CN113174111B - Modified ABS resin with good heat resistance and flame retardance and preparation method thereof - Google Patents
Modified ABS resin with good heat resistance and flame retardance and preparation method thereof Download PDFInfo
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- CN113174111B CN113174111B CN202110580778.4A CN202110580778A CN113174111B CN 113174111 B CN113174111 B CN 113174111B CN 202110580778 A CN202110580778 A CN 202110580778A CN 113174111 B CN113174111 B CN 113174111B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to the technical field of preparation of modified resin, and provides modified ABS resin with good heat resistance and flame retardance and a preparation method thereof. The continuous phase of the modified ABS resin is styrene-acrylonitrile copolymer, and the dispersed phase is composite powder with a three-layer structure. The inner layer of the composite powder is silicon dioxide, the middle layer is polybutadiene, and the outer layer is a silicon dioxide doped styrene-acrylonitrile-bis (3-maleimidophenyl) phenyl phosphine oxide terpolymer. By introducing silicon dioxide and a bis (3-maleimidophenyl) phenyl phosphine oxide chain segment into a dispersed phase structure, the heat resistance and the flame retardance of the ABS are obviously improved.
Description
Technical Field
The invention belongs to the technical field of modified resin preparation, and provides a modified ABS resin with good heat resistance and flame retardance and a preparation method thereof.
Background
ABS is a terpolymer of three monomers of acrylonitrile, butadiene and styrene, and has common performances of three components, wherein the acrylonitrile component endows the acrylonitrile copolymer with chemical corrosion resistance, heat resistance and surface hardness, the butadiene component endows the acrylonitrile copolymer with high elasticity and toughness, and the styrene component endows the styrene copolymer with good processability and electrical performance. Therefore, ABS has wide application in the fields of machinery, automobiles, electronics, construction, and the like.
The common synthetic process of ABS is as follows: firstly, polybutadiene latex is prepared by an emulsion method or a solution method, then SAN (styrene-acrylonitrile copolymer) is grafted on the surface of latex particles, grafting powder with a core-shell structure is prepared by the processes of emulsion breaking, suction filtration, drying and the like, and then the SAN and the grafting powder are mixed to obtain the ABS resin.
When ABS is used for housings of electronic and electrical devices (e.g., computers, digital control devices, transformers, etc.) or housings of household electrical appliances (e.g., hair dryers, microwave ovens, electric cookers, televisions, air conditioners, etc.), it is required to have good heat resistance and flame retardancy to ensure safe use. In view of the above, the invention provides a modified ABS resin and a preparation method thereof, aiming at improving the heat resistance and flame retardancy of ABS materials and further expanding the applications thereof in the fields of electronic devices, household appliances and the like.
Disclosure of Invention
In order to improve the heat resistance and the flame retardance of the ABS resin and further expand the application of the ABS resin in the fields of electronic equipment, household appliances and the like, the invention provides a modified ABS resin with good heat resistance and flame retardance and a preparation method thereof.
In order to realize the purpose, the invention relates to the following specific technical scheme:
the invention firstly provides a modified ABS resin with good heat resistance and flame retardance, which consists of a continuous phase and a disperse phase; the continuous phase is styrene-acrylonitrile copolymer; the dispersed phase is composite powder with a three-layer structure, wherein the inner layer is silicon dioxide, the middle layer is polybutadiene, the outer layer is silicon dioxide doped terpolymer, the inner layer and the middle layer are combined through a coupling agent, and the middle layer and the outer layer are combined in a graft copolymerization mode; the terpolymer is a styrene-acrylonitrile-bis (3-maleimidophenyl) phenyl phosphine oxide copolymer.
Generally, the dispersed phase of the ABS resin is grafted powder with a core-shell structure, the core layer is polybutadiene, the shell layer is a styrene-acrylonitrile copolymer, and the shell layer is combined with the core layer through a grafting reaction. The invention creatively adopts composite powder with a three-layer structure as a dispersion phase, silicon dioxide as an inner layer, bis (3-maleimidophenyl) phenyl phosphine oxide, styrene and acrylonitrile are copolymerized in an outer layer, and the silicon dioxide is used for doping the terpolymer, so that the heat resistance and the flame retardance of the ABS are obviously improved.
