CN114196185A - Polycarbonate alloy material and preparation method and application thereof - Google Patents
Polycarbonate alloy material and preparation method and application thereof Download PDFInfo
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- CN114196185A CN114196185A CN202111353685.4A CN202111353685A CN114196185A CN 114196185 A CN114196185 A CN 114196185A CN 202111353685 A CN202111353685 A CN 202111353685A CN 114196185 A CN114196185 A CN 114196185A
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- Prior art keywords
- alloy material
- toughening agent
- resin
- polycarbonate alloy
- acrylate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 76
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 239000012745 toughening agent Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 28
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 19
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical group C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 51
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- -1 acrylic ester Chemical class 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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)
Abstract
The invention discloses a polycarbonate alloy material and a preparation method and application thereof. The polycarbonate alloy material comprises the following components in parts by weight: 40-80 parts of PC resin; 5-25 parts of SAN resin; 2-10 parts of a toughening agent A; 1-8 parts of a toughening agent B. According to the invention, a certain amount of SAN resin is added into PC resin, and the acrylic ester graft copolymer containing acrylonitrile-styrene chain segments and the acrylic ester graft copolymer containing methyl methacrylate monomer skeletons with different acrylic ester rubber particle diameters are added at the same time, so that the toughness of the material can be effectively improved while the good fluidity is considered, the problem that the toughness and the fluidity of a polycarbonate material are difficult to maintain simultaneously in the prior art is solved, the polycarbonate alloy material with high toughness and high fluidity is prepared, and the processing requirement and the use requirement of a thin-wall part can be met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate alloy material and a preparation method and application thereof.
Background
Polycarbonate (PC) has outstanding impact resistance and heat resistance, good dimensional stability, low water absorption, and is widely used in the fields of automobiles and home appliances, but it has high melt viscosity and poor flowability, which causes difficulty in processing, and is limited in some light-weight applications (such as thin-walled parts such as thin-walled housings and structural members). Acrylonitrile-styrene copolymer (SAN) has high fluidity and good compatibility with PC, and the fluidity of the polycarbonate material can be effectively improved by blending the SAN with PC, but the impact resistance of the material is deteriorated. The addition of an ABS toughening agent in a PC/SAN alloy is a common technical means for improving toughness, wherein the addition of rubber can improve the impact resistance of the material, but due to the large molecular weight of the rubber, the fluidity of the material can be reduced after the addition of the rubber.
In the prior art, Chinese patent application CN102372915A discloses a high-impact high-fluidity PC/ASA alloy material, which is prepared by blending polycarbonate resin, ASA graft copolymer, SAN resin, compatilizer (ABS-g-MAH, ASA-g-MAH, PS-g-MAH) and auxiliary agents such as lubricant, dispersant, antioxidant and the like, but the toughness of the material is improved a little, and the notch impact strength of the final PC/ASA alloy material is lower than 40kJ/m2And the requirement of thin-wall parts on the toughness of the material cannot be met.
Chinese patent application CN107446330B discloses a high-impact PC/ASA alloy material, which effectively improves the impact property of the material mainly by adding a toughening agent methyl methacrylate/silicon/acrylate copolymer and a compatilizer EMA-GMA, but the added toughening agent and EMA-GMA can cause the poor fluidity of the material and the difficult processing of the material while playing the effects of chain extension and toughening.
The Chinese patent application CN102532851A discloses a PC alloy material, wherein the fluidity of the material is improved by adding a phosphorus flow promoter, but the addition of the flow promoter brings negative effects to the toughness of the material, and particularly the problem that the toughness of the material is greatly reduced due to easy aging in an outdoor humid environment is solved.
Therefore, there is still a certain difficulty in obtaining polycarbonate materials with both high toughness and high fluidity. The invention mainly researches a polycarbonate material with high toughness and good fluidity, can meet the use requirement of thin-wall parts on the material, and has important significance for further widening the application of the polycarbonate material and improving the market competitiveness of the polycarbonate material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a polycarbonate alloy material which has high toughness and high fluidity.
The invention also aims to provide a preparation method of the polycarbonate alloy material.
The invention further aims to provide application of the polycarbonate alloy material.
