CN110982238B - Polycarbonate alloy material and preparation method thereof - Google Patents
Polycarbonate alloy material and preparation method thereof Download PDFInfo
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- CN110982238B CN110982238B CN201911311628.2A CN201911311628A CN110982238B CN 110982238 B CN110982238 B CN 110982238B CN 201911311628 A CN201911311628 A CN 201911311628A CN 110982238 B CN110982238 B CN 110982238B
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- polycarbonate
- alloy material
- acrylonitrile
- styrene
- butadiene
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- 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
Abstract
The invention discloses a polycarbonate alloy material and a preparation method thereof, wherein the alloy material mainly comprises the following components: 20 to 85 parts by weight of a polycarbonate; 10-70 parts by weight of acrylonitrile-styrene-butadiene; 1-10 parts by weight of a fluorinated siloxane polymer. Compared with the common polycarbonate alloy material, the polycarbonate alloy material has the advantage that the pungent smell is remarkably reduced.
Description
Technical Field
The invention relates to a polycarbonate alloy material with low pungent smell and a preparation method thereof, belonging to the field of materials.
Background
The polycarbonate/acrylonitrile-styrene-butadiene alloy prepared by blending polycarbonate and acrylonitrile-styrene-butadiene according to a certain proportion is a polycarbonate modified product with mature technology, wide application range and huge yield at present. The polycarbonate/acrylonitrile-styrene-butadiene alloy achieves a good complementation of the properties of the two materials polycarbonate and acrylonitrile-styrene-butadiene: on one hand, the polycarbonate improves the heat resistance, tensile property and bending property of acrylonitrile-styrene-butadiene; on the other hand, the acrylonitrile-styrene-butadiene reduces the cost of the polycarbonate, improves the processability of the polycarbonate and reduces the internal stress of the polycarbonate product.
Polycarbonate/acrylonitrile-styrene-butadiene blends are widely used in the automotive field. However, because small molecules with pungent odor generated by degradation remain in acrylonitrile-styrene-butadiene, the common polycarbonate/acrylonitrile-styrene-butadiene blend cannot meet the requirement of automotive interior parts with high odor requirements.
Currently, there are two methods for acrylonitrile-styrene-butadiene preparation, bulk and emulsion. Due to the difference of the production process, the acrylonitrile-styrene-butadiene prepared by the bulk method contains smaller molecules with pungent odor than the acrylonitrile-styrene-butadiene prepared by the emulsion method. Thus, the odor of acrylonitrile-styrene-butadiene prepared by the bulk process is lower than that of acrylonitrile-styrene-butadiene prepared by the emulsion process. Acrylonitrile-styrene-butadiene prepared in bulk is generally selected as the starting material for the low odor polycarbonate/acrylonitrile-styrene-butadiene blend.
In addition, polycarbonate/acrylonitrile-styrene-butadiene blends are obtained by extrusion granulation, during which the rotation speed of the screw may affect the odor of the blend. On one hand, in the process of mixing materials by the extruder, the rotation of the screw can promote the diffusion of small molecules contained in acrylonitrile-styrene-butadiene, and the faster the rotation speed is, the more the small molecules are diffused, which is beneficial to reducing the odor of the blend; however, the shear force generated by the rotation of the screw may cause the degradation of the material, generating new small molecules, and the more rapid the rotation speed, the more severe the degradation, which may enhance the odor of the blend. Therefore, the problem that pungent odor cannot be removed still exists when acrylonitrile-styrene-butadiene prepared by a bulk method is used as a polycarbonate alloy material, and the application of acrylonitrile-styrene-butadiene in the field of products with high requirements on odor, such as automotive upholsteries and the like, is limited.
Disclosure of Invention
The invention aims to provide a polycarbonate alloy material and a preparation method thereof. The polycarbonate alloy material has extremely low odor.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polycarbonate alloy material, the alloy material comprising the following components:
20 to 85 parts by weight of a polycarbonate;
10-70 parts by weight of acrylonitrile-styrene-butadiene;
1 to 10 parts by weight of a fluorinated siloxane polymer;
preferably, the alloy material comprises the following components:
25 to 80 parts by weight of a polycarbonate;
15-65 parts by weight of acrylonitrile-styrene-butadiene;
2-8 parts by weight of a fluorinated siloxane polymer.