The principle of improving the heat resistance of the ABS in the technical scheme of the invention is as follows: (1) the outer layer of the composite powder is copolymerized by bis (3-maleimide phenyl) phenyl phosphine oxide, and the bis (3-maleimide phenyl) phenyl phosphine oxide contains rigid plane five-membered rings (maleimide rings), so that the heat resistance of the material can be improved; (2) the bis (3-maleimidophenyl) phenyl phosphine oxide is copolymerized with styrene and acrylonitrile through maleimide groups, and one molecule of the bis (3-maleimidophenyl) phenyl phosphine oxide contains two reactive maleimide groups, so that the copolymer can form chemical crosslinking, and the heat resistance of the ABS material is improved; (3) the outer layer of the composite powder is doped with silicon dioxide, and cyano with strong polarity in a copolymer chain segment can form strong interaction with the silicon dioxide to form a physical crosslinking point, so that the heat resistance of the ABS material is improved.
The principle of improving the flame retardance of the ABS by the technical scheme of the invention is as follows: (1) the outer layer of the composite powder is copolymerized by bis (3-maleimide phenyl) phenyl phosphine oxide, phosphorus-containing groups are decomposed when the material is burnt, the surface temperature of the material is reduced by absorbing heat, and a matrix is promoted to form a phosphorus-rich carbon layer; (2) the outer layer of the composite powder is doped with the terpolymer by adopting the silicon dioxide, and the silicon dioxide has low surface energy and is easy to migrate to the surface of the phosphorus-rich carbon layer, so that the phosphorus-rich carbon layer can be protected from being oxidized and degraded, the strength of the phosphorus-rich carbon layer can be improved, and a better protection effect is achieved; (3) the inner layer and the outer layer of the composite powder both contain silicon dioxide, which is beneficial to forming a silicon dioxide network, forming a more compact barrier layer when the material is burnt, weakening heat transfer and inhibiting the release of smoke.
The invention also provides a preparation method of the modified ABS resin with good heat resistance and flame retardance, which comprises the following preparation steps:
(1) adding dodecylbenzene sulfonic acid, hydroxyl silicone oil and a coupling agent into the silica sol, and carrying out ultrasonic treatment for 20-30 min to obtain modified silica sol;
(2) adding modified silica sol, disproportionated rosin soap, sodium dodecyl benzene sulfonate and persulfate initiator into deionized water, introducing nitrogen to remove air, vacuumizing, adding butadiene, heating to 40-45 ℃ for reaction, supplementing disproportionated rosin soap after reacting for 18-20 h, continuing to react for 12-15 h, supplementing disproportionated rosin soap again, continuing to react for 8-10 h, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding glucose, sodium pyrophosphate and ferrous sulfate into deionized water, completely dissolving, adding potassium hydroxide, rosin acid soap, silica-polybutadiene composite latex and silica sol, introducing nitrogen to remove air, heating to 60-65 ℃, then adding styrene, acrylonitrile, bis (3-maleimidophenyl) phenylphosphine and cumene hydroperoxide, reacting for 1-1.5 h, supplementing glucose, sodium pyrophosphate, ferrous sulfate and cumene hydroperoxide, heating to 80-85 ℃, continuing to react for 3-3.5 h, cooling to 60-65 ℃, adding an antioxidant, stirring for 30-40 min, discharging, stirring with a magnesium sulfate solution to break emulsion, curing, suction filtering and drying to obtain composite powder;
(4) and adding the composite powder and the styrene-acrylonitrile copolymer into a mixing roll for mixing, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
In the step (1), the silica sol is modified, so that the surface polarity of colloidal particles is reduced, the polybutadiene generated in the step (2) is coated on the surface of silica particles, and the inner layer and the middle layer of the composite powder can form good combination under the action of a coupling agent. Preferably, in the step (1), the raw materials comprise, by weight, 100 parts of silica sol, 0.1-0.15 part of dodecylbenzene sulfonic acid, 0.5-1 part of hydroxyl silicone oil and 0.5-0.7 part of a coupling agent.
Preferably, the silica sol has a silica content of 30 wt%.
Preferably, the hydroxyl silicone oil has a hydroxyl group content of 6%.
Preferably, the coupling agent is a silane coupling agent, and can be selected from one of kh-550, kh-560, kh-570 and kh-792.
