CN117887234A - Mineral filled PC/ABS alloy material with high rigidity, high toughness and low linear expansion and preparation method thereof - Google Patents
Mineral filled PC/ABS alloy material with high rigidity, high toughness and low linear expansion and preparation method thereof Download PDFInfo
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- CN117887234A CN117887234A CN202311803043.9A CN202311803043A CN117887234A CN 117887234 A CN117887234 A CN 117887234A CN 202311803043 A CN202311803043 A CN 202311803043A CN 117887234 A CN117887234 A CN 117887234A
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 46
- 239000011707 mineral Substances 0.000 title claims abstract description 46
- 229920007019 PC/ABS Polymers 0.000 title claims abstract description 30
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 21
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 17
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 9
- 239000004417 polycarbonate Substances 0.000 claims abstract description 9
- 239000012764 mineral filler Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004611 light stabiliser Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- -1 olefin anhydride Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 description 27
- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-rigidity high-toughness low-linear-expansion mineral filled PC/ABS alloy material and a preparation method thereof, wherein the material is prepared from the following raw materials in parts by weight: 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer (ABS); 60-80 parts of bisphenol A type Polycarbonate (PC), 10-25 parts of mineral filler, 0.5-2 parts of special dispersing agent, 0.5 part of light stabilizer and 0.5 part of antioxidant; the mineral filled PC/ABS alloy with high rigidity and high toughness obtained by adopting the technical scheme can be used for parts with high requirements on dimensional accuracy on automobiles or electronic appliances. Compared with the traditional non-reinforced non-filled PC/ABS alloy, the material has the advantages that the rigidity is obviously improved on the basis of keeping the high toughness of PC/ABS, and the application range of the PC/ABS alloy is expanded.
Description
Technical Field
The invention relates to a high-rigidity high-toughness low-linear-expansion mineral filled PC/ABS alloy and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
In recent years, the requirements of light weight and thin wall in the automobile and household electronic industry are that new requirements are put on the traditional PC/ABS alloy. The light weight requires the engineering plastic to have higher toughness and heat resistance to replace part of the metal material, while the thin wall requires the engineering plastic to have higher rigidity so that it does not deform or deforms less at a thinner wall thickness. In addition, the front end design of the parts is diversified, the installation precision of engineering plastics is required to be higher, the linear expansion coefficient of the engineering plastics is generally higher than that of metal or ceramic materials, the tolerance gap of plastic parts can be changed along with the alternation of four seasons, and the attractiveness and the use are affected, so that the PC/ABS with high rigidity, high toughness and low linear expansion is a significant subject in development.
The linear expansion coefficient of PC/ABS can be effectively reduced by adding mineral filler, and higher rigidity can be obtained. However, the introduction of minerals can greatly reduce the toughness of the material, and the three are difficult to achieve at the same time. Aiming at the problem, in CN104387740A, surface modification is attempted on mineral filler, then the obtained filler is introduced into PC/ABS, although the modified mineral powder can be better dispersed, the impact toughness is improved, the obtained alloy has lower rigidity, the cost of the mineral powder with surface modification is higher, and the process is more complicated. In CN104004332a, inorganic nanoparticles are introduced to reduce the shrinkage rate of the material, but the nanoscale cannot be achieved by minerals such as talcum powder and wollastonite which are common in the actual market, and if the minerals are required to be ground into nanoscale, the cost is greatly increased, so that the mass production is not facilitated. While barium sulfate, magnesium sulfate whisker and nano silica filler are introduced into CN111154247A, and high toughness can be obtained on the premise of reducing the linear expansion coefficient, high rigidity cannot be obtained because the micro morphology of the barium sulfate and the silica is square instead of the anisotropy of talcum powder and wollastonite.
To overcome the above drawbacks, we prefer to use talc or acicular wollastonite having a microstructure of platelets. Secondly, talcum powder and wollastonite are alkaline, and PC is degraded, so that mechanical properties are reduced, and therefore, a special dispersing agent with acidity is added, and further good dispersion of minerals can be facilitated in the acid-base neutralization process.
The finally obtained mineral filled PC/ABS alloy not only has high toughness of common PC/ABS, but also obtains lower linear expansion coefficient and higher rigidity.