The invention is realized by the following technical scheme:
the polycarbonate alloy material comprises the following components in parts by weight:
40-80 parts of PC resin;
5-25 parts of SAN resin;
2-10 parts of a toughening agent A;
1-8 parts of a toughening agent B;
the toughening agent A and the toughening agent B are selected from any one or more of acrylate graft copolymers with the acrylate rubber particle size of 50-200 nm or 300-800 nm;
the toughening agent A is an acrylate graft copolymer containing an acrylonitrile-styrene chain segment;
the toughening agent B is an acrylate graft copolymer containing a methyl methacrylate monomer skeleton;
in the polycarbonate alloy material, the weight ratio of a toughening agent with the acrylate rubber particle size of 50-200 nm to a toughening agent with the acrylate rubber particle size of 300-800 nm is (0.3-5): 1.
according to the invention, a certain amount of SAN resin is added into PC resin, and toughening agents with different acrylate rubber particle sizes are added at the same time, wherein the toughening agent B contains a methyl methacrylate monomer skeleton, has good compatibility with the PC resin, can be well dispersed in the PC phase, and plays a toughening role in the PC; the acrylonitrile-styrene chain segment in the toughening agent A has the same structure with SAN resin, has good compatibility with SAN resin, is more prone to be dispersed in SAN phase, can exert better toughening effect on SAN with poor toughness, further improves the toughness of the material, and simultaneously has good compatibility with the acrylate chain segment and PC resin, thereby effectively toughening and simultaneously improving the compatibility of two phases; the acrylate rubber with the particle size of 50-200 nm can be widely dispersed in a base material, microcracks can be prevented from being diffused when the material is impacted, the acrylate rubber with the particle size of 300-800 nm has a better effect on preventing large cracks when the material is impacted, the two copolymers are used according to a certain proportion, synergy is realized, the toughness of the material is effectively improved, and meanwhile, good fluidity is considered. Preferably, in the polycarbonate alloy material, the weight ratio of the toughening agent with the acrylate rubber particle size of 50-200 nm to the toughening agent with the acrylate rubber particle size of 300-800 nm is (0.5-3): 1.
preferably, the toughening agent A is an acrylate graft copolymer with the acrylate rubber particle size of 50-200 nm and an acrylate graft copolymer with the acrylate rubber particle size of 300-800 nm.
Preferably, the toughening agent B is an acrylate graft copolymer with the acrylate rubber particle size of 50-200 nm and an acrylate graft copolymer with the acrylate rubber particle size of 300-800 nm.
Preferably, the toughening agent A is an acrylate grafted acrylonitrile-styrene copolymer; the toughening agent B is an acrylate grafted methyl methacrylate copolymer.
Preferably, the weight ratio of the PC resin to the SAN resin is (2-9): 1; more preferably, the weight ratio of the PC resin to the SAN resin is (3-6): 1.
the PC resin is preferably a PC resin with the weight-average molecular weight of 15000-30000; more preferably a PC resin having a weight average molecular weight of 18000-25000.
Preferably, the content of acrylonitrile in the SAN resin is 18-35%; more preferably, the SAN resin has an acrylonitrile content of 22% to 28%.
The invention also provides a preparation method of the polycarbonate alloy material, which comprises the following steps: according to the proportion, the components are uniformly mixed and then added into a double-screw extruder for blending, and then are subjected to melt extrusion granulation to prepare the polycarbonate alloy material; wherein the extrusion temperature is 200-280 ℃; the screw rotation speed is 300-600 rpm.