Step (2) is a process of synthesizing polybutadiene on the surface of silica particles. Usually, polybutadiene latex is synthesized by an emulsion method, the particle size of the obtained polybutadiene is smaller, the particle size of rubber particles needs to be increased by agglomeration, but the particle size is difficult to control in the agglomeration process, and the phenomenon of uneven particle size is easy to occur. According to the invention, silica sol is added when polybutadiene latex is synthesized by an emulsion method, so that the generated polybutadiene particles grow by taking silica particles as cores, and colloidal particles with larger particle size (more than 300nm) can be obtained. In order to further improve the particle size uniformity, a main emulsifier (disproportionated rosin soap) was added in portions, the first addition amount being 60%, the second addition amount being 30%, and the third addition amount being 10% of the total amount.
Preferably, in the step (2), the raw materials comprise, by weight, 50 parts of deionized water, 50 parts of modified silica sol, 1-1.2 parts of disproportionated rosin soap, 0.1-0.2 part of sodium dodecyl benzene sulfonate, 0.1 part of persulfate initiator and 30 parts of butadiene.
The step (3) is a synthesis process of the outer layer, namely a process of forming a terpolymer by styrene, acrylonitrile and bis (3-maleimidophenyl) phenyl phosphine oxide, and a process of grafting and combining the terpolymer and the polybutadiene at the middle layer. In order to improve the degree of copolymerization reaction, an active agent (glucose, sodium pyrophosphate and ferrous sulfate) and an initiator (cumene hydroperoxide) are added in two times; the first adding amount of glucose, sodium pyrophosphate and ferrous sulfate is 75% of the total amount, and the second adding amount is 25% of the total amount; the first addition amount of cumene hydroperoxide was 85% of the total amount, and the second addition amount was 15% of the total amount.
Preferably, in the step (3), the raw materials comprise, by weight, 100 parts of deionized water, 0.2 part of glucose, 0.3 part of sodium pyrophosphate, 0.01-0.02 part of ferrous sulfate, 0.025 part of potassium hydroxide, 2-4 parts of abietic acid soap, 50 parts of silica-polybutadiene composite latex, 6-8 parts of silica sol, 12-15 parts of styrene, 5-7 parts of acrylonitrile, 3-4 parts of bis (3-maleimidophenyl) phenyl phosphine oxide, 0.25-0.3 part of cumene hydroperoxide and 0.01-0.02 part of antioxidant.
The bis (3-maleimidophenyl) phenylphosphine oxide may be prepared by the following method: preparing commercially available bis (3-aminophenyl) phenyl phosphine oxide or triphenyl phosphine oxide through nitration and reduction to obtain bis (3-aminophenyl) phenyl phosphine oxide, adding the bis (3-aminophenyl) phenyl phosphine oxide into tetrahydrofuran, adding maleic anhydride to form a transparent acylamino acid solution, adding sodium acetate and acetic anhydride, reacting at about 80 ℃ for 2 hours, adding ice water to precipitate, washing and drying. Wherein the composition comprises, by weight, 100 parts of tetrahydrofuran, 10-12 parts of bis (3-aminophenyl) phenylphosphine oxide, 7-8 parts of maleic anhydride, 0.8-1.2 parts of sodium acetate and 45-55 parts of acetic anhydride.
Finally, uniformly distributing the dispersed phase (composite powder with a three-layer structure) in the continuous phase (styrene-acrylonitrile copolymer) through high-temperature mixing to obtain the modified ABS resin with good heat resistance and flame retardance. Preferably, the mixing temperature is 180-190 ℃, and the mixing time is 5-10 min.
Preferably, in the step (4), the weight parts of the raw materials are 20-25 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer. The styrene-acrylonitrile copolymer is used as a continuous phase, wherein the molar ratio of styrene to acrylonitrile is 6: 4-7: 3.