The polycarbonate alloy material with low odor is one or more of aromatic polycarbonate and aliphatic polycarbonate, and bisphenol A polycarbonate is preferred. Preferably, the melt flow index of PC is between 3 and 65g/10min, preferably between 5 and 50g/10min, more preferably between 7 and 35g/10min at test conditions of 300 ℃ and 1.2 kg. The higher the melt index of PC, the better the fluidity of PC, and the better the fluidity of the composition; however, the higher the PC melt index, the lower the PC molecular weight, and the poorer the impact properties of the composition. Thus, an advantage of limiting the PC melt index is a balance of composition flowability and impact properties. The commercial products of polycarbonate which can be selected are CLARNATE series products of Wanhua chemistry, MAKROLON series products of Corsai, LEXAN series products of Sabbick, PANLITE series products of Dimai, TARFLON series products of Mitsubishi chemistry, PRIMALLOY series products of Mitsubishi chemistry, INFINO series products of Mitsubishi, LUPOY series products of LG chemistry, WONDERLITE series products of Qimei industry, etc. Such as a1077 produced by wanhua chemistry.
According to the polycarbonate alloy material, the acrylonitrile-styrene-butadiene is prepared by a bulk method, and preferably, the mass content of butadiene is 10-30%, the mass content of acrylonitrile is 15-35%, and the mass content of styrene is 50-70%. Preferably, the melt flow index of ABS is between 5 and 60g/10min, preferably between 8 and 50g/10min, at test conditions of 220 ℃ and 10 kg. Commercially available acrylonitrile-styrene-butadiene products are available from Shanghai Gaoqiao petrochemical company, Inc. (e.g., ABS-8391 from Shanghai Gaoqiao), POLYLAC series from Qimei industries, and MAGNUM series from Shengxi ao.
The low-odor polycarbonate alloy material has the advantages that the main chain of the fluorinated siloxane polymer is a soft and smooth organic silicon chain, the side chain is an organic fluorine chain, and the structural formula is shown as the formula (1):
wherein R is1And R2Each independently is a hydrogen atom, or a hydrocarbon group of carbon number 1 to 18, or a fluorocarbon group of carbon number 1 to 18, and R1And R2At least one of which is a fluorocarbon group, and n is 1 to 200, preferably 10 to 160. The mass content of fluorine in the fluorinated siloxane polymer is 10-50%. The number average molecular weight of the fluorinated siloxane is generally in the range of 2000-30000; preferably, the fluorinated siloxane polymer is one or more of hydroxy fluorosilicone oil, polytrifluoropropylmethylsiloxane, polymethylnonafluorohexylsiloxane, trifluoropropylmethylcyclotrisiloxane, vinyl fluorosilicone oil and the like.
The low-odor polycarbonate alloy material can be optionally added with 0.1-15 parts of other auxiliary agents; the auxiliary agent is selected from one or more of flame retardant, toughening agent, compatibilizer, antioxidant, lubricant, ultraviolet absorbent, infrared absorbent, heat stabilizer, metal deactivator, colorant, coupling agent, foaming agent, hydrolysis-resistant agent, chain extender, flow modifier, delustering agent, antistatic agent, reinforcing agent, filler, light diffusant, metal pigment and pearl powder.
The antioxidant is one or more of hindered phenol, phosphite, thioester, benzofuran, acryloyl modified phenol and hydroxylamine antioxidant.
The lubricant is one or more of fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and derivatives thereof, amide waxes, saturated hydrocarbons, polyolefin waxes and derivatives thereof, organic silicon and silicone powder, organic fluorine and the like.
The ultraviolet absorbent is one or a combination of more of benzophenone, benzotriazole, triazine, benzoate, cyanoacrylate and phenylimidazole.
Further, the polycarbonate alloy material with low odor is obtained by mixing the raw materials and then granulating the mixture by using a double-screw extruder, wherein the screw rotating speed is 700-1000 revolutions per minute, and preferably 800-950 revolutions per minute.