Disclosure of Invention
In order to achieve the aim, the invention provides a high-rigidity high-toughness low-linear-expansion mineral filled PC/ABS alloy and a preparation method thereof, wherein the PC/ABS alloy is prepared from the following raw materials in parts by weight: the material is prepared from the following raw materials in parts by weight: 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer (ABS); 60-80 parts of bisphenol A type Polycarbonate (PC), 10-25 parts of mineral filler, 0.5-2 parts of special dispersing agent, 0.5 part of light stabilizer and 0.5 part of antioxidant;
the PC is preferably melt-finger 10g/10min;
the mineral filler is common non-surface modified talcum or wollastonite or mica flakes and other minerals, and the mesh number of the mineral is more preferably 3000-10000;
the special dispersant is a polymer of alpha-olefin and olefin acid or olefin anhydride;
the light absorber is hindered amine light stabilizer and UV absorber;
the antioxidant is hindered phenol antioxidant and phosphite antioxidant.
The preparation method of the material comprises the following steps:
1) Firstly, preparing the mineral powder in claim 1 into mineral master batches with 75% concentration of an ABS base material: 25 parts of ABS,75 parts of mineral powder by weight, 0.5-2 parts of special dispersing agent and 0.2 part of antioxidant are uniformly mixed and then added into an internal mixer, fully banburying is carried out for 15min at 220 ℃, and then single screw extrusion is carried out to obtain mineral master batches of ABS base materials;
2) Mixing the dried mineral master batch, PC and the rest auxiliary agent, continuously and uniformly adding the mixture into a main machine barrel of a double-screw extruder with the screw diameter of 35mm and the length-diameter ratio L/D=40 by using a double-screw feeder, controlling the temperature of the main machine barrel to 90 ℃, 180 ℃, 240 ℃, 250 ℃ and 250 ℃ in a sectional manner, and cutting the extruded material into granules after cooling by using a water tank to obtain the product.
Compared with the prior art, the PC/ABS alloy prepared by the method has the advantages that on the basis of ensuring good toughness, minerals are introduced, so that the linear expansion coefficient of the alloy is reduced, and the rigidity of the material is improved.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the invention but not to limit it.
The raw materials used in the invention are as follows:
ABS: cheng Xi an Olympic Polymer (Zhangjinggang) Co., ltd., trade mark 8434;
PC: wanhua chemistry, brand A1100;
mineral powder: imperys, france, brand 00S;
special dispersing agent: japanese UMG, brand S601N;
an antioxidant: commercial 1076 and 618, holly, in a 1:1 ratio;
weather-resistant agent: 234 and 770DF, commercially available, in a 1:1 ratio;
the product performance testing method comprises the following steps:
vicat softening temperature: test condition B50 according to ISO 306;
notched impact toughness: test conditions were 23℃according to ISO 179-1;
melt index: test conditions according to ISO 1133-1: 260 ℃ x 5kg;
tensile properties: test conditions according to ISO 527: 50mm/min,23 ℃;
flexural modulus: test conditions according to ISO 178: 2mm/min,64mm;
flexural strength: test conditions according to ISO 178: 2mm/min,64mm;
linear expansion coefficient: according to ISO11359-2, the temperature ranges from minus 30 ℃ to 80 ℃;
where the linear expansion coefficient is required to indicate the flow direction and the perpendicular flow direction.
Comparative examples 1 to 3 and examples 1 to 4
Mixing the dried raw materials, continuously and uniformly adding the mixture into a main cylinder of a double-screw extruder with the screw diameter of 35mm and the length-diameter ratio of L/D=40 by using a double-screw feeder, the main machine barrel is controlled to have the temperature (from a feed inlet to a machine head outlet) of 90 ℃, 180 ℃, 220 ℃, 230 ℃ and 230 ℃ in a sectional manner, the rotating speed of the twin screw is 400-600 revolutions per minute, and the extruded material strip is cooled by a water tank and then cut into granules to obtain the product.
Example 5
The mineral powder is prepared into mineral master batches with 75% concentration of ABS base material: 25 parts of ABS,75 parts of mineral powder by weight, 0.5-2 parts of special dispersing agent and 0.2 part of antioxidant are uniformly mixed and then added into an internal mixer, fully banburying is carried out for 15min at 220 ℃, and then the mineral master batch of the ABS substrate is obtained through single screw extrusion. The subsequent steps are the same as in examples 1-4.
All the products obtained above were dried in a forced air oven at 85℃for 4 hours and then injection molded into standard bars and templates using a plastic injection molding machine at a temperature of 230 ℃. The molded bars and templates were immediately left at room temperature for at least 24 hours for performance testing and the test results are as follows.
