CN111117129A - Blow molding PMMA/ASA resin with ultrahigh melt strength and preparation method thereof - Google Patents

Blow molding PMMA/ASA resin with ultrahigh melt strength and preparation method thereof Download PDF

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CN111117129A
CN111117129A CN201911337994.5A CN201911337994A CN111117129A CN 111117129 A CN111117129 A CN 111117129A CN 201911337994 A CN201911337994 A CN 201911337994A CN 111117129 A CN111117129 A CN 111117129A
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resin
pmma
parts
melt strength
molecular weight
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董雨生
纪效均
蔡青
周文
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Shanghai Pret Material Technology Co Ltd
Chongqing Pret New Materials Co Ltd
Shanghai Pret Chemical New Materials Co Ltd
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Shanghai Pret Material Technology Co Ltd
Chongqing Pret New Materials Co Ltd
Shanghai Pret Chemical New Materials Co Ltd
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Priority to CN201911337994.5A priority Critical patent/CN111117129A/en
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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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a blow molding PMMA/ASA resin with ultrahigh melt strength and a preparation method thereof, wherein the raw materials comprise the following components in parts by weight: 15-35 parts of ASA rubber powder, 20-40 parts of AS resin, 40-60 parts of PMMA resin, 2.0-10.0 parts of compatilizer, 0.05-2.0 parts of processing aid, 0.05-2.0 parts of weather-resistant aid and 0.5-2.5 parts of black master batch. The raw materials are premixed in a high-speed mixer, and then the premixed material is extruded by a double-screw extruder to obtain the blow molding PMMA/ASA resin composition with ultrahigh melt strength. The PMMA/ASA resin provided by the invention has high melt strength, good anti-sagging performance of blow-molded parison, excellent weather resistance and scratch resistance, is very suitable for blow-molded parts such as automobile empennages, spoilers and the like, and has a spraying-free high bright black effect.

