CN112745616B - Modified acrylic ester polymer composition - Google Patents
Modified acrylic ester polymer composition Download PDFInfo
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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
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- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a modified PMMA/ASA polymer composition, which consists of the following components in parts by weight: 30-60 parts by weight of PMMA; 10-20 parts of a toughening agent; 5-10 parts of a compatilizer A; 0.5-2 parts by weight of a compatilizer B; 1-5 parts of an anti-scratching agent; 0.5-6 parts of processing aid. The disclosure also provides a method for preparing the modified PMMA/ASA polymer composition. The PMMA/ASA/MBS alloy resin composition with greatly improved impact strength, excellent scratch resistance, good surface gloss and good weather resistance is obtained by introducing two compatilizers with synergistic action.
Description
Technical Field
The disclosure relates to the field of polymer materials, in particular to an acrylic ester polymer composition PMMA/ASA/MBS and a preparation method thereof.
Background
Polymethyl methacrylate (PMMA), also known as acrylic or organic glass, has excellent optical properties, with a transparency of up to 92%. In addition, it has excellent weather resistance, mechanical strength, excellent heat and sound insulating performance, high luster, high coloring power and high scratch resistance. In the automotive field, PMMA resins are used for window glass, covers, instrument glass, lamps, signs and the like.
The ASA resin is an impact-resistant modified resin formed by copolymerizing terpolymers such as styrene, acrylonitrile, acrylic rubber and the like, has good mechanical and physical properties, is similar to the structure of the ABS, and reserves the excellent mechanical and physical properties of the ABS as engineering plastics. ASA has strong weather resistance and better high-temperature resistance, and in addition, ASA is an antistatic material and can reduce dust accumulation on the surface. Because the ASA resin structure does not contain unsaturated double bonds, the ASA resin can resist degradation, aging and fading caused by ultraviolet irradiation, and can greatly improve the aging resistance and weather resistance of the material. The ASA resin has good impact resistance, colorability and chemical resistance. The application of ASA resin to automobiles is mainly to exterior parts such as grilles, triangular blocks, pillar boards, and the like.
It is worth noting that the high-gloss, black and bright effect of the exterior trim of the automobile is difficult to be realized by direct injection molding of plastics, and a spraying process is usually required, and the spraying not only increases the cost, but also causes serious pollution to the environment. Based on the fact, the important significance is achieved in developing and designing materials which can be directly applied to injection molding parts without post-processing technologies such as spraying and the like, and PMMA/ASA alloy is one of the materials and has aging resistance and scraping resistance. However, the compatibility between PMMA and ASA is poor, so that the comprehensive mechanical properties of PMMA and ASA cannot meet the standard requirements of the automobile industry in particular.
CN106046643A discloses a high-compatibility PMMA/ASA alloy resin composition and a preparation method thereof, the invention prepares the PMMA/ASA alloy resin composition with excellent toughness, rigidity, heat resistance, hardness and weather resistance by controlling the proportion of PMMA to ASA, adding MMA-SAN, SMA and AS-g-MAH compatilizers and controlling the proportion of monomers in the compatilizers.
CN109337272A discloses a PMMA/ASA alloy resin composition with heat resistance and scratch resistance, which utilizes PMMA-g-GMA as a compatilizer to enable PMMA-g-GMA and SMA to generate copolymerization reaction to form covalent bonds in the blending process, thereby obtaining a PMMA copolymer with a branching result and a crosslinking structure, and preparing the PMMA/ASA alloy resin composition with excellent physical and mechanical properties and scratch resistance and heat resistance.
Compared with the prior art, the PMMA/ASA/MBS alloy resin composition has the advantages that two compatilizers with synergistic action are introduced, and the microstructures of the matrix resin, the toughening agent and the compatilizer are controlled, so that good compatibility among organic phases and between the organic phases and inorganic phases can be realized simultaneously, and the PMMA/ASA/MBS alloy resin composition with greatly improved impact strength, excellent scratch resistance, good surface gloss and good weather resistance is obtained.