The invention also provides application of the polycarbonate alloy material in thin-walled parts.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a certain amount of SAN resin is added into PC resin, and the acrylic ester graft copolymer containing acrylonitrile-styrene chain segments and the acrylic ester graft copolymer containing methyl methacrylate monomer skeletons with different acrylic ester rubber particle diameters are added at the same time, so that the toughness of the material can be effectively improved while the good fluidity is considered, the problem that the toughness and the fluidity of a polycarbonate material are difficult to maintain simultaneously in the prior art is solved, the polycarbonate alloy material with high toughness and high fluidity is prepared, and the processing requirement and the use requirement of a thin-wall part can be met.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw material sources used in the examples and comparative examples are as follows:
the raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PC resin 1: weight average molecular weight is 20000, PC H-2000F, Mitsubishi chemical;
PC resin 2: weight average molecular weight 30000, PC E-1000F, Mitsubishi chemical;
SAN resin 1: acrylonitrile content 25%, SAN NF2200AK, and stage reaction;
SAN resin 2: 20% of acrylonitrile, SAN 310N TR, brocade lake;
SAN resin 3: acrylonitrile content 32%, SAN 350N, brocade lake;
toughening agent A-1: acrylate graft acrylonitrile-styrene copolymer 1: the particle size of the acrylate rubber is 50-180nm, SX-006, Mitsubishi chemical;
toughening agent A-2: acrylate graft acrylonitrile-styrene copolymer 2: the particle size of the acrylate rubber is 350-500nm, XC640 and Jinhu lake;
toughening agent B-1: the acrylate grafted methyl methacrylate copolymer 1 has the acrylate rubber particle size of 50-180nm, Q800 and east China sea;
toughening agent B-2: the acrylate grafted methyl methacrylate copolymer 2 has the acrylate rubber particle size of 300-600nm, W-600A and Mitsubishi chemical.
Examples and comparative examples the preparation method of the polycarbonate alloy material: according to the mixture ratio of table 1/table 2, uniformly mixing the components, adding the mixture into a double-screw extruder for blending, and performing melt extrusion granulation to obtain a polycarbonate alloy material; wherein, the extrusion temperature is set to be 1-3 at 260 ℃, 4-5 at 245 ℃, 6-8 at 230 ℃ and 9-10 at 260 ℃; the screw speed was 400 rpm.
The related performance test method comprises the following steps:
melt flow rate: the test is carried out according to the standard ISO1133-2011, and the test condition is 260 ℃ and 5 kg;
notched izod impact strength: the test was carried out with reference to the standard ISO180-2019, 4mm thick injection molded notches.
Table 1: examples 1 to 19 the proportions (by weight) of the components and the results of the performance tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | |
| PC resin 1 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| PC resin 2 | ||||||||||
| SAN resin 1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| SAN resin 2 | 20 | |||||||||
| SAN resin 3 | 20 | |||||||||
| Flexibilizer A-1 | 4 | 4 | 4 | 4 | ||||||
| Flexibilizer A-2 | 6 | 4 | 2 | 4 | 2.5 | 2 | 7.5 | |||
| Flexibilizer B-1 | 4 | 4 | 6 | 7.5 | 8 | 2.5 | ||||
| Flexibilizer B-2 | 6 | 2 | 4 | 6 | 6 | |||||
| Notched impact strength kJ/m2 | 68.9 | 70.3 | 72.7 | 73.3 | 65.2 | 60.5 | 54.1 | 53.8 | 58.9 | 59.2 |
| Melt flow rate g/10min | 28.3 | 28.4 | 28.2 | 28.6 | 30.4 | 31.2 | 32.1 | 25.5 | 27.8 | 28.1 |
Table 1 is shown below:
| example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 | Example 19 | |
| PC resin 1 | 70 | 55 | 70 | 45 | 50 | 80 | 60 | 60 | |
| PC resin 2 | 60 | ||||||||
| SAN resin 1 | 20 | 10 | 25 | 25 | 5 | 20 | 15 | 20 | 20 |
| SAN resin 2 | |||||||||
| SAN resin 3 | |||||||||
| Flexibilizer A-1 | 4 | 4 | 4 | 10 | 2 | 7 | 1 | 3 | |
| Flexibilizer A-2 | 3 | 3 | 1 | ||||||
| Flexibilizer B-1 | 5 | 6 | 2 | ||||||
| Flexibilizer B-2 | 6 | 6 | 6 | 2 | 1 | 3 | 4 | ||
| Notched impact strength kJ/m2 | 62.5 | 60.1 | 59.6 | 63.2 | 65.6 | 67.8 | 68.4 | 73.5 | 76.5 |
| Melt flow rate g/10min | 20.1 | 23.3 | 32.5 | 34.1 | 25.8 | 31.6 | 26.7 | 29.5 | 30.5 |
Table 2: comparative examples 1-8, the proportion of each component (by weight) and the results of each performance test
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| PC resin 1 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| SAN resin 1 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Flexibilizer A-1 | 4 | 4 | 10 | |||||
| Flexibilizer A-2 | 6 | 4 | 10 | |||||
| Flexibilizer B-1 | 4 | 6 | 10 | |||||
| Flexibilizer B-2 | 6 | 6 | 10 | |||||
| Notched impact strength kJ/m2 | 47.9 | 49.5 | 40.7 | 48.5 | 35.9 | 41.1 | 38.3 | 43.8 |
| Melt flow rate g/10min | 28.5 | 27.7 | 31.3 | 19.6 | 33.5 | 19.9 | 32.8 | 19.2 |
As can be seen from the above examples and comparative examples, according to the invention, a certain amount of SAN resin is added into PC resin, and simultaneously, acrylate grafted acrylonitrile-styrene copolymer and acrylate grafted methyl methacrylate copolymer with different acrylate rubber particle sizes are added, so that the toughness of the material can be effectively improved, and good fluidity is also achieved, and the prepared polycarbonate alloy material has high toughness and good melt fluidity.
