator amount of claim 1, 17 is 1/2 mass of initiator added.
19. The agglomerating agent as claimed in claim 1 and 17, after emulsifying free radical reaction for 20-50min, adding the rest of the mixed monomer and the emulsifier dropwise, and adding the initiator with the reserved mass of 1/2 when the mixed monomer 1/3 is added dropwise.
20. The agglomerating agent of claim 1 mixed with a butyl acrylate latex for agglomeration in a dry basis ratio of 1: 1 (1-4), preferably 1: 4.
21. The preparation of the agglomerant of the preceding claims and its use under conditions of conventional free radical polymerization emulsion polymer agglomerant mechanisms of action, not limited to such conventional conditions.
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| CN103242478B (en) * | 2013-05-17 | 2015-04-22 | 合肥工业大学 | Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant |
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