Disclosure of Invention
The invention provides a modified PMMA/ASA polymer composition, which consists of the following components in parts by weight:
the weight average relative molecular mass of the PMMA (polymethyl methacrylate) resin is 50000-300000 g/mol;
the toughening agent is ASA (acrylate-styrene-acrylonitrile graft copolymer) rubber powder;
the compatilizer A is MBS (butadiene-styrene-methyl methacrylate graft copolymer) resin;
the compatilizer B is selected from organosilane compatilizers;
the anti-scratching agent is selected from one or more of organic silicon, calcium carbonate, magnesium stearate, molybdenum and glass fiber;
the processing aid comprises an antioxidant, a coloring agent, a lubricant and a release agent.
In a preferred embodiment, the modified PMMA/ASA polymer composition consists of the following components in parts by weight:
in a preferred embodiment, the PMMA (polymethyl methacrylate) resin has a weight average molecular weight of 150000-300000 g/mol.
In a preferred embodiment, the ASA (acrylate-styrene-acrylonitrile graft copolymer) rubber powder is a toughening agent which takes acrylate rubber as a core layer and takes styrene and acrylonitrile graft copolymer as a shell layer, the rubber phase of the core layer can greatly improve the impact strength of matrix resin, and the resin layer of the shell layer can improve the compatibility of the rubber powder and the matrix resin, so that the rubber powder is better dispersed in the matrix resin. The appropriate ASA rubber powder bulk density and particle size are beneficial to the mixing uniformity of the rubber powder and each component, and in the scheme, the bulk density of the ASA rubber powder is controlled to be 0.3-0.4 g/cm3The particle size (D50) of the ASA rubber powder is 50-200 μm. When the bulk density of the ASA rubber powder is less than 0.3g/cm3Or more than 0.4g/cm3When the particle size of the ASA rubber powder is less than 50 μm or more than 200 μm, the mixing uniformity of the ASA rubber powder and other components in the premixing and granulating stage can be obviously influenced.
The ASA gum powder may be prepared by: stirring and mixing 1700-1900 parts by weight of deionized water, 90-110 parts by weight of butyl acrylate and 2-5 parts by weight of emulsifier uniformly, adjusting the pH value of the mixture to 4-5 by using 0-2 parts by weight of pH value regulator, then adding 0.1-0.5 part by weight of initiator, and reacting for 0.3-1 hour at 55-65 ℃ to obtain polybutyl acrylate seed emulsion; adding 400-600 parts by weight of butyl acrylate into the polybutyl acrylate seed emulsion, stirring and mixing uniformly, then adding 0.3-1 part by weight of initiator, and reacting for 3 hours at 70 ℃ to obtain polybutyl acrylate emulsion; adding 280-320 parts by weight of styrene and 90-120 parts by weight of acrylonitrile into the polybutyl acrylate emulsion, stirring and mixing uniformly, then adding 0.5-1 part by weight of initiator, and reacting for 3-8 hours at 70-80 ℃ to obtain ASA emulsion; and (3) demulsifying the ASA emulsion, washing and drying to obtain the ASA rubber powder. The ASA gum powder may also be XC-500A available from Korea brocade lake.
The particle size of the latex particles in the emulsion for preparing the ASA rubber powder, the rubber phase content, the core-shell ratio and the rubber crosslinking degree in the ASA rubber powder have important influences on the crazing caused by rubber particles in the modified PMMA/ASA polymer composition and the induced shear yield, so that the particle size, the rubber phase content, the core-shell ratio and the rubber crosslinking degree of the latex particles need to be controlled properly, the particle size (D50) of the latex particles is controlled to be 100-500 nm, the rubber phase content is 40-80 wt%, the core-shell mass ratio is 1: 0.3-1: 1, and the rubber crosslinking degree is 75-95%.
When the particle size of latex particles in the emulsion for preparing the ASA rubber powder is less than 100nm, the rubber particles are easy to disperse unevenly due to agglomeration, and the rubber particles can not induce silver lines and shear yield when the PMMA/ASA polymer composition is impacted, so that the toughening effect can not be achieved; when the particle size of the latex particles in the emulsion for preparing the ASA rubber powder is larger than 500nm, the toughening effect of the ASA rubber powder on the PMMA/ASA polymer composition is hardly increased any more, and the flexural modulus, tensile strength, heat resistance and the like of the PMMA/ASA polymer composition are remarkably reduced. When the content of the rubber phase in the ASA rubber powder is lower than 40 wt%, the ASA rubber powder cannot achieve an obvious toughening effect on PMMA; when the rubber phase content is more than 80 wt%, the mixing compatibility of the ASA rubber powder with PMMA becomes poor, thereby affecting the impact strength of the PMMA/ASA polymer composition. When the mass ratio of the core shell in the ASA rubber powder is higher than 1:0.3, the mixing compatibility of the ASA rubber powder and PMMA is poor; when the mass ratio of the core shell is lower than 1:1, the rubber particles are not easy to initiate crazing, and the toughening effect is greatly reduced. When the rubber crosslinking degree in the ASA rubber powder is lower than 75%, the elasticity of rubber particles is not high, and the ideal toughening effect cannot be achieved; when the degree of crosslinking of the rubber is higher than 95%, the graft ratio of ASA is reduced, so that the mixing compatibility of the ASA rubber powder and PMMA is poor, and rubber phase induced voiding and shear banding capacity are reduced, which result in poor toughening effect.