Claims (10)
1. The polycarbonate alloy material is characterized by comprising the following components in parts by weight:
40-80 parts of PC resin;
5-25 parts of SAN resin;
2-10 parts of a toughening agent A;
1-8 parts of a toughening agent B;
the toughening agent A and the toughening agent B are selected from any one or more of acrylate graft copolymers with the acrylate rubber particle size of 50-200 nm or 300-800 nm;
the toughening agent A is an acrylate graft copolymer containing an acrylonitrile-styrene chain segment;
the toughening agent B is an acrylate graft copolymer containing a methyl methacrylate monomer skeleton;
in the polycarbonate alloy material, the weight ratio of a toughening agent with the acrylate rubber particle size of 50-200 nm to a toughening agent with the acrylate rubber particle size of 300-800 nm is (0.3-5): 1.
2. the polycarbonate alloy material according to claim 1, wherein the weight ratio of the toughening agent with the acrylate rubber particle size of 50-200 nm to the toughening agent with the acrylate rubber particle size of 300-800 nm in the polycarbonate alloy material is (0.5-3): 1.
3. the polycarbonate alloy material according to claim 1, wherein the toughening agent A is an acrylate graft copolymer with an acrylate rubber particle size of 50-200 nm and an acrylate graft copolymer with an acrylate rubber particle size of 300-800 nm.
4. The polycarbonate alloy material according to claim 1, wherein the toughening agent B is an acrylate graft copolymer with an acrylate rubber particle size of 50-200 nm and an acrylate graft copolymer with an acrylate rubber particle size of 300-800 nm.
5. The polycarbonate alloy material of claim 1, wherein the toughening agent a is an acrylate grafted acrylonitrile-styrene copolymer; the toughening agent B is an acrylate grafted methyl methacrylate copolymer.
6. The polycarbonate alloy material of claim 1, wherein the weight ratio of the PC resin to the SAN resin is (2-9): 1; preferably, the weight ratio of the PC resin to the SAN resin is (3-6): 1.
7. the polycarbonate alloy material according to claim 1, wherein the weight average molecular weight of the PC resin is 15000-30000; preferably, the weight average molecular weight of the PC resin is 18000-25000.
8. The polycarbonate alloy material of claim 1, wherein the SAN resin has an acrylonitrile content of 18% to 35%; preferably, the SAN resin contains 22% -28% of acrylonitrile.
9. The method for preparing the polycarbonate alloy material according to any one of claims 1 to 8, comprising the steps of: according to the proportion, the components are uniformly mixed and then added into a double-screw extruder for blending, and then are subjected to melt extrusion granulation to prepare the polycarbonate alloy material; wherein the extrusion temperature is 200-280 ℃; the screw rotation speed is 300-600 rpm.
10. Use of the polycarbonate alloy material according to any one of claims 1-8 in thin-walled articles.
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| CN115322551A (en) * | 2022-07-26 | 2022-11-11 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
| CN115584114A (en) * | 2022-08-25 | 2023-01-10 | 金发科技股份有限公司 | Polycarbonate alloy composition and preparation method and application thereof |
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| CN114196185B (en) | 2024-02-13 |
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