(1) Test results obtained by directly blending, extruding and granulating all raw materials
From the test results of the above table, it can be seen that:
1. as can be seen from example 1 and comparative examples 1-2, on the one hand, only the addition of mineral powder to PC/ABS has a significant increase in rigidity, i.e. flexural strength and flexural modulus, in particular flexural modulus, but a substantial decrease in toughness. On the other hand, the mineral powder and the special dispersing agent are simultaneously introduced, so that the influence of the mineral powder on toughness can be weakened as much as possible while the higher rigidity is maintained, and the notch impact strength of the embodiment 1 is somewhat reduced compared with that of the comparative example 1, but can still be regarded as a high-toughness material.
2. As can be seen from examples 1 to 4 and comparative examples 1 to 3, increasing the amount of the ore powder increases the rigidity of PC/ABS, while the toughness decreases, and when the amount of the ore powder exceeds 25 parts by weight, even if a special dispersant is added, the substantial decrease in toughness cannot be counteracted. In addition, the dosage of the special dispersing agent is increased, and the toughness is not greatly improved.
3. It can be seen from examples 1 and 5 that the ore powder is first made into a masterbatch and then added, and is directly added in a one-step process, the former can obtain higher toughness. And the master batch can avoid more dust pollution in production, but the production cost is higher than that of the master batch. Therefore, a material manufacturer can flexibly select the two modes according to the actual demands, and the two modes can obtain the mineral filled PC/ABS alloy with high rigidity, high toughness and low linear expansion.
While specific embodiments of the present invention have been described, it should be understood that the invention is not limited to the particular embodiments described above, and modifications within the scope of the invention should be made.
Claims (10)
1. A high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material is characterized in that: the material is prepared from the following raw materials in parts by weight: 20-40 parts by weight of acrylonitrile-butadiene-styrene copolymer (ABS); 60-80 parts of bisphenol A type Polycarbonate (PC), 10-25 parts of mineral filler, 0.5-2 parts of special dispersing agent, 0.5 part of light stabilizer and 0.5 part of antioxidant.
2. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the melt index of the ABS is 10-15g/10min.
3. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the PC is preferably phosgene-process bisphenol A polycarbonate with a melt index of 10g/10 min.
4. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the mineral filler is common mineral such as non-surface modified talcum or wollastonite or mica sheet.
5. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 4, wherein the material is characterized in that: the mesh number of the mineral filler is between 3000 and 10000.
6. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the special dispersant is a polymer of alpha-olefin and olefin acid or olefin anhydride.
7. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 6, wherein the material is characterized in that: the special dispersant is a polymer of AS and an olefine acid or an olefine anhydride.
8. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the light absorber is hindered amine light stabilizer and UV absorber.
9. The high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy material according to claim 1, wherein: the antioxidant is hindered phenol antioxidant and phosphite antioxidant.
10. The method for preparing the high-rigidity high-toughness low-linear-expansion mineral-filled PC/ABS alloy according to any one of claims 1 to 9, characterized by comprising the steps of:
1) Firstly, preparing the mineral powder in claim 1 into mineral master batches with 75% concentration of an ABS base material: 25 parts of ABS,75 parts of mineral powder by weight, 0.5-2 parts of special dispersing agent and 0.2 part of antioxidant are uniformly mixed and then added into an internal mixer, fully banburying is carried out for 15min at 220 ℃, and then single screw extrusion is carried out to obtain mineral master batches of ABS base materials;
2) Mixing the dried mineral master batch, PC and the rest auxiliary agent, continuously and uniformly adding the mixture into a main machine barrel of a double-screw extruder with the screw diameter of 35mm and the length-diameter ratio L/D=40 by using a double-screw feeder, controlling the temperature of the main machine barrel to be 90 ℃, 180 ℃, 240 ℃, 250 ℃ and 250 ℃ in sequence from a feeding port to a machine head outlet, cooling the extruded material by using a water tank, and cutting the extruded material into granules to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311803043.9A CN117887234A (en) | 2023-12-26 | 2023-12-26 | Mineral filled PC/ABS alloy material with high rigidity, high toughness and low linear expansion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311803043.9A CN117887234A (en) | 2023-12-26 | 2023-12-26 | Mineral filled PC/ABS alloy material with high rigidity, high toughness and low linear expansion and preparation method thereof |
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| Publication Number | Publication Date |
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| CN117887234A true CN117887234A (en) | 2024-04-16 |
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| CN202311803043.9A Pending CN117887234A (en) | 2023-12-26 | 2023-12-26 | Mineral filled PC/ABS alloy material with high rigidity, high toughness and low linear expansion and preparation method thereof |
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| Country | Link |
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| CN (1) | CN117887234A (en) |
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2023
- 2023-12-26 CN CN202311803043.9A patent/CN117887234A/en active Pending
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