The invention provides a modified ABS resin with good heat resistance and flame retardance and a preparation method thereof, and the modified ABS resin has the following beneficial effects: the continuous phase of the modified ABS resin prepared by the method is styrene-acrylonitrile copolymer, and the dispersed phase is composite powder with a three-layer structure. By adopting composite powder with a three-layer structure as a dispersion phase, taking silicon dioxide as an inner layer, copolymerizing bis (3-maleimidophenyl) phenyl phosphine oxide with styrene and acrylonitrile in the outer layer and doping the terpolymer with the silicon dioxide, the heat resistance and the flame retardance of the ABS are obviously improved. Compared with the unmodified ABS resin, the glass transition temperature Tg of the modified ABS resin prepared by the invention is improved by more than 25 ℃, the Vicat softening temperature VST is improved by more than 15 ℃, the oxygen index is improved by more than 6 percent, and the V-1 combustion grade can be achieved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 0.1 part of dodecylbenzene sulfonic acid, 1 part of hydroxyl silicone oil and 0.7 part of kh-550 silane coupling agent into 100 parts of silica sol, and carrying out ultrasonic treatment for 20min to obtain modified silica sol;
(2) adding 50 parts of modified silica sol, 0.6 part of disproportionated rosin soap, 0.1 part of sodium dodecyl benzene sulfonate and 0.1 part of potassium persulfate into 50 parts of deionized water, introducing nitrogen to remove air, vacuumizing, adding 30 parts of butadiene, heating to 45 ℃ for reaction, supplementing 0.3 part of disproportionated rosin soap after reacting for 18 hours, continuing to react for 12 hours, supplementing 0.1 part of disproportionated rosin soap again, continuing to react for 9 hours, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding 0.15 part of glucose, 0.225 part of sodium pyrophosphate and 0.015 part of ferrous sulfate into 100 parts of deionized water, completely dissolving, adding 0.025 part of potassium hydroxide, 3 parts of rosin acid soap, 50 parts of silica-polybutadiene composite latex and 6 parts of silica sol, introducing nitrogen to remove air, heating to 65 ℃, adding 12 parts of styrene, 7 parts of acrylonitrile, 3 parts of bis (3-maleimidophenyl) phenyl phosphine oxide and 0.255 part of cumene hydroperoxide, reacting for 1 hour, supplementing 0.05 part of glucose, 0.075 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.045 part of cumene hydroperoxide, heating to 85 ℃, continuing to react for 3.5 hours, cooling to 65 ℃, adding 0.02 part of antioxidant 1010, stirring for 30 minutes, discharging, stirring and suction filtering by using a magnesium sulfate solution, curing, demulsifying and drying to obtain composite powder;
(4) adding 20 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer (the molar ratio of styrene to acrylonitrile is 6:4) into a mixing roll, mixing for 5min at 190 ℃, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
Example 2
(1) Adding 0.15 part of dodecylbenzene sulfonic acid, 0.5 part of hydroxyl silicone oil and 0.5 part of kh-550 silane coupling agent into 100 parts of silica sol, and carrying out ultrasonic treatment for 20min to obtain modified silica sol;
(2) adding 50 parts of modified silica sol, 0.72 part of disproportionated rosin soap, 0.2 part of sodium dodecyl benzene sulfonate and 0.1 part of potassium persulfate into 50 parts of deionized water, introducing nitrogen to remove air, vacuumizing, adding 30 parts of butadiene, heating to 40 ℃ for reaction, supplementing 0.36 part of disproportionated rosin soap after reacting for 20 hours, continuing to react for 12 hours, supplementing 0.12 part of disproportionated rosin soap again, continuing to react for 10 hours, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding 0.15 part of glucose, 0.225 part of sodium pyrophosphate and 0.015 part of ferrous sulfate into 100 parts of deionized water, completely dissolving, adding 0.025 part of potassium hydroxide, 3 parts of rosin acid soap, 50 parts of silica-polybutadiene composite latex and 6.5 parts of silica sol, introducing nitrogen to remove air, heating to 60 ℃, adding 15 parts of styrene, 5 parts of acrylonitrile, 3.2 parts of bis (3-maleimidophenyl) phenylphosphine and 0.255 part of cumene hydroperoxide, reacting for 1.5h, adding 0.05 part of glucose, 0.075 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.045 part of cumene hydroperoxide, heating to 80 ℃, continuing to react for 3h, cooling to 60 ℃, adding 0.01 part of antioxidant 1010, stirring for 40min, discharging, stirring with magnesium sulfate solution, carrying out suction filtration, curing, demulsifying, drying to obtain composite powder;
(4) adding 22 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer (the molar ratio of styrene to acrylonitrile is 6:4) into a mixing mill, mixing for 10min at 180 ℃, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
Example 3
(1) Adding 0.13 part of dodecylbenzene sulfonic acid, 0.8 part of hydroxyl silicone oil and 0.6 part of kh-550 silane coupling agent into 100 parts of silica sol, and carrying out ultrasonic treatment for 30min to obtain modified silica sol;