Description

Blow molding PMMA/ASA resin with ultrahigh melt strength and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer material processing, in particular to a blow molding PMMA/ASA resin composition with ultrahigh melt strength and a preparation method thereof.
Background
The PMMA/ASA resin has excellent weather resistance, impact resistance and colorability, and can obtain a spraying-free appearance with high brilliant black and Piano black painting effect by dyeing with a proper amount of coloring agent. The PMMA/ASA resin can be prepared into a spraying-free high-brightness black product by a plurality of forming methods such as extrusion, injection molding, blow molding and the like, so the PMMA/ASA resin is widely applied to the fields of automobiles, electronic appliances, light industry and household appliances and the like, and can replace paint to realize the substantial cost reduction.
In recent years, with the promotion of cost reduction of automobiles and the increase of the control force of the country on environmental pollution, automobile empennages, spoilers and the like generally adopt ABS resin blow-molded exterior trimming parts, and because the exterior trimming parts need a two-step paint spraying process to make up the defects of weather resistance, glossiness and blackness of the ABS resin, PMMA/ASA is gradually selected as a substitute material. However, the conventional PMMA/ASA resin has low melt strength, so that the parison is easy to sag during blow molding to cause uneven wall thickness of a product, and better blow molding is difficult to perform. CN109851968A reports that the melt strength of the material is increased by adding a cross-linking agent, but the cross-linking reaction is not easy to control, and the cross-linking reaction also affects the glossiness of PMMA/ASA resin.
Disclosure of Invention
The invention aims to provide a blow-molding PMMA/ASA resin with ultrahigh melt strength and a preparation method thereof, which are used for solving the problems that the existing PMMA/ASA resin is low in melt strength and a blow-molding parison sags.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the blow molding PMMA/ASA resin with ultrahigh melt strength comprises the following raw materials in parts by weight:
Figure BDA0002331481820000011
Figure BDA0002331481820000021
in the above PMMA/ASA resin:
the weight-average molecular weight of the ASA rubber powder is 100,000-500,000g/mol, the content of the acrylate rubber is 40-60%, and the number-average particle diameter of the rubber is 100-800 nm.
The weight average molecular weight of the AS resin is 1000,000-8000,000g/mol, and the AS resin with high molecular weight can obviously provide the melt strength of the composition. In view of better processability of the resin, it is preferably 3000,000-5000,000 g/mol.
The PMMA resin has a weight average molecular weight of 100,000-200,000 g/mol. If the molecular weight is too low, the melt of the composition becomes brittle and is not easy to blow; too high a molecular weight affects its processability.
The compatilizer is at least one of St/MAH-g-MMA graft copolymer (styrene/maleic anhydride grafted methyl methacrylate copolymer) and St/AA-g-MMA graft copolymer (styrene/acrylic acid grafted methyl methacrylate copolymer), wherein the weight average molecular weight of the St/MAH-g-MMA graft copolymer is 40,000-150,000g/mol, and the weight average molecular weight of the St/AA-g-MMA graft copolymer is 40,000-150,000 g/mol.
In the St/MAH-g-MMA graft copolymer, the molar ratio of St (styrene), MAH (maleic anhydride) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40.
In the St/AA-g-MMA graft copolymer, the molar ratio of St (styrene), AA (acrylate) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40.
The processing aid comprises a lubricant and a release agent. The lubricant is pentaerythritol stearate or ethylene bis-stearamide, and the release agent is a silicone release agent.
The weather-resistant auxiliary agent comprises an antioxidant and a light-resistant aging auxiliary agent. The antioxidant is hindered phenol antioxidant or phosphite antioxidant, and the light-resistant aging auxiliary agent is one or more of salicylate, benzophenone, UV absorbent of benzyl triazole and hindered amine free radical scavenger.
The black master batch is a high-concentration black master batch prepared by adding dye black into AS serving AS a matrix.
The invention also provides a preparation method of the blow molding PMMA/ASA with ultrahigh melt strength, which comprises the following steps:
(1) preparing the materials according to the components and the contents;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the blow-molding PMMA/ASA resin composition with ultrahigh melt strength.
Compared with the prior art, the invention has the following advantages:
the AS resin with high molecular weight is selected from the raw material aspect, and the prepared PMMA/ASA resin with ultrahigh melt strength has stable and controllable performance while the high melt strength of the system is ensured; the St/MAH-g-MMA graft copolymer (styrene/maleic anhydride grafted methyl methacrylate copolymer) and the St/AA-g-MMA graft copolymer (styrene/acrylic acid grafted methyl methacrylate copolymer) with higher grafting rates are selected as the compatilizer, so that the compatibility of PMMA and ASA components can be obviously improved, and the melt strength of the formed in-situ composite copolymer can be further improved. The preparation method and the technical process of the invention are simple, the cost is low, the melt strength is high and stable in the processing process, and the invention is very suitable for industrial production.
Detailed Description
The following examples and comparative examples use raw material information:
the weight-average molecular weight of the ASA rubber powder is 100,000-500,000g/mol, the content of the acrylate rubber is 40-60%, and the number-average particle size of the rubber is 100-800 nm;
the weight average molecular weight of the AS resin is 1000,000-8000,000g/mol, preferably 3000,000-5000,000 g/mol;
