CN114106481A - Toughened polystyrene filling master batch and preparation method thereof - Google Patents
Toughened polystyrene filling master batch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a toughened polystyrene filling master batch and a preparation method thereof, wherein the polystyrene filling master batch comprises the following raw materials in parts by weight: 80-100 parts of modified polystyrene, 1-3 parts of plasticizer, 10-15 parts of flame retardant, 1-3 parts of anti-aging agent and 8-10 parts of graphene; the intermediate 5 is processed to obtain an intermediate 6, styrene and 4-vinylbenzyl chloride are polymerized to obtain pre-modified polystyrene, the pre-modified polystyrene reacts with the intermediate 6, so that chlorine atom sites on the pre-modified polystyrene react with alcoholic hydroxyl groups on the intermediate 6 to form cross-linked macromolecules, and the modified polystyrene is prepared.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a toughened polystyrene filling master batch and a preparation method thereof.
Background
Polystyrene resin is divided into general polystyrene (GPPS) and High Impact Polystyrene (HIPS), and is widely applied to the fields of electric appliance shells, daily necessities, toys, packaging materials and the like, along with the continuous development of the society, petroleum resources are more and more in short supply, the recycling of plastics is an inevitable trend, the impact performance of the polystyrene material is greatly reduced after being processed for many times, a certain amount of toughening agent must be added to meet the requirement, the traditional toughening agent has a general toughening effect, and the toughening component is separated out after being used for a long time, so that the strength of the polystyrene is reduced again, the polystyrene is easy to be damaged or broken in the using process, and the normal use and the attractiveness of plastic products are seriously influenced;
in view of the technical problem in this respect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a toughened polystyrene filling master batch and a preparation method thereof, which solve the problems that the toughness of polystyrene is low at the present stage and the polystyrene is easy to damage under the action of external force in the using process by modifying the polystyrene.
The purpose of the invention can be realized by the following technical scheme:
the toughened polystyrene filling master batch comprises the following raw materials in parts by weight: 80-100 parts of modified polystyrene, 1-3 parts of plasticizer, 10-15 parts of flame retardant, 1-3 parts of anti-aging agent and 8-10 parts of graphene;
the toughened polystyrene filling master batch comprises the following steps:
step S1: adding the modified polystyrene, the plasticizer, the flame retardant, the anti-aging agent and the graphene into a high-speed mixer, and mixing for 15-20min at the rotating speed of 600-800r/min to obtain a premix;
step S2: pouring the premix into a hot mixer, discharging to a cold mixer when the premix is hot mixed to 180 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 190-200 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: and cutting the materials into granules in a first area of 200 ℃, a second area of 215 ℃, a third area of 220 ℃, a fourth area of 225 ℃, a fifth area of 230 ℃ and a machine head of 225 ℃ to obtain the toughened polystyrene filling master batch.
Furthermore, the plasticizer is one or more of diisooctyl sebacate, dioctyl adipate and di-n-butyl adipate which are mixed in any proportion, the flame retardant is one or more of antimony trioxide, magnesium hydroxide and aluminum hydroxide which are mixed in any proportion, and the anti-aging agent is one or more of secondary diarylamine, p-phenylenediamine and diphenylamine which are mixed in any proportion.
Further, the modified polystyrene is prepared by the following steps:
step A1: adding nitrobenzene into a reaction kettle, stirring and adding acetone under the conditions that the rotation speed is 150-200r/min and the temperature is 13-18 ℃, stirring for 10-15min, adding concentrated sulfuric acid, continuously reacting for 2-3h under the condition that the temperature is 18-20 ℃, cooling to 0 ℃, preserving heat for 30-40min, filtering to remove filtrate, adding filter cakes, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 6-8h under the condition that the temperature is 80-90 ℃ to prepare an intermediate 1;
the reaction process is as follows:
step A2: dissolving the intermediate 1 in N, N-dimethylformamide, adding cuprous chloride, stirring and introducing hydrogen under the conditions of a rotation speed of 150-;
the reaction process is as follows:
step A3: uniformly mixing the intermediate 4, methyl eleostearate, toluene and sodium methoxide, carrying out reflux reaction for 10-15h at the rotation speed of 150-;
the reaction process is as follows:
step A4: uniformly mixing styrene, 4-vinylbenzyl chloride, azodiisobutyronitrile, dibenzoyl peroxide, polyvinyl alcohol and sodium chloride solution, stirring at the rotation speed of 200-300r/min and the temperature of 20-25 ℃, heating to the temperature of 65-70 ℃, reacting for 2-3h, heating to the temperature of 90-95 ℃, reacting for 15-20h to obtain pre-modified polystyrene, dissolving the pre-modified polystyrene in N, N-dimethylformamide, adding an intermediate 6 and sodium hydroxide, and reacting for 10-15h at the rotation speed of 200-300r/min and the temperature of 40-50 ℃ to obtain the modified polystyrene.