(2) adding 50 parts of modified silica sol, 0.66 part of disproportionated rosin soap, 0.15 part of sodium dodecyl benzene sulfonate and 0.1 part of potassium persulfate into 50 parts of deionized water, introducing nitrogen to remove air, vacuumizing, adding 30 parts of butadiene, heating to 40 ℃ for reaction, supplementing 0.33 part of disproportionated rosin soap after reacting for 19 hours, continuing to react for 15 hours, supplementing 0.11 part of disproportionated rosin soap again, continuing to react for 8 hours, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding 0.15 part of glucose, 0.225 part of sodium pyrophosphate and 0.015 part of ferrous sulfate into 100 parts of deionized water, completely dissolving, adding 0.025 part of potassium hydroxide, 3 parts of abietic acid soap, 50 parts of silica-polybutadiene composite latex and 7 parts of silica sol, introducing nitrogen to remove air, heating to 62 ℃, adding 12 parts of styrene, 7 parts of acrylonitrile, 3.5 parts of bis (3-maleimidophenyl) phenylphosphine and 0.255 part of cumene hydroperoxide, reacting for 1.2h, supplementing 0.05 part of glucose, 0.075 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.045 part of cumene hydroperoxide, heating to 82 ℃, continuing to react for 3.3h, cooling to 62 ℃, adding 0.015 part of antioxidant 1010, stirring for 35min, discharging, stirring with magnesium sulfate solution, curing, filtering, and drying to obtain composite powder;
(4) adding 23 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer (the molar ratio of styrene to acrylonitrile is 6:4) into a mixing mill, mixing for 8min at 185 ℃, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
Example 4
(1) Adding 0.1 part of dodecylbenzene sulfonic acid, 0.8 part of hydroxyl silicone oil and 0.7 part of kh-550 silane coupling agent into 100 parts of silica sol, and carrying out ultrasonic treatment for 25min to obtain modified silica sol;
(2) adding 50 parts of modified silica sol, 0.66 part of disproportionated rosin soap, 0.2 part of sodium dodecyl benzene sulfonate and 0.1 part of potassium persulfate into 50 parts of deionized water, introducing nitrogen to remove air, vacuumizing, adding 30 parts of butadiene, heating to 42 ℃ for reaction, supplementing 0.33 part of disproportionated rosin soap after reacting for 19 hours, continuing to react for 13 hours, supplementing 0.11 part of disproportionated rosin soap again, continuing to react for 9 hours, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding 0.15 part of glucose, 0.225 part of sodium pyrophosphate and 0.015 part of ferrous sulfate into 100 parts of deionized water, completely dissolving, adding 0.025 part of potassium hydroxide, 2 parts of abietic acid soap, 50 parts of silica-polybutadiene composite latex and 7.5 parts of silica sol, introducing nitrogen to remove air, heating to 65 ℃, adding 15 parts of styrene, 5 parts of acrylonitrile, 3.8 parts of bis (3-maleimidophenyl) phenylphosphine and 0.255 part of cumene hydroperoxide, reacting for 1.5h, supplementing 0.05 part of glucose, 0.075 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.045 part of cumene hydroperoxide, heating to 85 ℃, continuing to react for 3h, cooling to 65 ℃, adding 0.01 part of antioxidant 1010, stirring for 40min, discharging, stirring with magnesium sulfate solution, curing, filtering, and drying to obtain composite powder;
(4) adding 24 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer (the molar ratio of styrene to acrylonitrile is 6:4) into a mixing roll, mixing for 5min at 190 ℃, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
Example 5
(1) Adding 0.15 part of dodecylbenzene sulfonic acid, 0.5 part of hydroxyl silicone oil and 0.6 part of kh-550 silane coupling agent into 100 parts of silica sol, and carrying out ultrasonic treatment for 22min to obtain modified silica sol;
(2) adding 50 parts of modified silica sol, 0.6 part of disproportionated rosin soap, 0.18 part of sodium dodecyl benzene sulfonate and 0.1 part of potassium persulfate into 50 parts of deionized water, introducing nitrogen to remove air, vacuumizing, adding 30 parts of butadiene, heating to 45 ℃ for reaction, supplementing 0.3 part of disproportionated rosin soap after reacting for 18 hours, continuing to react for 13 hours, supplementing 0.1 part of disproportionated rosin soap again, continuing to react for 8 hours, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding 0.15 part of glucose, 0.225 part of sodium pyrophosphate and 0.015 part of ferrous sulfate into 100 parts of deionized water, completely dissolving, adding 0.025 part of potassium hydroxide, 4 parts of abietic acid soap, 50 parts of silica-polybutadiene composite latex and 8 parts of silica sol, introducing nitrogen to remove air, heating to 60 ℃, adding 13.5 parts of styrene, 6 parts of acrylonitrile, 4 parts of bis (3-maleimidophenyl) phenylphosphine and 0.255 part of cumene hydroperoxide, reacting for 1h, supplementing 0.05 part of glucose, 0.075 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 0.045 part of cumene hydroperoxide, heating to 80 ℃, continuing to react for 3.5h, cooling to 60 ℃, adding 0.01 part of antioxidant 1010, stirring for 40min, discharging, stirring by using a magnesium sulfate solution, curing, filtering, and drying to obtain composite powder;
(4) adding 25 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer (the molar ratio of styrene to acrylonitrile is 6:4) into a mixing mill, mixing for 10min at 180 ℃, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
Comparative example 1
Silica sol is not used in the preparation process, namely: the composite powder consists of two layers, the inner layer does not contain silicon dioxide, the outer layer is styrene-acrylonitrile-bis (3-maleimidophenyl) phenyl phosphine oxide terpolymer which is not doped with silicon dioxide, and other preparation conditions are completely consistent with those of the embodiment 5.
