CN113278116A - ASA non-breaking white high-rubber powder, ASA non-breaking white film and preparation method thereof - Google Patents
ASA non-breaking white high-rubber powder, ASA non-breaking white film and preparation method thereof Download PDFInfo
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention belongs to the field of high polymer materials, and relates to ASA resin non-folding white high-rubber powder and an ASA non-folding white film and a preparation method thereof. The invention provides a preparation method of ASA non-broken white high-glue powder, which comprises the following steps: step 1), reacting acrylate, a cross-linking agent, 0.5-5% of an emulsifier, an electrolyte and an initiator; step 2), dropwise adding a mixed solution consisting of acrylic ester and a cross-linking agent and an initiator into the reaction system for reaction; and 3) dropwise adding a mixed solution of styrene and acrylonitrile and an initiator into the reaction system to obtain the ASA high-rubber powder. The invention indicates that ASA non-broken white high-rubber powder with the particle size of 50-120 nm is synthesized by a specific method for the first time, and the obtained ASA non-broken white high-rubber powder can be used for preparing an ASA non-broken white film; thereby widening the application range of the ASA rubber powder.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to ASA resin non-folding white high-rubber powder and an ASA non-folding white film and a preparation method thereof.
Background
Compared with ABS, the ASA resin is a ternary graft copolymer composed of acrylonitrile (A), styrene (S) and acrylic ester (A), and because the butadiene rubber is replaced by the acrylic ester rubber without double bonds, the weather resistance is essentially improved and is about 10 times higher than that of ABS, and other mechanical properties, processing performance, electric insulation and chemical resistance are similar to those of ABS. In addition, ASA has good colorability and excellent weatherability of the resin itself, and can be dyed in various vivid colors without fading easily. The product processed by the ASA resin does not need surface protection such as paint spraying, coating, electroplating and the like, can be directly used outdoors, is exposed in the sun for 9-15 months, and has almost no reduction in impact strength and elongation and almost no change in color. ASA films are widely used outdoors because of their excellent weather resistance.
With the development of ASA resin synthesis technology in recent years, emulsion graft resin blending has become one of the main methods, and its superiority has been gradually shown. The emulsion grafting and blending method comprises three steps: preparing acrylic ester latex; grafting and copolymerizing acrylonitrile and styrene on the acrylic latex; and blending the product of graft copolymerization with resin. The process comprises the following steps: synthesis of crosslinked acrylate (PBA) latex → agglomeration process → emulsion graft copolymerization toughening agent → agglomeration → washing → drying → blending with SAN (AS) resin → ASA resin. However, the film product prepared by ASA prepared by the existing method has low refractivity of white light, thereby limiting the use of the film product.
Disclosure of Invention
Aiming at the defects, the invention provides an ASA non-folding white high-adhesive powder, an ASA non-folding white film and a preparation method thereof, wherein the obtained ASA film is a non-folding white film, and the non-folding white film is as follows: when the ASA film product is applied, no whitening mark is generated when the product is subjected to forming operations such as bending, folding and pressing, and the like, so that the original color of the folded (or bent) part of the product is kept.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of ASA non-breaking white high-rubber powder, which comprises the following steps:
step 1), putting 100-400 parts by weight of deionized water, 5-30 parts by weight of acrylate, 0.01-15 parts by weight of a cross-linking agent, 0.5-5 parts by weight of an emulsifier, 0.1-1 part by weight of an electrolyte and 0.001-0.1 part by weight of an initiator into a polymerization kettle with a stirring device and a cooler; then replacing the mixture with inert gas for at least three times, stirring and heating to 65-80 ℃ (preferably 75 ℃), reacting for 0.5-2 hours (preferably 1 hour), and preserving heat for 0.5-2 hours (preferably 1 hour);
step 2), dropwise adding a mixed solution consisting of 40-50 parts by weight of acrylic ester and 0.1-15 parts by weight of a cross-linking agent and 0.02-0.2 part by weight of an initiator into the reaction system within 1-5 hours, and preserving heat for 0.5-2 hours (preferably 1 hour) at 70-80 ℃ (preferably 75 ℃);
step 3), dropwise adding 30-50 parts by weight of mixed solution consisting of styrene and acrylonitrile and 0.01-0.2 part by weight of initiator into the reaction system within 1-3 hours, controlling the reaction temperature to be 70-80 ℃ (preferably 75 ℃), and then preserving heat for 0.5-2 hours (preferably 1 hour) at 75-80 ℃ (preferably 80 ℃) after dropwise adding; finally, filtering, salting out, washing and drying the obtained emulsion to obtain ASA high-rubber powder (emulsion graft copolymerization toughening body); wherein the mass ratio of the styrene to the acrylonitrile is as follows: 70-80: 30 to 20.