The low-odor polycarbonate alloy material can selectively use the additives according to the performance characteristics of the product, and achieves the purposes of improving the processing performance and the thermal-oxidative aging resistance of the polycarbonate alloy.
The invention also provides a preparation method of the low-odor polycarbonate alloy material, which comprises the following steps:
(1) premixing: adding polycarbonate, acrylonitrile-styrene-butadiene, fluorinated siloxane polymer and optional auxiliary agent into a mixer according to the proportion and stirring to obtain premix;
(2) extruding: and granulating the obtained premix by using a double-screw extruder at the screw rotating speed of 700-1000 revolutions per minute to obtain the low-odor polycarbonate alloy material granules.
The invention has the positive effects that: the reduction in odor of polycarbonate alloys is achieved by the addition of fluorinated siloxane polymers and by setting high extruder screw speeds. The high extruder screw speed greatly promotes the dispersion of the irritating small molecules originally contained in the raw material. The fluorinated siloxane polymer has lower viscosity than polycarbonate and acrylonitrile-styrene-butadiene, and is easier to deform and bear most of strong shearing force generated by high-speed rotation of the screw in the process of mixing materials by the screw of the extruder. Thus, the shear forces to which the polycarbonate and acrylonitrile-styrene-butadiene are subjected can be relatively weak, which does not cause significant degradation of the polycarbonate and acrylonitrile-styrene-butadiene to produce small molecules. Meanwhile, the fluorinated siloxane polymer is stable in molecular structure, and although the fluorinated siloxane polymer bears the strong shearing force generated by high-speed rotation of most screws, the fluorinated siloxane polymer cannot be degraded to generate small molecules. Combining the above factors, the fluorinated siloxane polymer and the high extruder screw speed settings synergistically achieve the goal of preparing low odor polycarbonate/acrylonitrile-styrene-butadiene blends.
Detailed Description
The invention is further described below in connection with the following examples for the purpose of better understanding and practice, but the invention is not limited to the examples listed and is intended to include any other known variations within the scope of the invention as claimed.
The preparation process of the materials is as follows: in both the comparative example and the embodiment, according to the corresponding formula, the materials such as polycarbonate, acrylonitrile-styrene-butadiene and the like are put into a high-speed mixer to be uniformly mixed, the temperature of the sleeve of the extruder is 250 ℃ plus the temperature, the rotating speed of the screw of the extruder is 1000rpm plus the temperature, and the mixture is subjected to the procedures of blending, strip pulling, water cooling, air drying, grain cutting and drying to obtain the product.
The performance test was as follows:
and (3) odor test: the polycarbonate alloy bars were tested for odor according to standard VDA 270.
The compositions of the comparative examples and examples are as follows:
a1107: bisphenol A polycarbonate produced by an interfacial phosgene method has a melt flow index of 10g/10min (300 ℃,1.2kg), and is produced by Wanhua chemical group Limited company;
ABS-8391: acrylonitrile-styrene-butadiene prepared by a bulk method is produced by Shanghai Gaoqiao petrochemical company Limited;
DX-8011: hydroxy fluorosilicone oil, produced by Daxi corporation;
PMNFHS: polymethylnonafluorohexylsiloxane, manufactured by Mirrida;
D3F: trifluoropropylmethylcyclotrisiloxane, produced by Xinrunde corporation;
AX 8900: a compatibilizer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, manufactured by arkema;
1010: antioxidants, manufactured by basf corporation;
168: antioxidants, manufactured by basf corporation;
PETS: pentaerythritol stearate, lubricant, manufactured by the company LONGSHA, USA.
The formulations and properties of the polycarbonate/acrylonitrile-styrene-butadiene alloy materials of comparative examples 1-5 and examples 1-6 are detailed in Table 1.