In a preferred embodiment, the MBS (butadiene-styrene-methyl methacrylate graft copolymer) resin is a compatibilizer having a butadiene rubber or styrene-butadiene rubber as a core layer and then styrene and methyl methacrylate are grafted in sequence to form a shell layer. Styrene and methyl methacrylate in the shell layer can well improve the compatibility of PMMA and ASA, and the core layer can provide a certain toughening effect. The proper size of the MBS resin particles is beneficial to the mixing uniformity of the resin and each component, and the size (D50) of the resin particles is controlled to be 50-200 mu m in the scheme. The MBS resin is obtained by agglomerating and drying emulsion with the particle size (D50) of 100-500 nm, the grafting rate of the latex particles is 40-100%, the molar ratio of styrene to methyl methacrylate in a grafting layer is 4: 6-6: 4, and the rubber phase content in the resin is 30-50 wt%.
The MBS resin may be prepared by: stirring and mixing 2200-2400 parts by weight of deionized water, 90-110 parts by weight of butadiene, 20-40 parts by weight of styrene, 1-5 parts by weight of emulsifier and 0.3-1 part by weight of stabilizer uniformly, then adding 0.2-0.6 part by weight of initiator, and reacting at 55-65 ℃ for 0.2-1 hour to obtain butylbenzene seed emulsion; adding 300-500 parts by weight of butadiene and 100-140 parts by weight of styrene into the styrene-butadiene seed emulsion, stirring and mixing uniformly, then adding 0.6-1 part by weight of initiator, and reacting for 2 hours at 70-80 ℃ to obtain styrene-butadiene emulsion; adding 300-500 parts by weight of methyl methacrylate, 300-500 parts by weight of styrene and 1-3 parts by weight of antioxidant into the butylbenzene emulsion, stirring and mixing uniformly, then adding 1-3 parts by weight of initiator, and reacting for 4-6 hours at 70-80 ℃ to obtain MBS emulsion; and demulsifying, washing and drying the MBS emulsion to obtain the MBS resin. The MBS resin may also be EM-500 from LG chemistry, EXL2620 from DOW chemistry. When the particle size of latex particles in the emulsion for preparing the MBS resin is more than 500nm or less than 100nm, the MBS resin and the ASA rubber powder are not well mixed and dispersed, so that the compatibilization effect of the MBS resin is poor, and the synergistic toughening effect of the MBS resin and the ASA rubber powder is poor. When the grafting rate of the latex particles in the MBS resin is lower than 40 percent, the MBS cannot increase the compatibility of PMMA and ASA rubber powder. When styrene and methyl methacrylate in the MBS resin graft layer are less than 4:6 or more than 6:4, the MBS as a compatibilizer has poor effect of increasing the compatibility of PMMA and ASA rubber powder. When the content of the rubber phase in the MBS resin is lower than 30 wt%, the MBS resin cannot generate a synergistic effect with the ASA rubber powder to achieve a better toughening effect; when the rubber phase content is higher than 50 wt%, the MBS as a compatilizer has poor effect of increasing the compatibility of PMMA and ASA rubber powder.
In a preferred embodiment, one end of the organosilane-based compatilizer has one and only one organic group selected from one of vinyl group, amino group, epoxy group and methacryloxy group, and the other end of the organosilane-based compatilizer is an alkoxy silicon group. The organic group can react with PMMA, ASA and MBS but not generate cross linking, the alkoxy silicon group at the other end of the compatilizer can react with the scratch-resistant agent, on one hand, the compatibility between organic phases and the compatibility between the organic phases and inorganic phases are improved, on the other hand, the carbon-carbon double bond in the MBS is consumed, and the weather resistance of the polymer composition, such as the performances of light resistance, temperature change resistance and humidity change resistance, is improved.
