CN112341782A - PC/ABS alloy material with low butadiene residue and preparation method thereof - Google Patents
PC/ABS alloy material with low butadiene residue and preparation method thereof Download PDFInfo
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- CN112341782A CN112341782A CN202011204857.7A CN202011204857A CN112341782A CN 112341782 A CN112341782 A CN 112341782A CN 202011204857 A CN202011204857 A CN 202011204857A CN 112341782 A CN112341782 A CN 112341782A
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- alloy material
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- antioxidant
- maleimide
- butadiene
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000956 alloy Substances 0.000 title claims abstract description 64
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 150000001993 dienes Chemical class 0.000 claims abstract description 40
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 41
- 239000000155 melt Substances 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006757 chemical reactions by type Methods 0.000 claims description 20
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 3
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 150000001923 cyclic compounds Chemical class 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 description 19
- 229920000515 polycarbonate Polymers 0.000 description 19
- 239000000243 solution Substances 0.000 description 10
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 241001061260 Emmelichthys struhsakeri Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention relates to a PC/ABS alloy material with low butadiene residue and a preparation method thereof, wherein the PC/ABS alloy material comprises the following components in parts by weight: PC resin: 40-75 parts; ABS resin: 24.4-55 parts; diene reactive modifier: 0.5-4 parts; antioxidant: 0.1 to 1 portion. The diene reactive modifier is prepared by compounding a copolymer with a maleimide-containing side group and active carbon. According to the invention, double bonds in the copolymer with the maleimide-containing side group and butadiene can perform interaction reaction to generate a cyclic compound, and the 'opportunity' of the double bonds of the maleimide in the copolymer contacting with the butadiene can be increased by virtue of the higher specific surface area of the activated carbon, so that the residual amount of the butadiene in the PC/ABS alloy material is further effectively reduced, the residual amount of the butadiene is substantially reduced, the odor of the material is improved, and the requirements of odor of various high-end automobile host factories and the residual amount of the butadiene are met.
Description
Technical Field
The invention relates to the field of high-molecular modified materials, in particular to a PC/ABS alloy material with low butadiene residue and a preparation method thereof.
Background
The Polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) alloy integrates the advantages of the PC and the acrylonitrile-butadiene-styrene (ABS), so that on one hand, the heat resistance, the impact strength and the tensile strength of the ABS material are improved, on the other hand, the melt viscosity of the PC is reduced, the processability is improved, the stress sensitivity of an injection molding product is weakened, and the PC/acrylonitrile-butadiene-styrene (ABS) alloy is widely applied to the fields of automobiles, electronics, office equipment and the like. With the rapid development of the automobile industry and the continuous improvement of the living standard of people in recent years, consumers put higher demands on automobiles, namely: while safety, beauty and comfort are emphasized, high environmental protection is emphasized, and especially the quality of air in a vehicle is more and more concerned and emphasized by consumers and automobile manufacturers. Therefore, interior materials for automobiles which emit less odor are becoming more popular. The PC/ABS alloy material as an important material for automotive interior parts has the advantages that the emission and the odor are mainly derived from the following aspects: monomer micromolecules and PC/ABS alloy material modification processing aids remained in the early synthesis stage of raw materials of each component, and PC and ABS components are heated to be molten and decomposed under the action of high shear of a screw. Among these, the polybutadiene in the ABS component decomposes into butadiene species upon thermal shearing, which is among a class of carcinogens. Therefore, some high-end automobile host factories such as Benz, Baoma, and land Rover have clear index requirements on the residual amount of butadiene in styrene materials such as ABS and PC/ABS alloy materials.