Comparative example 2
Bis (3-maleimidophenyl) phenylphosphine oxide was not used in the preparation, i.e.: the outer layer of the composite powder is silicon dioxide doped styrene-acrylonitrile binary copolymer, and other preparation conditions are completely consistent with those of example 5.
Comparative example 3
Neither silica sol nor bis (3-maleimidophenyl) phenylphosphineoxide was used in the preparation, i.e.: the composite powder is of a conventional core-shell structure, the core is polybutadiene, the shell is a styrene-acrylonitrile binary copolymer which is not doped with silicon dioxide, and other preparation conditions are completely consistent with those of the embodiment 5.
And (3) performance testing: (1) the prepared ABS resin is molded into a sample wafer with the thickness of 1mm by compression molding on a flat vulcanizing machine, then a sample specimen with the thickness of 30mm multiplied by 10mm multiplied by 1mm is prepared by a sample preparation machine, and DMA test is carried out at the frequency of 1Hz and the heating rate of 3 ℃/min within the range of-100 to 160 ℃ to obtain the glass transition temperature Tg; preparing a sample strip in the same way, and testing by adopting a Vicat softening point tester under the condition of 50 ℃/h (5 +/-0.5 ℃/6min) to obtain the Vicat softening temperature VST; (2) the prepared ABS resin is molded and formed into a sample piece with the thickness of 3.2mm on a flat vulcanizing machine, then a sample strip with the thickness of 80mm multiplied by 10mm multiplied by 3.2mm is manufactured by a sample making machine, and the limit oxygen index is tested according to GB 2406-2009; (3) specimens of 125 mm. times.13 mm. times.3.2 mm were prepared using a sampling machine and tested for vertical burning ratings according to GB/T2408-2008. The data obtained are shown in Table 1.
Table 1:
Claims (10)
1. a modified ABS resin with good heat resistance and flame retardance is characterized in that:
the modified ABS resin consists of a continuous phase and a dispersed phase;
the continuous phase is styrene-acrylonitrile copolymer;
the dispersed phase is composite powder with a three-layer structure, wherein the inner layer is silicon dioxide, the middle layer is polybutadiene, the outer layer is silicon dioxide doped terpolymer, the inner layer and the middle layer are combined through a coupling agent, and the middle layer and the outer layer are combined in a graft copolymerization mode; the terpolymer is a styrene-acrylonitrile-bis (3-maleimidophenyl) phenyl phosphine oxide copolymer.