Further, in step 1) and step 2), the acrylate is selected from the group consisting of: at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, or isooctyl acrylate.
Further, in step 1) and step 2), the crosslinking agent is selected from: at least one of divinylbenzene, ethylene glycol diacrylate, monoethylene glycol diacrylate, allyl methacrylate, or diallyl maleate.
Further, in the step 1), the emulsifier is at least one of an anionic emulsifier or a nonionic emulsifier.
Still further, the anionic emulsifier comprises: alkyl (aryl) ether sulfates, sodium dodecyl (benzene) sulfonate, sodium dodecyl sulfate, sodium alkyl diphenyl ether disulfonate, dihexyl sulfosuccinate sodium salt, potassium oleate, or sodium N-lauroyl sarcosinate.
Still further, the nonionic emulsifier comprises: nonylphenol polyoxyethylene ether compounds, fatty ester compounds or alkylolamide compounds.
Further, in step 1), the electrolyte comprises hydrochloric acid, sulfuric acid inorganic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or phosphate.
Further, in steps 1) to 3), the initiator includes a thermal decomposition type initiator or a redox type initiator.
Still further, the thermal decomposition type initiator is selected from: potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide or tert-butyl hydroperoxide.
Still further, the redox initiator is selected from: persulfate-bisulfite or hydrogen peroxide-ferrous salt. In order to reduce the interference of metal ions such as calcium, magnesium, iron and the like on the polymerization reaction, a chelating agent (EDTA) is added into the redox system.
The second technical problem to be solved by the invention is to provide ASA non-breaking white high rubber powder which is prepared by adopting the method.
Furthermore, the average latex particle size of the ASA non-whitening high-rubber powder is 50-120 nm, whitening deterioration is caused when the particle size is too large, and whitening reduction is reduced.
The third technical problem to be solved by the invention is to provide an ASA non-folding white film, which is prepared by taking the ASA non-folding white high-rubber powder as a raw material.
Further, the ASA non-breaking white film prepared by taking the ASA non-breaking white high-rubber powder as a raw material adopts the following method: mixing dry ASA non-breaking white high-glue powder with SAN (AS) (styrene and acrylonitrile copolymer (resin)) resin and functional additives, granulating by using a double-screw extruder, and preparing a membrane by using a membrane drawing machine, thereby obtaining an ASA non-breaking white membrane; wherein the ASA non-broken white high-rubber powder, the SAN and the functional additive have the mass ratio: 20-70 parts of ASA non-breaking white high rubber powder, 30-80 parts of SAN and 0.01-2 parts of functional additive.
Further, the functional auxiliary agent is: auxiliary agents such as an antioxidant, a UV agent, a pigment and the like; such as 0.01 to 0.5 weight portion of antioxidant, 0.01 to 0.5 weight portion of UV agent and 0.1 to 1 weight portion of mold release agent.
Further, the dried ASA non-broken white high-glue powder is dried by the following method: 1) drying by an airflow spraying method; 2) dewatering and drying in a coagulation demulsification mode.
The invention has the beneficial effects that:
the invention indicates that ASA non-broken white high-rubber powder with the particle size of 50-120 nm is synthesized by a specific method for the first time, and the obtained ASA non-broken white high-rubber powder can be used for preparing an ASA non-broken white film; thereby widening the application range of the ASA rubber powder.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
In the first step, 200L of deionized water, 10g of butyl acrylate, 0.5g of monoethylene glycol diacrylate, 0.05g of allyl methacrylate, 2g of sodium lauryl sulfate, 0.5g of sodium bicarbonate and 0.02g of potassium persulfate were put into a polymerization reactor equipped with a stirrer and a cooler, and then replaced with nitrogen gas three times, stirred and heated. The reaction temperature is controlled at 75 ℃, the reaction is carried out for 1 hour, and the temperature is kept for 1 hour.
In the second step, a mixture of 50g of butyl acrylate, 5g of monoethylene glycol diacrylate and 0.5g of allyl methacrylate and 0.05g of potassium persulfate were added dropwise over 2.5 hours. The reaction temperature was controlled at 75 ℃ and the temperature was maintained for 1 hour after the addition.
In the third step, a mixture of styrene (30 g), acrylonitrile (10 g), and potassium persulfate (0.04 g) were added dropwise over 1.5 hours. The reaction temperature is controlled at 75 ℃, the temperature is kept for 1 hour after the dripping is finished, and then the temperature is kept for 1 hour at 80 ℃ to obtain the latex-like graft copolymerization emulsion with the average grain diameter of 60 nm.