In a preferred embodiment, the scratch-resistant agent is one of silicone, calcium carbonate, magnesium stearate, molybdenum and glass fiber, and the scratch-resistant agent can be uniformly and firmly combined with PMMA, ASA and MBS through the compatilizer B, so as to achieve better effect of improving the scratch resistance of the polymer composition.
In a preferred embodiment, the antioxidant, colorant, lubricant and release agent are processing aids well known in PMMA extrusion granulation. The antioxidant is preferably hindered phenol antioxidant or phosphite antioxidant, such as antioxidant 1010 and antioxidant 168; the coloring agent is black dye and carbon black; the lubricant is preferably pentaerythritol stearate or ethylene bis stearamide; the release agent is preferably a silicone-based release agent, such as dimethyl silicone. In the processing aid, the mass ratio of the antioxidant to the coloring agent to the lubricant to the mold release agent is (1-3): (0.5-1.5): (0.5-1.5): 1, the product can achieve better processing performance and material performance.
The present disclosure also provides a method for preparing a modified PMMA/ASA polymer composition, comprising the steps of:
(1) weighing PMMA resin, a toughening agent, a compatilizer A and a processing aid in parts by weight, and uniformly mixing to obtain a premix 1;
(2) weighing the compatilizer B and the anti-scratch agent according to the weight parts to obtain premix 2;
(3) and (2) further uniformly mixing the premix 1 and the premix 2, adding the mixture into a double-screw extruder in a main feeding mode, and cooling and granulating to obtain the modified PMMA/ASA polymer composition.
In a preferred embodiment, in step (3), premix 1 is fed to the twin-screw extruder by a main feeding method, and then premix 2 is fed to the twin-screw extruder by a side feeding method.
In a preferred embodiment, the premix is fed into a twin-screw extruder, melt-extruded at an extrusion temperature of 200-240 ℃ and a screw rotation speed of 300-500 rpm, and cooled for granulation.
Advantageous effects
The modified PMMA/ASA polymer composition material disclosed by the invention has the characteristics of high impact strength and good scratch resistance, has higher surface gloss and weather resistance, can effectively expand the application range of PMMA/ASA materials, and has good application prospects.
The impact strength of the modified PMMA/ASA polymer composition obtained after cooling and granulation is improved by more than 60 percent compared with that of a commercialized PMMA/ASA alloy material, the scratch resistance of the modified PMMA/ASA polymer composition is improved by more than 80 percent compared with that of the commercialized PMMA/ASA alloy material, and the surface glossiness and the weather resistance of the modified PMMA/ASA polymer composition are basically not reduced.
Compared with the prior art, the PMMA/ASA/MBS alloy resin composition has the advantages that two compatilizers with synergistic action are introduced, and the microstructures of the matrix resin, the toughening agent and the compatilizer are controlled, so that good compatibility among organic phases and between the organic phases and inorganic phases can be realized simultaneously, and the PMMA/ASA/MBS alloy resin composition with greatly improved impact strength, excellent scratch resistance, good surface gloss and good weather resistance is obtained.
The ASA rubber powder is used in the method, the toughening effect of the ASA rubber powder is better than that of ASA resin, and the transparency and the glossiness of PMMA/ASA are guaranteed at the same time. The ASA resin is a blend of ASA rubber powder and SAN (styrene-acrylonitrile copolymer) resin, and the ASA rubber powder has a toughening effect, and the SAN resin has poor toughness, so that the toughening effect of the ASA rubber powder is better than that of the ASA resin. In addition, the addition of SAN adversely affects the clarity and gloss of PMMA/ASA. And the scratch-resistant agent can obviously improve the scratch-resistant performance of the material.
Detailed Description
The present disclosure will be described in further detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail with reference to embodiments.