The reaction process is as follows:
further, the dosage ratio of nitrobenzene, acetone and concentrated sulfuric acid in the step A1 is 0.1mol:0.08mol:6mL, the mass fraction of the concentrated sulfuric acid is 98%, and the dosage ratio of filter cake, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride is 0.1mol:0.15mol:0.2g:200 mL.
Further, the molar ratio of the intermediate 1 to the cuprous chloride in the step A2 is 2:1, the molar ratio of the intermediate 2 to the maleic anhydride is 1:2, and the molar ratio of the intermediate 3 to the p-propenyl benzyl alcohol is 1: 2.
Further, the using amount ratio of the intermediate 4, methyl eleostearate, toluene and sodium methoxide in the step A3 is 1mmol:2.2mmol:10mL:0.025g, and the using amount ratio of the intermediate 5, potassium carbonate and tetraethylammonium bromide is 3.8g:8.5g:1.5 g.
Further, the mass ratio of the styrene to the 4-vinylbenzyl chloride in the step A4 is 3:1, the mass ratio of the azodiisobutyronitrile to the styrene to the 4-vinylbenzyl chloride is 1.5%, the mass ratio of the dibenzoyl peroxide to the styrene to the 4-vinylbenzyl chloride is 2%, and the mass ratio of the pre-modified polystyrene to the intermediate 6 to the sodium hydroxide is 3:1: 10.
The invention has the following beneficial effects:
the invention prepares modified polystyrene in the process of preparing a toughened polystyrene filling master batch, the modified polystyrene takes nitrobenzene and acetone as raw materials, after reaction, N-bromosuccinimide is used for processing to prepare an intermediate 1, the intermediate 1 is subjected to reduction reaction with hydrogen under the action of cuprous chloride to convert nitro on the intermediate 1 into amino to prepare an intermediate 2, the intermediate 2 is subjected to reaction with maleic anhydride to prepare an intermediate 3, the intermediate 3 is subjected to reaction with p-propenyl benzyl alcohol to prepare an intermediate 4, the intermediate 4 is subjected to ester exchange reaction with methyl eleostearate to prepare an intermediate 5, the intermediate 5 is processed to prepare an intermediate 6, styrene and 4-vinylbenzyl chloride are polymerized to prepare pre-modified polystyrene, the pre-modified polystyrene is reacted with the intermediate 6 to react chlorine atom sites on the pre-modified polystyrene with alcoholic hydroxyl on the intermediate 6, and forming a cross-linked polymer to prepare modified polystyrene, wherein the molecules of the modified polystyrene contain a large amount of flexible aliphatic long chains, and the cross-linked chains are bismaleimide structures which have good toughness and are compounded with graphene, so that the toughness of the prepared polystyrene filling master batch is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The toughened polystyrene filling master batch comprises the following raw materials in parts by weight: 80 parts of modified polystyrene, 1 part of diisooctyl sebacate, 10 parts of antimony trioxide, 1 part of secondary diarylamine and 8 parts of graphene;
the toughened polystyrene filling master batch comprises the following steps:
step S1: adding modified polystyrene, diisooctyl sebacate, antimony trioxide, an anti-aging agent and graphene into a high-speed mixer, and mixing at the rotating speed of 600r/min for 15min to obtain a premix;
step S2: pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is 160 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 190 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: and cutting the materials into granules in a first area of 200 ℃, a second area of 215 ℃, a third area of 220 ℃, a fourth area of 225 ℃, a fifth area of 230 ℃ and a machine head of 225 ℃ to obtain the toughened polystyrene filling master batch.