The obtained emulsion was filtered, and then salted out with 1% calcium chloride aqueous solution, washed with water, filtered, and dried to obtain powder ASA highpowder powder (graft copolymer toughening agent) without whitening.
30 parts of the graft copolymer toughening body, 70 parts of AS resin, 0.4 part of antioxidant, 0.4 part of UV, 0.1 part of release agent and pigment are mixed, a double-screw extruder is used for granulation, a sample is prepared by using a double-roller pull sheet, the whitening performance of the sample is detected, and the detection result is shown in Table 1. The specific detection method for whitening comprises the following steps: the prepared film is folded into dead marks, and whether white marks exist at the folding corners or whether the folding corners are light or heavy is observed.
Example 2
In the first step, 200L of deionized water, 15g of butyl acrylate, 0.5g of monoethylene glycol diacrylate, 0.15g of allyl methacrylate, 1.5g of sodium lauryl sulfate, 0.45g of sodium bicarbonate and 0.015g of potassium persulfate were put into a polymerization reactor equipped with a stirrer and a cooler, and then replaced with nitrogen gas three times, stirred and heated. The reaction temperature is controlled at 75 ℃, the reaction is carried out for 1 hour, and the temperature is kept for 1 hour.
In the second step, a mixture of 45g of butyl acrylate, 4.5g of monoethylene glycol diacrylate and 0.45g of allyl methacrylate and 0.045g of potassium persulfate were added dropwise over 2 hours. The reaction temperature was controlled at 75 ℃ and the temperature was maintained for 1 hour after the addition.
Third, a mixed solution of 38g of styrene and 2g of acrylonitrile and 0.04g of potassium persulfate were added dropwise over 1.5 hours. The reaction temperature is controlled at 75 ℃, the temperature is kept for 1 hour after the dripping is finished, and then the temperature is kept for 1 hour at 80 ℃ to obtain the latex graft copolymer emulsion with the average grain diameter of 80 nm.
The other steps are the same as in example 1.
Example 3
In the first step, 200L of deionized water, 10g of butyl acrylate, 1g of monoethylene glycol diacrylate, 0.1g of allyl methacrylate, 1.0g of sodium lauryl sulfate, 0.4g of sodium bicarbonate and 0.01g of potassium persulfate were put into a polymerization reactor equipped with a stirrer and a cooler, and then replaced with nitrogen gas three times, stirred and heated. The reaction temperature is controlled at 75 ℃, the reaction is carried out for 1 hour, and the temperature is kept for 1 hour.
In the second step, a mixture of 45g of butyl acrylate, 5g of monoethylene glycol diacrylate and 0.45g of allyl methacrylate and 0.045g of potassium persulfate were added dropwise over 1.5 hours. The reaction temperature was controlled at 75 ℃ and the temperature was maintained for 1 hour after the addition.
In the third step, a mixture of styrene 33g, acrylonitrile 12g and potassium persulfate 0.045g were added dropwise over 2 hours. The reaction temperature is controlled at 75 ℃, the temperature is kept for 1 hour after the dripping is finished, and then the temperature is kept for 1 hour at 80 ℃ to obtain the latex graft copolymer emulsion with the average grain diameter of 105 nm.
The other steps are the same as in example 1.
Example 4
The same procedure as in example 1 was repeated, except that sodium lauryl sulfate (1.0 g) and sodium hydrogencarbonate (0.4 g) were added.
Comparative example 1
20 parts of a graft copolymerization toughening agent A (XC 500A of Korea brocade lake) in the existing market, 80 parts of AS resin, 0.4 part of antioxidant, 0.4 part of UV, 0.1 part of release agent and pigment are mixed and granulated by a double-screw extruder to obtain ASA resin, and the sample preparation detection results are shown in Table 1.
Comparative example 2
30 parts of graft copolymerization toughening body modifier A in the existing market, 70 parts of AS resin and the like in the comparative example 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Folding white | Is free of | + | +++ | +++ | ++++ | +++++ |
The number + represents the degree of turning white; according to the detection result, the ASA non-breaking white high-adhesive powder can be prepared by the method.