Examples
Example 1
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 50000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 300nm, and the bulk density of the rubber powder is 0.35g/cm3The rubber powder particle size (D50) is 100 mu m, the rubber phase content is 60 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1: 0.6, the crosslinking degree of the rubber is 75 percent; the MBS resin is obtained by agglomerating and drying emulsion with the particle size of latex particles (D50) of 300nm, the particle size of resin particles (D50) is 100 mu m, the grafting rate of the resin latex particles is 80 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 6:4, and the rubber phase content in the resin is 50wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 1010: black dye: pentaerythritol stearate: the mass ratio of the dimethyl silicone is 1:0.5:0.5: 1.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 200 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Example 2
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 150000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 100nm, and the bulk density of the rubber powder is 0.30g/cm3The rubber powder particle size (D50) is 50 μm, the rubber phase content is 40 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1:0.3, the crosslinking degree of the rubber is 80 percent; the MBS resin is obtained by agglomerating and drying emulsion with 100nm of latex particle size (D50), the particle size (D50) of resin particles is 50 mu m, the grafting ratio of the resin latex particles is 40 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 4:6, and the content of a rubber phase in the resin is 30wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 1010: black dye: pentaerythritol stearate: the mass ratio of the dimethyl silicone is 1:0.5:1: 1.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 210 ℃ and the screw rotating speed of 350 r/min, and cooling and granulating to obtain the polymer composition.
Example 3
According to different weight parts of the following table 1, the following raw material components are respectively weighed: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the weight average molecular weight of the PMMA resin is 2000000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 500nm, and the bulk density of the rubber powder is 0.40g/cm3The rubber powder particle size (D50) is 200 mu m, the rubber phase content is 80 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1:1, the crosslinking degree of the rubber is 80 percent; the MBS resin is obtained by agglomerating and drying emulsion with the particle size of latex particles (D50) of 500nmThe particle diameter (D50) of the resin particles is 200 μm, the grafting ratio of the resin emulsion particles is 100 percent, the molar ratio of styrene to methyl methacrylate in the grafting layer is 6:4, and the content of rubber phase in the resin is 50wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of the dimethyl silicone is 1:1:1: 1.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 220 ℃ and the screw rotating speed of 400 rpm, and cooling and granulating to obtain the polymer composition.
Example 4
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 250000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 400nm, and the bulk density of the rubber powder is 0.35g/cm3The rubber powder particle size (D50) is 200 μm, the rubber phase content is 50 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1: 0.8, the crosslinking degree of the rubber is 85 percent; the MBS resin is obtained by agglomerating and drying emulsion with the particle size of latex particles (D50) of 400nm, the particle size of resin particles (D50) is 150 mu m, the grafting rate of the resin latex particles is 90 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 5:5, and the rubber phase content in the resin is 50wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of the dimethyl silicone is 2:1.5:1.5: 1.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 240 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the polymer composition.
Example 5
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 300000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 300nm, and the bulk density of the rubber powder is 0.35g/cm3The rubber powder particle size (D50) is 100 μm, the rubber phase content is 70 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1: 0.9, the crosslinking degree of the rubber is 90 percent; the MBS resin is obtained by agglomerating and drying emulsion with the particle size of latex particles (D50) of 300nm, the particle size of resin particles (D50) is 100 mu m, the grafting rate of the resin latex particles is 60 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 6:4, and the rubber phase content in the resin is 50wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of dimethyl silicone is 3:1.5:1.5: 1.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 240 ℃ and the screw rotating speed of 500 rpm, and cooling and granulating to obtain the polymer composition.
Example 6
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 50000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 100nm, and the bulk density of the rubber powder is 0.30g/cm3The rubber powder particle size (D50) is 50 μm, the rubber phase content is 40 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1:0.3, crosslinking of the rubberThe degree is 75%; the MBS resin is obtained by agglomerating and drying emulsion with the particle size of latex particles (D50) of 300nm, the particle size of resin particles (D50) is 100 mu m, the grafting rate of the resin latex particles is 60 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 6:4, and the rubber phase content in the resin is 50wt percent; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of dimethyl silicone is 3:1.5:1.5: 1.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 220 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Example 7
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, compatilizer B, magnesium stearate and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 50000 g/mol; the ASA rubber powder is obtained by agglomerating and drying emulsion with the particle size (D50) of latex particles of 300nm, and the bulk density of the rubber powder is 0.35g/cm3The rubber powder particle size (D50) is 100 μm, the rubber phase content is 70 wt%, and the mass ratio of the polybutyl acrylate core layer to the styrene-acrylonitrile shell layer is 1: 0.9, the crosslinking degree of the rubber is 90 percent; the MBS resin is obtained by agglomerating and drying emulsion with 100nm of latex particle diameter (D50), the particle diameter (D50) of resin particles is 50 mu m, the grafting rate of the resin latex particles is 40 percent, the molar ratio of styrene to methyl methacrylate in a grafting layer is 4:6, and the rubber phase content in the resin is 30 wt%; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of dimethyl silicone is 3:1.5:1.5: 1.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 220 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Comparative example 1
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder and processing aids; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has a weight average molecular weight of 100000 g/mol; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is antioxidant 1010: black dye: pentaerythritol stearate: the mass ratio of the dimethyl silicone is 1:0.5:0.5: 1.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 200 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Comparative example 2
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, a compatilizer B and a processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 100000 g/mol; the compatilizer B is 3-methacryloxypropyltrimethoxysilane; the processing aid is as follows: antioxidant 1010: black dye: pentaerythritol stearate: the mass ratio of the dimethyl silicone is 1:0.5:1: 1.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 200 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Comparative example 3
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA rubber powder, MBS resin, magnesium stearate and processing aids; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 100000 g/mol; the processing aid is as follows: antioxidant 168: carbon black: ethylene bis stearamide: the mass ratio of the dimethyl silicone is 1:1:1: 1.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 200 ℃ and the screw rotating speed of 300 revolutions per minute, and cooling and granulating to obtain the polymer composition.