The modified polystyrene is prepared by the following steps:
step A1: adding nitrobenzene into a reaction kettle, stirring and adding acetone under the conditions that the rotating speed is 150r/min and the temperature is 13 ℃, stirring for 10min, adding concentrated sulfuric acid, continuously reacting at 18 ℃ for 2h, cooling to 0 ℃, preserving heat for 30min, filtering to remove filtrate, adding filter cakes, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting at 80 ℃ for 6h to prepare an intermediate 1;
step A2: dissolving the intermediate 1 in N, N-dimethylformamide, adding cuprous chloride, stirring and introducing hydrogen under the conditions of a rotation speed of 150r/min, a temperature of 110 ℃ and illumination for reacting for 1h to prepare an intermediate 2, uniformly mixing the intermediate 2, maleic anhydride and toluene, reacting for 3h under the conditions of a rotation speed of 200r/min and a temperature of 110 ℃ to prepare an intermediate 3, uniformly mixing the intermediate 3, p-propenyl benzyl alcohol, Raney's nickel and N, N-dimethylformamide, and performing reflux reaction for 15h under the conditions of a rotation speed of 200r/min and a temperature of 130 ℃ to prepare an intermediate 4;
step A3: uniformly mixing the intermediate 4, methyl eleostearate, toluene and sodium methoxide, carrying out reflux reaction for 10 hours at the rotation speed of 150r/min and the temperature of 150 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in N, N-dimethylformamide, adding potassium carbonate and tetraethylammonium bromide, and carrying out reflux reaction for 2 hours at the temperature of 155 ℃ to obtain an intermediate 6;
step A4: uniformly mixing styrene, 4-vinylbenzyl chloride, azodiisobutyronitrile, dibenzoyl peroxide, polyvinyl alcohol and a sodium chloride solution, stirring at the rotation speed of 200r/min and the temperature of 20 ℃ for 30min, heating to the temperature of 65 ℃, reacting for 2h, heating to the temperature of 90 ℃, reacting for 15h to obtain pre-modified polystyrene, dissolving the pre-modified polystyrene in N, N-dimethylformamide, adding an intermediate 6 and sodium hydroxide, and reacting at the rotation speed of 200r/min and the temperature of 40 ℃ for 10h to obtain the modified polystyrene.
Example 2
The toughened polystyrene filling master batch comprises the following raw materials in parts by weight: 90 parts of modified polystyrene, 2 parts of dioctyl adipate, 13 parts of magnesium hydroxide, 2 parts of p-phenylenediamine and 9 parts of graphene;
the toughened polystyrene filling master batch comprises the following steps:
step S1: adding modified polystyrene, dioctyl adipate, magnesium hydroxide, p-phenylenediamine and graphene into a high-speed mixer, and mixing for 18min at the rotating speed of 900r/min to obtain a premix;
step S2: pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is 170 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 195 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: and cutting the materials into granules in a first area of 200 ℃, a second area of 215 ℃, a third area of 220 ℃, a fourth area of 225 ℃, a fifth area of 230 ℃ and a machine head of 225 ℃ to obtain the toughened polystyrene filling master batch.
The modified polystyrene is prepared by the following steps:
step A1: adding nitrobenzene into a reaction kettle, stirring and adding acetone under the conditions that the rotating speed is 180r/min and the temperature is 15 ℃, stirring for 13min, adding concentrated sulfuric acid, continuously reacting for 2.5h under the condition that the temperature is 19 ℃, cooling to 0 ℃, preserving the temperature for 35min, filtering to remove filtrate, adding filter cakes, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 7h under the condition that the temperature is 85 ℃ to prepare an intermediate 1;
step A2: dissolving the intermediate 1 in N, N-dimethylformamide, adding cuprous chloride, stirring and introducing hydrogen under the conditions of a rotation speed of 180r/min, a temperature of 115 ℃ and illumination for reacting for 1.3h to obtain an intermediate 2, uniformly mixing the intermediate 2, maleic anhydride and toluene, reacting for 4h under the conditions of a rotation speed of 300r/min and a temperature of 115 ℃ to obtain an intermediate 3, uniformly mixing the intermediate 3, p-propenyl benzyl alcohol, raney nickel and N, N-dimethylformamide, and performing reflux reaction for 18h under the conditions of a rotation speed of 200r/min and a temperature of 135 ℃ to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 4, methyl eleostearate, toluene and sodium methoxide, carrying out reflux reaction for 13 hours at the rotation speed of 180r/min and the temperature of 155 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in N, N-dimethylformamide, adding potassium carbonate and tetraethylammonium bromide, and carrying out reflux reaction for 2.5 hours at the temperature of 158 ℃ to obtain an intermediate 6;
step A4: uniformly mixing styrene, 4-vinylbenzyl chloride, azodiisobutyronitrile, dibenzoyl peroxide, polyvinyl alcohol and a sodium chloride solution, stirring at the rotation speed of 300r/min and the temperature of 23 ℃ for 35min, heating to the temperature of 68 ℃, reacting for 2.5h, heating to the temperature of 93 ℃, reacting for 18h to obtain pre-modified polystyrene, dissolving the pre-modified polystyrene in N, N-dimethylformamide, adding an intermediate 6 and sodium hydroxide, and reacting at the rotation speed of 200r/min and the temperature of 45 ℃ for 13h to obtain the modified polystyrene.