2. A preparation method of modified ABS resin with good heat resistance and flame retardance is characterized by comprising the following specific steps:
(1) adding dodecylbenzene sulfonic acid, hydroxyl silicone oil and a coupling agent into the silica sol, and carrying out ultrasonic treatment for 20-30 min to obtain modified silica sol;
(2) adding modified silica sol, disproportionated rosin soap, sodium dodecyl benzene sulfonate and persulfate initiator into deionized water, introducing nitrogen to remove air, vacuumizing, adding butadiene, heating to 40-45 ℃ for reaction, supplementing disproportionated rosin soap after reacting for 18-20 h, continuing to react for 12-15 h, supplementing disproportionated rosin soap again, continuing to react for 8-10 h, and naturally cooling to obtain silicon dioxide-polybutadiene composite latex;
(3) adding glucose, sodium pyrophosphate and ferrous sulfate into deionized water, completely dissolving, adding potassium hydroxide, rosin acid soap, silica-polybutadiene composite latex and silica sol, introducing nitrogen to remove air, heating to 60-65 ℃, then adding styrene, acrylonitrile, bis (3-maleimidophenyl) phenylphosphine oxide and cumene hydroperoxide, reacting for 1-1.5 h, supplementing glucose, sodium pyrophosphate, ferrous sulfate and cumene hydroperoxide, heating to 80-85 ℃, continuing to react for 3-3.5 h, cooling to 60-65 ℃, adding an antioxidant, stirring for 30-40 min, discharging, stirring with magnesium sulfate solution to demulsify, curing, filtering, and drying to obtain composite powder;
(4) and adding the composite powder and the styrene-acrylonitrile copolymer into a mixing roll for mixing, cooling and discharging to obtain the modified ABS resin with good heat resistance and flame retardance.
3. The method for preparing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein the method comprises the steps of: the silica content of the silica sol is 30 wt%; the hydroxyl content of the hydroxyl silicone oil is 6%; the coupling agent is one of kh-550, kh-560, kh-570 and kh-792.
4. The method for preparing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein the method comprises the steps of: in the step (1), the raw materials comprise, by weight, 100 parts of silica sol, 0.1-0.15 part of dodecylbenzene sulfonic acid, 0.5-1 part of hydroxyl silicone oil and 0.5-0.7 part of coupling agent.
5. The method for producing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein: in the step (2), the raw materials comprise, by weight, 50 parts of deionized water, 50 parts of modified silica sol, 1-1.2 parts of disproportionated rosin soap, 0.1-0.2 part of sodium dodecyl benzene sulfonate, 0.1 part of persulfate initiator and 30 parts of butadiene.
6. The method for producing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein: in the step (2), the disproportionated rosin soap is added in three times, wherein the adding amount of the first time is 60 percent of the total amount, the adding amount of the second time is 30 percent of the total amount, and the adding amount of the third time is 10 percent of the total amount.
7. The method for preparing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein the method comprises the steps of: in the step (3), the raw materials comprise, by weight, 100 parts of deionized water, 0.2 part of glucose, 0.3 part of sodium pyrophosphate, 0.01-0.02 part of ferrous sulfate, 0.025 part of potassium hydroxide, 2-4 parts of rosin acid soap, 50 parts of silica-polybutadiene composite latex, 6-8 parts of silica sol, 12-15 parts of styrene, 5-7 parts of acrylonitrile, 3-4 parts of bis (3-maleimidophenyl) phenyl phosphine oxide, 0.25-0.3 part of cumene hydroperoxide and 0.01-0.02 part of antioxidant.
8. The method for producing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein: in the step (3), glucose, sodium pyrophosphate, ferrous sulfate and cumene hydroperoxide are added in two times; the first adding amount of glucose, sodium pyrophosphate and ferrous sulfate is 75% of the total amount, and the second adding amount is 25% of the total amount; the first addition amount of cumene hydroperoxide was 85% of the total amount, and the second addition amount was 15% of the total amount.
9. The method for producing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein: in the step (4), the raw materials comprise, by weight, 20-25 parts of composite powder and 100 parts of styrene-acrylonitrile copolymer; in the styrene-acrylonitrile copolymer, the molar ratio of styrene to acrylonitrile is 6: 4-7: 3.