Comparative example 4
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
The following raw material components are respectively weighed according to different weight part ratios as shown in the following table 1: PMMA resin, ASA resin, MBS resin, compatilizer B and processing aid; and premixing for 5 minutes in a high-speed mixer to obtain the premix. Wherein the PMMA resin has the weight average molecular weight of 50000 g/mol; the ASA resin has a rubber content of 20 wt%, the compatibilizer B is selected from AS-g-MAH, and the processing aids are: hindered phenol antioxidant: the mass ratio of pentaerythritol stearate to dimethyl silicone is 2:1:1, and 0.5 part by weight of black master batch is additionally added, wherein the black master batch is formed by mixing and injection molding of a carrier, carbon black and an auxiliary agent, the carrier is polyethylene wax, and the content of the carbon black is 50 wt%.
Feeding the premix into a double-screw extruder, performing melt extrusion at the extrusion temperature of 200 ℃ and the screw rotating speed of 200 r/min, and cooling and granulating to obtain the polymer composition.
The composition of the modified PMMA/ASA polymer composition is shown in Table 1 below.
TABLE 1 composition of modified PMMA/ASA Polymer compositions
| Number of | PMMA | ASA rubber powder | MBS resin | Compatibilizer B | Magnesium stearate | Processing aid |
| Example 1 | 40 | 10 | 5 | 2 | 1 | 0.5 |
| Example 2 | 50 | 10 | 5 | 2 | 1 | 0.6 |
| Example 3 | 60 | 10 | 5 | 2 | 1 | 0.7 |
| Example 4 | 60 | 20 | 10 | 2 | 2 | 0.8 |
| Example 5 | 60 | 15 | 8 | 2 | 2 | 0.8 |
| Example 6 | 50 | 20 | 10 | 2 | 3 | 1.5 |
| Example 7 | 60 | 20 | 6 | 1 | 4 | 2 |
| Comparative example 1 | 60 | 20 | 0 | 0 | 0 | 0.8 |
| Comparative example 2 | 60 | 20 | 0 | 2 | 0 | 0.8 |
| Comparative example 3 | 60 | 20 | 10 | 0 | 2 | 0.8 |
| Comparative example 4 | 35 | 30 | 5 | 1 | 0 | 0.6 |
The test method comprises the following steps:
charpy notched impact strength: the impact energy is 4J according to the test of ISO 179-1:2010 (E);
gloss: the test angle was 20 ° according to ASTM D2457;
scratch resistance: the change in L value before and after scratching was tested according to GMW14688, method 1, at a load of 10N. The smaller the Δ L value, the better the scratch resistance.
Weather resistance: the irradiation energy was 2500kJ/m as tested according to SAE J2527 standard2And testing the color difference delta E value.
The test results of examples and comparative examples are shown in table 2 below.