Example 3
The toughened polystyrene filling master batch comprises the following raw materials in parts by weight: 100 parts of modified polystyrene, 3 parts of plasticizer, 15 parts of flame retardant, 3 parts of diphenylamine and 10 parts of graphene;
the toughened polystyrene filling master batch comprises the following steps:
step S1: adding modified polystyrene, di-n-butyl adipate, aluminum hydroxide, diphenylamine and graphene into a high-speed mixer, and mixing at the rotating speed of 800r/min for 20min to obtain a premix;
step S2: pouring the premix into a hot mixer, discharging to a cold mixer when the temperature of the premix is up to 180 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 200 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: and cutting the materials into granules in a first area of 200 ℃, a second area of 215 ℃, a third area of 220 ℃, a fourth area of 225 ℃, a fifth area of 230 ℃ and a machine head of 225 ℃ to obtain the toughened polystyrene filling master batch.
The modified polystyrene is prepared by the following steps:
step A1: adding nitrobenzene into a reaction kettle, stirring and adding acetone under the conditions that the rotating speed is 200r/min and the temperature is 18 ℃, stirring for 15min, adding concentrated sulfuric acid, continuously reacting for 3h under the condition that the temperature is 20 ℃, cooling to 0 ℃, preserving the temperature for 40min, filtering to remove filtrate, adding filter cakes, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, and reacting for 8h under the condition that the temperature is 90 ℃ to prepare an intermediate 1;
step A2: dissolving the intermediate 1 in N, N-dimethylformamide, adding cuprous chloride, stirring and introducing hydrogen under the conditions of a rotation speed of 200r/min, a temperature of 120 ℃ and illumination for reacting for 1.5 hours to prepare an intermediate 2, uniformly mixing the intermediate 2, maleic anhydride and toluene, reacting for 5 hours under the conditions of a rotation speed of 300r/min and a temperature of 120 ℃ to prepare an intermediate 3, uniformly mixing the intermediate 3, p-propenyl benzyl alcohol, Raney's nickel and N, N-dimethylformamide, and performing reflux reaction for 20 hours under the conditions of a rotation speed of 300r/min and a temperature of 140 ℃ to prepare an intermediate 4;
step A3: uniformly mixing the intermediate 4, methyl eleostearate, toluene and sodium methoxide, carrying out reflux reaction for 15 hours at the rotation speed of 200r/min and the temperature of 160 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in N, N-dimethylformamide, adding potassium carbonate and tetraethylammonium bromide, and carrying out reflux reaction for 3 hours at the temperature of 160 ℃ to obtain an intermediate 6;
step A4: uniformly mixing styrene, 4-vinylbenzyl chloride, azodiisobutyronitrile, dibenzoyl peroxide, polyvinyl alcohol and a sodium chloride solution, stirring at the rotation speed of 300r/min and the temperature of 25 ℃ for 40min, heating to the temperature of 70 ℃, reacting for 3h, heating to the temperature of 95 ℃, reacting for 20h to obtain pre-modified polystyrene, dissolving the pre-modified polystyrene in N, N-dimethylformamide, adding an intermediate 6 and sodium hydroxide, and reacting at the rotation speed of 300r/min and the temperature of 50 ℃ for 15h to obtain the modified polystyrene.
Comparative example 1
This comparative example uses polystyrene instead of modified polystyrene, in comparison with example 1, and the rest of the procedure is the same.
Comparative example 2
This patent is a polystyrene disclosed in chinese patent CN 102627812A.
Comparative example 3
This patent is a polystyrene disclosed in chinese patent CN 106751086A.