At present, in order to improve the problem of smell in a vehicle and improve the comfort level, a fragrance agent is mostly added to cover and hide, although the unpleasant smell of plastic is reduced or changed into a relatively acceptable smell, the smell problem is not fundamentally solved. There is also a method of adding a small molecule deodorant, which usually contains water, and although the odor of the material can be improved, the PC material is not resistant to hydrolysis, and the performance of the material is seriously affected, which in turn affects the normal use of the product. In addition, no report is found about the reduction of the residual amount of butadiene in PC/ABS alloy materials. Therefore, a PC/ABS alloy material with low butadiene residue without losing material performance is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a PC/ABS alloy material with excellent performance and low butadiene residual quantity and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a PC/ABS alloy material with low butadiene residue comprises the following components in parts by weight:
PC resin: 40-75 parts;
ABS resin: 24.4-55 parts;
diene reactive modifier: 0.5-4 parts;
antioxidant: 0.1 to 1 portion.
The PC resin is bisphenol A aromatic PC, and the melt index is 5-30 g/10 min.
The molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
The diene reactive modifier is prepared by compounding a copolymer with a maleimide-containing side group and active carbon. Wherein the mass ratio of the copolymer with the maleimide-containing side group to the active carbon is 5-20: 1. The copolymer with the maleimide-containing side group is any one or the combination of more than two of polystyrene with the maleimide-containing side group, styrene-acrylonitrile copolymer with the maleimide-containing side group and styrene-acrylonitrile-butadiene copolymer with the maleimide-containing side group. The aperture of the activated carbon is 50-100 nm.
The antioxidant is a hindered classified antioxidant or phosphite antioxidant, and comprises any one or a combination of more than two of a commercially available antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618.
The preparation method of the PC/ABS alloy material with low butadiene residue comprises the following steps:
(1) preparation of diene reactive modifier
Dissolving the copolymer with the maleimide-containing side group and the activated carbon in an excessive acetone solution according to a certain weight ratio, carrying out ultrasonic dissolution at 50-70 ℃, fully soaking for 4-10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding PC resin, ABS resin, diene reactive modifier and antioxidant into a mixer for premixing, and controlling the rotating speed of the mixer to be 100-300 r/min and the mixing time to be 5-20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and carrying out granulation to prepare the PC/ABS alloy material with low butadiene residue.
Compared with the prior art, the invention has the following beneficial effects:
the diene reaction type modifier is prepared by a method of compounding a copolymer with a maleimide-containing side group and active carbon, wherein the copolymer with the maleimide-containing side group is attached to the inner surface and the outer surface of the active carbon. On one hand, the surface of the activated carbon has the copolymer, so that the activated carbon has good dispersibility in the PC/ABS alloy material, and the performance of the alloy material is not influenced. In addition, due to the excellent adsorption effect of the activated carbon, organic small molecules such as benzene, toluene, styrene, butadiene and the like in the PC/ABS alloy material can be adsorbed, so that the residual butadiene content of the material is reduced, and the odor of the material is improved. On the basis, double bonds in the copolymer with the maleimide on the side group can perform interaction reaction with butadiene to generate a cyclic compound, and the 'opportunity' of the double bonds of the maleimide in the copolymer contacting with the butadiene can be increased by means of the higher specific surface area of the activated carbon, so that the residual amount of the butadiene in the PC/ABS alloy material is further effectively reduced, the residual amount of the butadiene is substantially reduced, the odor of the material is improved, and the requirements of odor and residual amount of the butadiene in various high-end automobile host factories are met.
Detailed Description
The technical features of the present invention will be further explained with reference to the following embodiments. 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.