10. The method for producing a modified ABS resin having excellent heat resistance and flame retardancy as claimed in claim 2, wherein: in the step (4), the mixing temperature is 180-190 ℃ and the mixing time is 5-10 min.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101037A (en) * | 1991-08-27 | 1992-03-31 | Virginia Tech Intellectual Properties, Inc. | Bis(maleimido) phenoxy phenylphosphine oxide |
| DE19914807C1 (en) * | 1999-03-31 | 2000-06-29 | Bollig & Kemper Gmbh & Co Kg | Multilayer coating system with soft-feel effect, e.g. for interior plastic parts in cars, comprises pigmented basecoat and pigmented soft-feel topcoat |
| CN1369511A (en) * | 2001-02-12 | 2002-09-18 | 上海绿纳化工材料技术有限公司 | Process for preparing hybridized substance with core-shell structre from organic high-molecular material and nano inorganic material |
| CN101115615A (en) * | 2005-02-08 | 2008-01-30 | 诺瓦化学公司 | Foamed sheet containing a styrenic copolymer |
| JP2008255269A (en) * | 2007-04-06 | 2008-10-23 | Unitika Ltd | Resin composition and molded article prepared by molding the same |
| CN102782035A (en) * | 2010-01-07 | 2012-11-14 | 莱恩化学有限责任公司 | Compositions with compatibilized silica, nitrile rubber, styrene butadiene rubber, elastomeric compounds, and/or recycled materials |
| CN104193994A (en) * | 2014-08-30 | 2014-12-10 | 海安南京大学高新技术研究院 | Flame-retardant heat-resistant bismaleimide resin and preparation method thereof |
| CN105492476A (en) * | 2013-06-28 | 2016-04-13 | 三菱丽阳株式会社 | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article |
| KR20160068681A (en) * | 2014-12-05 | 2016-06-15 | 주식회사 엘지화학 | Heat resistance resin and method for preparing the resin |
| CN107177190A (en) * | 2016-03-10 | 2017-09-19 | 台燿科技股份有限公司 | Resin composition and use thereof |
| CN109971175A (en) * | 2019-03-18 | 2019-07-05 | 苏州生益科技有限公司 | Modified maleimide resin combination and its prepreg and laminate of preparation |
| CN109983046A (en) * | 2017-10-27 | 2019-07-05 | 株式会社Lg化学 | Graft copolymer, the thermoplastic resin composition comprising graft copolymer and thermoplastic resin composition preparation method |
-
2021
- 2021-05-26 CN CN202110580778.4A patent/CN113174111B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101037A (en) * | 1991-08-27 | 1992-03-31 | Virginia Tech Intellectual Properties, Inc. | Bis(maleimido) phenoxy phenylphosphine oxide |
| DE19914807C1 (en) * | 1999-03-31 | 2000-06-29 | Bollig & Kemper Gmbh & Co Kg | Multilayer coating system with soft-feel effect, e.g. for interior plastic parts in cars, comprises pigmented basecoat and pigmented soft-feel topcoat |
| CN1369511A (en) * | 2001-02-12 | 2002-09-18 | 上海绿纳化工材料技术有限公司 | Process for preparing hybridized substance with core-shell structre from organic high-molecular material and nano inorganic material |
| CN101115615A (en) * | 2005-02-08 | 2008-01-30 | 诺瓦化学公司 | Foamed sheet containing a styrenic copolymer |
| JP2008255269A (en) * | 2007-04-06 | 2008-10-23 | Unitika Ltd | Resin composition and molded article prepared by molding the same |
| CN102782035A (en) * | 2010-01-07 | 2012-11-14 | 莱恩化学有限责任公司 | Compositions with compatibilized silica, nitrile rubber, styrene butadiene rubber, elastomeric compounds, and/or recycled materials |
| CN105492476A (en) * | 2013-06-28 | 2016-04-13 | 三菱丽阳株式会社 | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article |
| CN104193994A (en) * | 2014-08-30 | 2014-12-10 | 海安南京大学高新技术研究院 | Flame-retardant heat-resistant bismaleimide resin and preparation method thereof |
| KR20160068681A (en) * | 2014-12-05 | 2016-06-15 | 주식회사 엘지화학 | Heat resistance resin and method for preparing the resin |
| CN107177190A (en) * | 2016-03-10 | 2017-09-19 | 台燿科技股份有限公司 | Resin composition and use thereof |
| CN109983046A (en) * | 2017-10-27 | 2019-07-05 | 株式会社Lg化学 | Graft copolymer, the thermoplastic resin composition comprising graft copolymer and thermoplastic resin composition preparation method |
| CN109971175A (en) * | 2019-03-18 | 2019-07-05 | 苏州生益科技有限公司 | Modified maleimide resin combination and its prepreg and laminate of preparation |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis of a novel organic-inorganic hybrid mesoporous silica and its flame retardancy application in PC/ABS;wei ping 等;《POLYMER DEGRADATION AND STABILITY》;20130531;第98卷(第5期);第1022-1029页 * |
| 无卤阻燃ABS体系的性能;沈惠玲;《天津科技大学学报》;20131231;第28卷(第6期);第28-31页 * |
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