Claims (10)
1. A preparation method of ASA non-breaking white high-glue powder is characterized by comprising the following steps:
step 1), putting 100-400 parts by weight of deionized water, 5-30 parts by weight of acrylate, 0.01-15 parts by weight of a cross-linking agent, 0.5-5 parts by weight of an emulsifier, 0.1-1 part by weight of an electrolyte and 0.001-0.1 part by weight of an initiator into a polymerization kettle with a stirring device and a cooler; then, replacing the mixture with inert gas for at least three times, stirring and heating the mixture to 65-80 ℃, reacting for 0.5-2 hours, and preserving heat for 0.5-2 hours;
step 2), dropwise adding a mixed solution consisting of 40-50 parts by weight of acrylic ester and 0.1-15 parts by weight of a cross-linking agent and 0.02-0.2 part by weight of an initiator into the reaction system within 1-5 hours, and preserving heat for 0.5-2 hours at 70-80 ℃ after dropwise adding;
step 3), dropwise adding 30-50 parts by weight of mixed solution consisting of styrene and acrylonitrile and 0.01-0.2 part by weight of initiator into the reaction system within 1-3 hours, controlling the reaction temperature at 70-80 ℃, and then preserving heat at 75-80 ℃ for 0.5-2 hours after dropwise adding; finally, filtering, salting out, washing and drying the obtained emulsion to obtain high rubber powder ASA; wherein the mass ratio of the styrene to the acrylonitrile is as follows: 70-80: 30 to 20.
2. The method for preparing ASA non-breaking white high-adhesive powder according to claim 1, wherein in step 1) and step 2), the acrylate is selected from the group consisting of: at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, or isooctyl acrylate.
3. The process for preparing ASA non-breaking white high-gum powder according to claim 1 or 2, characterized in that in step 1) and step 2), the crosslinking agent is selected from: at least one of divinylbenzene, ethylene glycol diacrylate, monoethylene glycol diacrylate, allyl methacrylate, or diallyl maleate.
4. The method for preparing ASA non-breaking white high-gum powder according to any one of claims 1 to 3, wherein in the step 1), the emulsifier is at least one of an anionic emulsifier or a nonionic emulsifier;
further, the anionic emulsifier comprises: alkyl (aryl) ether sulfates, sodium dodecyl (benzene) sulfonate, sodium dodecyl sulfate, sodium alkyl diphenyl ether disulfonate, dihexyl sulfosuccinate sodium salt, potassium oleate, or sodium N-lauroyl sarcosinate;
further, the nonionic emulsifier comprises: nonylphenol polyoxyethylene ether compounds, fatty ester compounds or alkylolamide compounds.
5. The method for preparing ASA breaking-free white-high adhesive powder according to any one of claims 1 to 4, wherein in the step 1), the electrolyte comprises hydrochloric acid, sulfuric acid inorganic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or phosphate.
6. The method for preparing ASA non-breaking white high-adhesive powder according to any one of claims 1 to 5, wherein in the steps 1) to 3), the initiator comprises a thermal decomposition type initiator or a redox type initiator;
further, the thermal decomposition type initiator is selected from: potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, cumene hydroperoxide or tert-butyl hydroperoxide;
further, the redox initiator is selected from: persulfate-bisulfite or hydrogen peroxide-ferrous salt.
7. ASA non-breaking white high rubber powder is characterized in that the high rubber powder is prepared by the method of any one of claims 1 to 6.
8. The ASA non-breaking white high-rubber powder according to claim 7, wherein the average latex particle size of the ASA non-breaking white high-rubber powder is 50-120 nm.
9. An ASA non-breaking white film is characterized in that the ASA non-breaking white film is prepared by taking ASA non-breaking white high-rubber powder as a raw material, and the ASA non-breaking white high-rubber powder is prepared by the method of any one of claims 1 to 6 or the ASA non-breaking white high-rubber powder of claim 7 or 8.
10. The ASA non-refractive white film according to claim 9, wherein the ASA non-refractive white film is prepared by the following method: mixing dry ASA non-breaking white high-rubber powder with SAN (AS) resin and functional additives, granulating by using a double-screw extruder, and preparing a film by using a film drawing machine, thereby obtaining an ASA non-breaking white film; wherein the ASA non-broken white high-rubber powder, the SAN and the functional additive have the mass ratio: 20-70 parts of ASA non-breaking white high rubber powder, 30-80 parts of SAN and 0.01-2 parts of functional additive;
further, the functional auxiliary agent is: an antioxidant, a UV agent or a pigment;
further, the dried ASA non-broken white high-glue powder is dried by the following method: 1) an air-stream spraying method; 2) a method for dewatering and drying in a coagulation demulsification mode.
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| CN116589724A (en) * | 2023-06-19 | 2023-08-15 | 新乡市创美科技股份有限公司 | ASA (ASA) non-folding white film preparation process |
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