Comparative example 1
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
adding 70 parts of PC resin (with the melt index of 5g/10min), 30 parts of ABS resin (with the melt index of 15g/10min), 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 100r/min, and mixing for 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Comparative example 2
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side group and activated carbon (with the aperture of 50nm) according to the weight ratio of 24: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 50 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 70 parts of PC resin (with the melt index of 5g/10min), 30 parts of ABS resin (with the melt index of 15g/10min), 1 part of diene reaction type modifier, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 100r/min and the mixing time to be 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Comparative example 3
(1) Preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side groups and activated carbon (with the aperture of 75nm) according to the weight ratio of 3: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 60 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 70 parts of PC resin (with the melt index of 5g/10min), 30 parts of ABS resin (with the melt index of 15g/10min), 1 part of diene reaction type modifier, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 100r/min and the mixing time to be 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 1
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side group and activated carbon (with the aperture of 50nm) according to the weight ratio of 5: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 50 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 70 parts of PC resin (with the melt index of 5g/10min), 30 parts of ABS resin (with the melt index of 15g/10min), 1 part of diene reaction type modifier, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 100r/min and the mixing time to be 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 2
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a maleimide-containing side group and activated carbon (with the aperture of 100nm) according to a weight ratio of 20: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 70 ℃, soaking for 10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 70.6 parts of PC resin (with a melt index of 30g/10min), 24.4 parts of ABS resin (with a melt index of 15g/10min), 4 parts of diene reactive modifier, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixer for premixing, controlling the rotating speed of the mixer to be 300r/min, and mixing for 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 600r/min and controlling the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 3
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing styrene-acrylonitrile-butadiene with a maleimide-containing side group and activated carbon (with the aperture of 80nm) according to the weight ratio of 10: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 70 ℃, soaking for 8 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
42 parts of PC resin (the melt index is 20g/10min), 55 parts of ABS resin (the melt index is 30g/10min), 3 parts of diene reaction type modifier, 10760.3 parts of antioxidant and 6180.4 parts of antioxidant are added into a mixing stirrer for premixing, the rotating speed of the mixer is controlled to be 250r/min, and the mixing time is 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 400r/min and controlling the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 4
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing styrene-acrylonitrile-butadiene containing maleimide on a side group, polystyrene containing maleimide on a side group (the mass ratio of the styrene-acrylonitrile-butadiene containing maleimide on the side group to the polystyrene containing maleimide on the side group is 1:1) and active carbon (with the aperture of 50nm) according to the weight ratio of 12: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 60 ℃, soaking for 9 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 63 parts of PC resin (with a melt index of 20g/10min), 35 parts of ABS resin (with a melt index of 30g/10min), 2 parts of diene reaction type modifier, 10760.3 parts of antioxidant and 6180.4 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 250r/min and the mixing time to be 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 400r/min and controlling the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 5
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a side group containing maleimide, polystyrene with a side group containing maleimide (the mass ratio of the styrene-acrylonitrile copolymer with the side group containing maleimide to the polystyrene with the side group containing maleimide is 2:1) and activated carbon (with a pore diameter of 75nm) according to a weight ratio of 15: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 65 ℃, soaking for 10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 65 parts of PC resin (with a melt index of 10g/10min), 33 parts of ABS resin (with a melt index of 20g/10min), 2 parts of diene reaction type modifier, 10980.3 parts of antioxidant and 6180.6 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 250r/min and the mixing time to be 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 450r/min and controlling the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 6
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a side group containing maleimide, polystyrene with a side group containing maleimide (the mass ratio of the styrene-acrylonitrile copolymer with the side group containing maleimide to the polystyrene with the side group containing maleimide is 2:1) and activated carbon (with a pore diameter of 100nm) according to a weight ratio of 8: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 55 ℃, soaking for 7 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 61.5 parts of PC resin (with a melt index of 15g/10min), 35 parts of ABS resin (with a melt index of 8g/10min), 3.5 parts of diene reaction type modifier, 10100.2 parts of antioxidant and 6180.4 parts of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 150r/min, and mixing for 15 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 500r/min and controlling the vacuum degree to be-0.07 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
Example 7
A PC/ABS alloy material with low butadiene residue and a preparation method thereof comprise the following steps:
(1) preparation of diene reactive modifier
The method comprises the following steps of (1) taking a copolymer with a maleimide-containing side group as a polystyrene with a maleimide-containing side group, a styrene-acrylonitrile copolymer with a maleimide-containing side group, a styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group (the copolymer with a maleimide-containing side group is a polystyrene with a maleimide-containing side group, the styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group is prepared, and the mass ratio of the styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group to active carbon (the aperture is 80nm) in a weight ratio of 16: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 65 ℃, soaking for 5 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of PC/ABS alloy material
Adding 50 parts of PC resin (the melt index is 15g/10min), 48.5 parts of ABS resin (the melt index is 8g/10min), 1.5 parts of diene reaction type modifier, 10760.15 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 200r/min, and mixing for 10 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 550r/min and controlling the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the PC/ABS alloy material.
