CN112661909B - Preparation method of flame-retardant agglomerating agent for building material field - Google Patents
Preparation method of flame-retardant agglomerating agent for building material field Download PDFInfo
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- 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
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Abstract
The invention relates to a preparation method of a flame-retardant agglomerating agent for the field of building materials, which regulates and controls the particle size of acrylate rubber to further prepare flame-retardant ASA resin. 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
The application is a divisional application with the application number of 201910966962.5, the application date of 2019.10.12 and the invention name of 'a preparation method of flame-retardant ASA resin for building materials'.
Technical Field
The invention relates to a preparation technology of a flame retardant agglomerating agent, and the particle size of acrylate rubber is regulated and controlled by the agglomerating agent to further prepare flame retardant ASA resin, and the ASA resin containing flame retardant groups is particularly suitable for the field of building materials such as resin concrete, paint, resin tiles and the like.
Background
ASA resins are ternary graft copolymers composed of acrylate-styrene-acrylonitrile, invented by BASF of germany, and 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 uniformly mixing; shenzhen Shang Ke gathers new material Limited to apply for a patent a fire-retardant ASA material and its preparation method, disclose a fire-retardant ASA material and its preparation method, the fire-retardant ASA material of this invention is prepared from following component by weight percent: 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 for the field of building materials, in particular to a flame-retardant agglomerating agent for realizing the purpose of flame retardance of 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.
A preparation method of a flame-retardant agglomerating agent for the field of building materials 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 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 of mono-alkenyl carboxylic acid monomers, 1/2 mass of mono-alkenyl flame retardant monomers, 1/2 mass of the emulsifier and 1/2 mass of the initiator, mixing the rest materials in a reactor, stirring, controlling rotation speed and reaction temperature, adding 1/2 mass of initiator, reacting for 20-50min, adding dropwise the rest mixed monomer and the reserved emulsifier, the residual mixed monomer is a mixture of reserved 2/3 mass monoalkenyl carboxylic acid monomers and reserved 1/2 mass monoalkenyl flame retardant monomers, when the mixture is dripped into 1/3 mass of mixed monomer, initiator of reserved 1/2 mass is added, and after the reaction is finished, agglomerant emulsion is obtained.
Agglomerating agent emulsion and butyl acrylate emulsion in a dry-basis mass ratio of 1: (4-10) the agglomerating agent emulsion is added to the stirred butyl acrylate emulsion, the temperature and the stirring speed are controlled, and the average particle size of the agglomerating emulsion is about 350-550nm after a period of time.
The butyl acrylate emulsion is prepared by mixing and dispersing 100 parts by mass of butyl acrylate, 0.1-2.0 parts by mass of a cross-linking agent and 0.01-0.8 part by mass of an emulsifying agent into 150 parts by mass of deionized water, adding an initiator, controlling the reaction temperature and the stirring speed, and reacting for a period of time to obtain the emulsion.
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;
wherein the monoalkenyl 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 monoalkenyl carboxylic acid monomer can be acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, isocrotonic acid, vinyl benzoic acid, hexenoic acid and other monomers containing monoalkenyl and carboxylic acid groups, and methacrylic acid is preferred;
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-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 benzene sulfonate, potassium dodecyl sulfate, saturated potassium abietate and the like, and the sodium dodecyl benzene sulfonate and the sodium dodecyl sulfate are preferably selected;
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; mixing the flame-retardant agglomerating agent emulsion and the butyl acrylate emulsion according to the mass ratio of 1: 4, adding the agglomerating agent emulsion into the stirred butyl acrylate emulsion, controlling the temperature to be 45-80 ℃ and the stirring speed to be 100-550 rpm, and after 50min, ensuring that the average particle size of the agglomerating emulsion is about 350-550 nm; 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% 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 the ASA resin.
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 (8)
1. A preparation method of a flame-retardant agglomerating agent for the field of building materials is characterized by comprising the following steps: 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 to obtain mixed monomer; calculated by taking the total mass of the mixed monomers as 100 parts by mass, the addition amount of the emulsifier is 1-10 parts by mass, the molecular weight regulator is 0.01-0.5 part by mass, the initiator is 0.1-1 part by mass, and the deionized water is 100-200 parts by mass; weighing monomer, emulsifier, molecular weight regulator and deionized water, reserving 2/3 mass of mono-alkenyl carboxylic acid monomer, reserving 1/2 mass of mono-alkenyl flame retardant monomer, reserving 1/2 mass of emulsifier and reserving 1/2 mass of initiator, mixing mono-alkenyl carboxylic acid ester monomer, 1/3 mass of mono-alkenyl carboxylic acid monomer, 1/2 mass of mono-alkenyl flame retardant monomer, 1/2 mass of emulsifier, molecular weight regulator and deionized water in a reactor, starting stirring, controlling the rotating speed of 100 and 500rpm and the reaction temperature of 45-80 ℃, adding 1/2 mass of initiator, after reacting for 20-50min, dropwise adding residual mixed monomer and reserved emulsifier, wherein the residual mixed monomer is a mixture of reserved 2/3 mass of mono-alkenyl carboxylic acid monomer and reserved 1/2 mass of mono-alkenyl flame retardant monomer, when the residual amount of the mixed monomer 1/3 is added dropwise, the initiator with the reserved mass of 1/2 is added, and the flame-retardant agglomerating agent is obtained after the reaction is finished.
2. The method of claim 1, wherein said monoalkenyl carboxylic acid ester monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and pentyl methacrylate.
3. The method of claim 1, wherein said monoalkenyl carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, isocrotonic acid, vinyl benzoic acid, and hexenoic acid.
4. The method of claim 1 wherein the mono-alkenyl flame retardant monomer is a mono-alkenyl substituent-containing organohalide monomer having the formula: RX; wherein: r is an unsaturated olefin aliphatic chain segment containing 2-18 carbon atoms, and is selected from vinyl, propenyl, isopropenyl, isopentenyl, 3-pentenyl, 6-octenyl, tetramethylvinyl, 1-heptenyl, methacryloxypropyl or methacryloxy; x is F, Cl, Br, I halogen or halogen-containing derivative.
5. The method of claim 1 wherein the emulsifier is selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium saturated fatty acid, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, and potassium saturated rosin.
6. The method of claim 1, wherein the initiator is selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.
7. The method of preparing a flame retardant agglomerating agent for use in the building material field of claim 1 wherein said molecular weight regulator is selected from the group consisting of tertiary dodecyl mercaptan and dodecyl mercaptan.
8. The method of claim 1, wherein the monoalkenyl carboxylic acid ester monomer is used in an amount of 70 parts, the monoalkenyl carboxylic acid monomer is used in an amount of 20 parts, the monoalkenyl flame retardant monomer is used in an amount of 10 parts, the emulsifier is used in an amount of 0.8 part, the molecular weight modifier is used in an amount of 0.05 part, the initiator is used in an amount of 0.5 part, and the deionized water is used in an amount of 150 parts.
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