the weight average molecular weight of the PMMA resin is 100,000-200,000 g/mol;
the weight average molecular weight of the St/MAH-g-MMA graft copolymer (styrene/maleic anhydride grafted methyl methacrylate copolymer) is 40,000-150,000g/mol, and the molar ratio of St (styrene), MAH (maleic anhydride) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40;
the weight average molecular weight of the St/AA-g-MMA graft copolymer (styrene/acrylic acid grafted methyl methacrylate copolymer) is 40,000-150,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40
The lubricant is pentaerythritol stearate or ethylene bis-stearamide, the release agent is a silicone release agent, the antioxidant is a hindered phenol antioxidant or phosphite antioxidant, and the light-resistant aging auxiliary agent is one or more of salicylate, benzophenone, the benzyl triazole UV absorbent and hindered amine free radical scavenger.
Performance evaluation method and test standard thereof
The PMMA/ASA resin composition was subjected to a conventional mechanical property test, and the surface of the blow-molded article was observed, and the gloss and L value were measured to evaluate the blackness and brightness of the surface, and the results are shown in Table 1.
Charpy notched impact strength: according to ISO 179-1: 2010(E) standard test, impact energy 4J;
vicat softening temperature: tested according to ISO 306:2013(E) Standard B50;
bending strength: testing according to ISO 178:2010(E) standard, wherein the testing speed is 2 mm/min;
flexural modulus: testing according to ISO 178:2010(E) standard, wherein the testing speed is 2 mm/min;
melt flow rate: tested according to ISO 1133-1:2011(E) Standard B, at 220 ℃ 10 kg;
gloss: the 60 ° gloss of the injection molded plaques was tested using a cunica minolta Multigloss 268 gloss instrument as tested by ASTM D2457.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 20 parts of AS resin, 60 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 2
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 35 parts of ASA resin, 20 parts of AS resin, 40 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin was 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 3
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 20 parts of ASA resin, 30 parts of AS resin, 45 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 4
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 40 parts of AS resin, 40 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 5
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 6
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 7
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is a mixture of St/MAH-g-MMA graft copolymer and St/AA-g-MMA graft copolymer, the weight average molecular weight of the compatilizer is 80,000g/mol, the molar ratio of St (styrene), MAH (maleic anhydride) and MMA (methyl methacrylate) in the polymer is 20:40:20, and the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer is 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 8
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 100,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 9
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 500,000g/mol, the content of acrylate rubber is 45%, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 10
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 1000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 11
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 7000, 000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 12
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 40,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 13
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 130,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 14
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 250:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 15
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer was 20:40: 40.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 16
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/MAH-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), St (maleic anhydride), MMA (methyl methacrylate) in the polymer is 100:25: 30.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Example 17
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 80:40: 30.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Comparative example 1
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 100,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 500,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Comparative example 2
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 15 parts of AS resin, 65 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 150,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Comparative example 3
The ultrahigh melt strength blow molding resin PMMA/ASA composition is prepared from the following raw materials in parts by weight: 15 parts of ASA resin, 25 parts of AS resin, 55 parts of PMMA resin, 4 parts of compatilizer, 0.1 part of processing aid, 0.1 part of weather-resistant aid and 1.0 part of black master batch.
In the raw materials, the weight-average molecular weight of the ASA resin is 300,000g/mol, the content of acrylate rubber is 45 percent, and the number-average particle diameter of the rubber is 150 nm; the weight average molecular weight of the AS resin is 5000,000 g/mol; the weight average molecular weight of the PMMA resin is 50,000 g/mol; the compatilizer is St/AA-g-MMA graft copolymer, and the weight average molecular weight of the compatilizer is 80,000 g/mol; the molar ratio of St (styrene), AA (acrylic acid) and MMA (methyl methacrylate) in the polymer was 20:40: 20.
(1) Premixing the raw materials in a high-speed mixer;
(2) and (2) melting and extruding the premix obtained in the step (1) through a double-screw extruder at the extrusion temperature of 180 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the blow-molded PMMA/ASA resin composition with ultrahigh melt strength.
Table 1: test data for examples 1-17 and comparative examples 1-3
Figure BDA0002331481820000131