According to the PC/ABS alloy material prepared in the comparison column 1 and the examples 1-7, test sample strips are prepared according to the same injection molding process conditions, and the specific evaluation methods of mechanical properties, odor and butadiene residual quantity are as follows:
tensile strength: testing according to ISO527 standard;
flexural strength and modulus: testing according to ISO178 standard;
vicat softening temperature: testing according to ISO306 standard;
notched impact strength (23 ℃ and-30 ℃): testing according to ISO179-1 standard;
odor characteristics were tested according to VDA270 standard (20 g);
the butadiene residual was tested in accordance with DIN EN 13130.
As can be seen from the above table, the invention can significantly reduce the butadiene residual quantity of the PC/ABS alloy material and improve the odor of the material by adding a certain amount of reactive modifier. As in example 2, 4 parts of odor eliminating agent was added, the odor grade was 3, and the residual butadiene content was 0.2 ug/g. The PC/ABS alloy material with low butadiene residue prepared by the invention can meet the requirements of high-end vehicles such as gallop and BMW on the emission performance of automobile materials, and has wide application prospect.
Claims (9)
1. The PC/ABS alloy material with low butadiene residue is characterized by comprising the following components in parts by weight:
PC resin: 40-75 parts;
ABS resin: 24.4-55 parts;
diene reactive modifier: 0.5-4 parts;
antioxidant: 0.1 to 1 portion.
2. The PC/ABS alloy material with low butadiene residue content as claimed in claim 1, wherein the PC resin is bisphenol A aromatic PC, and the melt index is 5-30 g/10 min.
3. The PC/ABS alloy material with low butadiene residue content as claimed in claim 1, wherein the molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
4. The PC/ABS alloy material with low butadiene residue content as claimed in claim 1, wherein the diene reactive modifier is compounded from a copolymer with maleimide on the side group and activated carbon. Wherein the mass ratio of the copolymer with the maleimide-containing side group to the active carbon is 5-20: 1.
5. The PC/ABS alloy material with low butadiene residue content as claimed in claim 4, wherein the maleimide-containing copolymer is any one or a combination of two or more of a maleimide-containing polystyrene, a maleimide-containing styrene-acrylonitrile copolymer and a maleimide-containing styrene-acrylonitrile-butadiene copolymer.
6. The PC/ABS alloy material with low butadiene residue content as claimed in claim 4, wherein the pore diameter of the activated carbon is 50-100 nm.
7. The PC/ABS alloy material with low residual butadiene content as claimed in claim 1, wherein the antioxidant is a hindered antioxidant or phosphite antioxidant.
8. The PC/ABS alloy material with low butadiene residue content as claimed in claim 7, wherein the antioxidant is any one or a combination of more than two of commercially available antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant 618.
9. The preparation method of the PC/ABS alloy material with low residual butadiene content according to any one of claims 1-8, characterized by comprising the following steps:
(1) preparation of diene reactive modifier
Dissolving a copolymer with a maleimide-containing side group and activated carbon in an excessive acetone solution according to a certain weight ratio, performing ultrasonic dissolution at 50-70 ℃, fully soaking for 4-10 hours, filtering, and drying to obtain a diene reaction type modifier for later use;
(2) preparation of PC/ABS alloy material
Adding PC resin, ABS resin, diene reactive modifier and antioxidant into a mixer for premixing, and controlling the rotating speed of the mixer to be 100-300 r/min and the mixing time to be 5-20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and carrying out granulation to prepare the PC/ABS alloy material with low butadiene residue.
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