The results of testing the flexural strength and flexural modulus of the polystyrenes prepared in examples 1-3 and comparative examples 1-3 according to the GB/T3682-;
as can be seen from the above table, the flexural strength of the polystyrene prepared in examples 1-3 is 263MPa, the flexural modulus is 8035 8050MPa, the tensile strength is 33.5-34.1MPa, and the elongation at break is 181.8-183.3%, which are much higher than the polystyrene prepared in comparative examples 1-3, indicating that the polystyrene prepared in the invention has excellent toughness and mechanical strength.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A toughened polystyrene filling master batch is characterized in that: the feed comprises the following raw materials in parts by weight: 80-100 parts of modified polystyrene, 1-3 parts of plasticizer, 10-15 parts of flame retardant, 1-3 parts of anti-aging agent and 8-10 parts of graphene;
the modified polystyrene is prepared by the following steps:
step A1: adding nitrobenzene into a reaction kettle, stirring, adding acetone, stirring, adding concentrated sulfuric acid, reacting, cooling, preserving heat, filtering to remove filtrate, and mixing and reacting a filter cake, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride to prepare an intermediate 1;
step A2: dissolving the intermediate 1 in N, N-dimethylformamide, adding cuprous chloride, stirring, introducing hydrogen, reacting to obtain an intermediate 2, mixing the intermediate 2, maleic anhydride and toluene for reaction to obtain an intermediate 3, and mixing the intermediate 3, p-propenyl benzyl alcohol, Raney nickel and N, N-dimethylformamide for reflux reaction to obtain an intermediate 4;
step A3: mixing the intermediate 4, methyl eleostearate, toluene and sodium methoxide for reflux reaction to prepare an intermediate 5, dissolving the intermediate 5 in N, N-dimethylformamide, adding potassium carbonate and tetraethylammonium bromide, and performing reflux reaction to prepare an intermediate 6;
step A4: uniformly mixing styrene, 4-vinylbenzyl chloride, azodiisobutyronitrile, dibenzoyl peroxide, polyvinyl alcohol and a sodium chloride solution, heating for reaction again to obtain pre-modified polystyrene, dissolving the pre-modified polystyrene in N, N-dimethylformamide, and adding the intermediate 6 and sodium hydroxide for reaction to obtain the modified polystyrene.
2. The toughened polystyrene filling masterbatch as claimed in claim 1, wherein: the plasticizer is one or more of diisooctyl sebacate, dioctyl adipate and di-n-butyl adipate which are mixed in any proportion, the flame retardant is one or more of antimony trioxide, magnesium hydroxide and aluminum hydroxide which are mixed in any proportion, and the anti-aging agent is one or more of secondary diarylamine, p-phenylenediamine and diphenylamine which are mixed in any proportion.
3. The toughened polystyrene filling masterbatch as claimed in claim 1, wherein: the dosage ratio of the nitrobenzene, the acetone and the concentrated sulfuric acid in the step A1 is 0.1mol:0.08mol:6mL, the mass fraction of the concentrated sulfuric acid is 98%, and the dosage ratio of the filter cake, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.1mol:0.15mol:0.2g:200 mL.
4. The toughened polystyrene filling masterbatch as claimed in claim 1, wherein: the molar ratio of the intermediate 1 to the cuprous chloride in the step A2 is 2:1, the molar ratio of the intermediate 2 to the maleic anhydride is 1:2, and the molar ratio of the intermediate 3 to the p-propenyl benzyl alcohol is 1: 2.
5. The toughened polystyrene filling masterbatch as claimed in claim 1, wherein: the dosage ratio of the intermediate 4, the methyl eleostearate, the toluene and the sodium methoxide in the step A3 is 1mmol:2.2mmol:10mL:0.025g, and the dosage ratio of the intermediate 5, the potassium carbonate and the tetraethylammonium bromide is 3.8g:8.5g:1.5 g.
6. The toughened polystyrene filling masterbatch as claimed in claim 1, wherein: the mass ratio of the styrene to the 4-vinylbenzyl chloride in the step A4 is 3:1, the mass ratio of the azodiisobutyronitrile to the styrene to the 4-vinylbenzyl chloride is 1.5%, the mass ratio of the dibenzoyl peroxide to the styrene to the 4-vinylbenzyl chloride is 2%, and the mass ratio of the pre-modified polystyrene to the intermediate 6 to the sodium hydroxide is 3:1: 10.
7. The method for preparing the toughened polystyrene filling master batch as claimed in claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
step S1: adding the modified polystyrene, the plasticizer, the flame retardant, the anti-aging agent and the graphene into a high-speed mixer, and mixing for 15-20min at the rotating speed of 600-800r/min to obtain a premix;
step S2: pouring the premix into a hot mixer, discharging to a cold mixer when the premix is hot mixed to 180 ℃, and then starting cold mixing to room temperature to obtain dry mixture; melting and blending the dry mixture at 190-200 ℃, granulating after passing through a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature of each area of the double-screw extruder is set as follows: and cutting the materials into granules in a first area of 200 ℃, a second area of 215 ℃, a third area of 220 ℃, a fourth area of 225 ℃, a fifth area of 230 ℃ and a machine head of 225 ℃ to obtain the toughened polystyrene filling master batch.
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Application publication date: 20220301 |