Claims (10)

1. An ultrahigh melt strength blow molded PMMA/ASA resin characterized by: the feed comprises the following raw materials in parts by weight:
Figure 3
2. an ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the weight-average molecular weight of the ASA rubber powder is 100,000-500,000g/mol, the content of the acrylate rubber is 40-60%, and the number-average particle diameter of the rubber is 100-800 nm.
3. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the weight average molecular weight of the AS resin is 1000,000-8000,000g/mol, and the AS resin with high molecular weight can obviously provide the melt strength of the composition. In view of better processability of the resin, it is preferably 3000,000-5000,000 g/mol.
4. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the PMMA resin has a weight average molecular weight of 100,000-200,000 g/mol. If the molecular weight is too low, the melt of the composition becomes brittle and is not easy to blow; too high a molecular weight affects its processability.
5. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the compatilizer is at least one of St/MAH-g-MMA graft copolymer (styrene/maleic anhydride grafted methyl methacrylate copolymer) and St/AA-g-MMA graft copolymer (styrene/acrylic acid grafted methyl methacrylate copolymer), wherein the weight average molecular weight of the St/MAH-g-MMA graft copolymer is 40,000-150,000g/mol, and the weight average molecular weight of the St/AA-g-MMA graft copolymer is 40,000-150,000 g/mol.
6. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 5 wherein: in the St/MAH-g-MMA graft copolymer, the molar ratio of St (styrene), MAH (maleic anhydride) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40.
7. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 5 wherein: in the St/AA-g-MMA graft copolymer, the molar ratio of St (styrene), AA (acrylate) and MMA (methyl methacrylate) in the polymer is 20-300: 20-40.
8. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the processing aid comprises a lubricant and a release agent; the lubricant is pentaerythritol stearate or ethylene bis-stearamide, and the release agent is a silicone release agent.
9. An ultra-high melt strength blow molded PMMA/ASA resin as claimed in claim 1 wherein: the weather-resistant auxiliary agent comprises an antioxidant and a light-resistant aging auxiliary agent; the antioxidant is hindered phenol antioxidant or phosphite antioxidant, and the light-resistant aging auxiliary agent is one or more of salicylate, benzophenone, UV absorbent of benzyl triazole and hindered amine free radical scavenger; the black master batch is a high-concentration black master batch prepared by adding dye black into AS serving AS a matrix.
10. A process for the preparation of ultra high melt strength blow molded PMMA/ASA according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
(1) preparing the materials according to the components and the contents;
(2) premixing the raw materials in the step (1) in a high-speed mixer;
(3) and (3) melting and extruding the premix obtained in the step (2) through a double-screw extruder at the extrusion temperature of 180-250 ℃ and the screw rotating speed of 200-500 r/min, and cooling and granulating to obtain the blow-molding PMMA/ASA resin composition with ultrahigh melt strength.
CN201911337994.5A 2019-12-23 2019-12-23 Blow molding PMMA/ASA resin with ultrahigh melt strength and preparation method thereof Pending CN111117129A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690222A (en) * 2020-07-09 2020-09-22 东莞市奥能工程塑料有限公司 PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof
CN112552614A (en) * 2020-12-14 2021-03-26 武汉金发科技有限公司 High-gloss black scratch-resistant PMMA/ASA composite material and preparation method thereof
CN112608564A (en) * 2020-11-30 2021-04-06 金发科技股份有限公司 High-weather-resistance ASA material and preparation method and application thereof
CN113088013A (en) * 2021-05-20 2021-07-09 上海金山锦湖日丽塑料有限公司 UVC-resistant ASA resin composition and preparation method thereof
CN113121939A (en) * 2021-03-30 2021-07-16 柳州炜林纳新材料科技有限责任公司 Composite resin material, preparation method thereof and automobile part

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105175925A (en) * 2015-10-27 2015-12-23 上海锦湖日丽塑料有限公司 Ultrahigh melt strength blow-molded ABS resin composition and preparation method thereof
CN105504569A (en) * 2015-12-30 2016-04-20 上海普利特复合材料股份有限公司 Wear-resistant ASA/PMMA (acrylonitrile-styrene-acrylate/polymethylmethacrylate) blend material with high weather resistance and high gloss and preparation method thereof
CN109851968A (en) * 2018-12-28 2019-06-07 上海锦湖日丽塑料有限公司 A kind of superelevation melt strength blow molding resins composition and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105175925A (en) * 2015-10-27 2015-12-23 上海锦湖日丽塑料有限公司 Ultrahigh melt strength blow-molded ABS resin composition and preparation method thereof
CN105504569A (en) * 2015-12-30 2016-04-20 上海普利特复合材料股份有限公司 Wear-resistant ASA/PMMA (acrylonitrile-styrene-acrylate/polymethylmethacrylate) blend material with high weather resistance and high gloss and preparation method thereof
CN109851968A (en) * 2018-12-28 2019-06-07 上海锦湖日丽塑料有限公司 A kind of superelevation melt strength blow molding resins composition and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690222A (en) * 2020-07-09 2020-09-22 东莞市奥能工程塑料有限公司 PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof
CN112608564A (en) * 2020-11-30 2021-04-06 金发科技股份有限公司 High-weather-resistance ASA material and preparation method and application thereof
CN112552614A (en) * 2020-12-14 2021-03-26 武汉金发科技有限公司 High-gloss black scratch-resistant PMMA/ASA composite material and preparation method thereof
CN112552614B (en) * 2020-12-14 2024-04-09 武汉金发科技有限公司 High-gloss black scratch-resistant PMMA/ASA composite material and preparation method thereof
CN113121939A (en) * 2021-03-30 2021-07-16 柳州炜林纳新材料科技有限责任公司 Composite resin material, preparation method thereof and automobile part
CN113088013A (en) * 2021-05-20 2021-07-09 上海金山锦湖日丽塑料有限公司 UVC-resistant ASA resin composition and preparation method thereof
CN113088013B (en) * 2021-05-20 2022-07-15 上海金山锦湖日丽塑料有限公司 UVC-resistant ASA resin composition and preparation method thereof

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