TABLE 2 Performance testing of examples and comparative examples
From the above examples 1-7, it can be seen that the modified PMMA/ASA polymer compositions obtained by the present disclosure have good notched impact strength, scratch resistance and weatherability, and also have good gloss at the same time. As can be seen from comparative examples 1 and 2, when the MBS resin was not contained in the polymer composition, the resulting polymer composition had low notched impact strength and also had poor scratch resistance. As can be seen from comparative example 3, when the compatibilizer B was not contained in the polymer composition, the scratch resistance of the resulting polymer composition was lowered and the weather resistance was deteriorated. As can be seen from comparative example 4, when the ASA resin content is more than 20 parts by weight, the impact strength of the PMMA/ASA polymer composition is not significantly improved and the gloss is greatly reduced.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (7)
1. The modified PMMA/ASA polymer composition is characterized by comprising the following components in parts by weight:
30-60 parts by weight of PMMA;
10-20 parts of a toughening agent;
5-10 parts of a compatilizer A;
0.5-2 parts by weight of a compatilizer B;
1-5 parts of an anti-scratching agent;
0.5-6 parts by weight of a processing aid;
the weight average relative molecular mass of the PMMA polymethyl methacrylate resin is 50000-300000 g/mol;
the toughening agent is ASA acrylate-styrene-acrylonitrile graft copolymer rubber powder;
the compatilizer A is MBS butadiene-styrene-methyl methacrylate graft copolymer resin;
the compatilizer B is selected from organosilane compatilizers;
the ASA acrylate-styrene-acrylonitrile graft copolymer rubber powder is obtained by agglomerating and drying emulsion with the particle size D50 of 100-500 nm, and the bulk density of the rubber powder is 0.3-0.4 g/cm3The particle size D50 of the rubber powder is 50-200 μm, the content of a rubber phase in the rubber powder is 40-80 wt%, the mass ratio of a polybutyl acrylate core layer to a polystyrene-acrylonitrile shell layer is 1: 0.3-1: 1, and the degree of rubber crosslinking is 75-95%;
the particle size D50 of the MBS resin is 50-200 mu m, the MBS resin is obtained by agglomerating and drying emulsion with the particle size D50 of 100-500 nm, the grafting rate of the latex particles is 40-100%, the molar ratio of styrene to methyl methacrylate in a grafting layer is 4: 6-6: 4, and the rubber phase content in the resin is 30-50 wt%;
one end of the organosilane compatilizer has only one organic group, the organic group is one of vinyl, amino, epoxy and methacryloxy, and the other end of the organosilane compatilizer is an alkoxy silicon group;
the anti-scratching agent is selected from one or more of organic silicon, calcium carbonate, magnesium stearate, molybdenum and glass fiber;
the processing aid comprises an antioxidant, a coloring agent, a lubricant and a release agent.
2. The modified PMMA/ASA polymer composition of claim 1, which is composed of the following components in parts by weight:
30-50 parts by weight of PMMA;
10-15 parts of a toughening agent;
5-7 parts of a compatilizer A;
0.5-1 part by weight of a compatilizer B;
1-5 parts of an anti-scratching agent;
1.5-3 parts of a processing aid.
3. The modified PMMA/ASA polymer composition of claim 1 or 2, wherein the PMMA polymethylmethacrylate resin has a weight average molecular weight of 150000-300000 g/mol.
4. The modified PMMA/ASA polymer composition of claim 1 or claim 2 wherein the mass ratio of the antioxidant, the colorant, the lubricant and the release agent in the processing aid is (1-3): (0.5-1.5): (0.5-1.5): 1.
5. the modified PMMA/ASA polymer composition of claim 1 or claim 2 wherein the antioxidant is selected from the group consisting of hindered phenolic antioxidants and phosphite antioxidants; the coloring agent is selected from black dye and carbon black; the lubricant is selected from pentaerythritol stearate or ethylene bis stearamide; the release agent is selected from silicone release agents.
6. A process for the preparation of a modified PMMA/ASA polymer composition according to claim 1 or 2, comprising the steps of:
(1) weighing PMMA resin, a toughening agent, a compatilizer A and a processing aid in parts by weight, and uniformly mixing to obtain a premix 1;
(2) weighing the compatilizer B and the anti-scratch agent according to the weight parts to obtain premix 2;
(3) the premix 1 and the premix 2 can be further uniformly mixed, then the mixture is added into a double-screw extruder in a main feeding mode, and the polymer composition is obtained after cooling and granulation.
7. The preparation method as set forth in claim 6, wherein in the step (3), the premix 1 is fed into the twin-screw extruder by a main feeding manner, and then the premix 2 is fed into the twin-screw extruder by a side feeding manner.
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