By comparing examples 1-6 with comparative examples 1-5, it can be seen that increasing the extruder screw speed without adding PTFPMS did not significantly reduce the odor of the polycarbonate/acrylonitrile-styrene-butadiene alloy material. At lower extruder screw speeds (200 rpm), the addition of PTFPMS did not reduce the odor of the polycarbonate/acrylonitrile-styrene-butadiene alloy material. While the addition of PTFPMS at high extruder screw speeds (700-.
Under the condition of not adding PTFPMS, the rotating speed of the screw of the extruder is increased, original irritant micromolecules contained in the raw materials of the polycarbonate/acrylonitrile-styrene-butadiene alloy material are volatilized and accelerated to be reduced, but strong shearing at the high rotating speed of the screw of the extruder can cause the polycarbonate/acrylonitrile-styrene-butadiene to be degraded to generate a large amount of new irritant micromolecules, so that the rotating speed of the screw of the extruder is increased, and the odor of the polycarbonate/acrylonitrile-styrene-butadiene alloy material cannot be obviously reduced.
At a lower extruder screw rotation speed (200 rpm), the volatilization rate of the originally contained irritant small molecules in the raw materials of the polycarbonate/acrylonitrile-styrene-butadiene alloy material is slower and a large amount of the irritant small molecules are reserved, and meanwhile, the weak shearing at the low extruder screw rotation speed does not cause the obvious degradation of the polycarbonate/acrylonitrile-styrene-butadiene so as to generate a large amount of new irritant small molecules. After the PTFPMS is added, the volatilization and degradation processes of small molecules of the polycarbonate/acrylonitrile-styrene-butadiene alloy material are not obviously influenced, so that the odor of the odor polycarbonate/acrylonitrile-styrene-butadiene alloy material is not obviously changed.
Under the conditions of setting high screw rotation speed of the extruder (700-; on the other hand, the fluorinated siloxane polymer has lower viscosity than polycarbonate and acrylonitrile-styrene-butadiene, and is easier to deform to bear most of strong shearing force generated by high-speed rotation of the screw in the process of mixing materials by the screw of the extruder, so that the shearing force applied to the polycarbonate and the acrylonitrile-styrene-butadiene is relatively weaker, and the polycarbonate and the acrylonitrile-styrene-butadiene cannot be obviously degraded to generate small molecules. Meanwhile, the fluorinated siloxane polymer is stable in molecular structure, and although the fluorinated siloxane polymer bears the strong shearing force generated by high-speed rotation of most screws, the fluorinated siloxane polymer cannot be degraded to generate small molecules. The fluorinated siloxane polymer and the set high extruder screw speed synergistically achieve the goal of producing low odor polycarbonate/acrylonitrile-styrene-butadiene blends.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims.
Claims (14)
1. A polycarbonate alloy material, characterized in that the alloy material comprises the following components:
20 to 85 parts by weight of a polycarbonate;
10-70 parts by weight of acrylonitrile-styrene-butadiene;
1 to 10 parts by weight of a fluorinated siloxane polymer;
the polycarbonate alloy material is obtained by mixing the components and then granulating by using a double-screw extruder, wherein the rotating speed of the screw is 700-1000 revolutions per minute.
2. The polycarbonate alloy material of claim 1, wherein the alloy material comprises the following components:
25 to 80 parts by weight of a polycarbonate;
15-65 parts by weight of acrylonitrile-styrene-butadiene;
2-8 parts by weight of a fluorinated siloxane polymer.
3. The polycarbonate alloy material of claim 1, wherein the polycarbonate is one or more of an aromatic polycarbonate and an aliphatic polycarbonate.
4. The polycarbonate alloy material of claim 3, wherein the polycarbonate is a bisphenol A polycarbonate.
5. The polycarbonate alloy material of claim 3, wherein the polycarbonate has a melt flow index of between 3 and 65g/10min at test conditions of 300 ℃ and 1.2 kg.
6. The polycarbonate alloy material of claim 5, wherein the polycarbonate has a melt flow index of between 5 and 50g/10min at test conditions of 300 ℃ and 1.2 kg.
7. The polycarbonate alloy material of claim 6, wherein the polycarbonate has a melt flow index of between 7 and 35g/10min at test conditions of 300 ℃ and 1.2 kg.
8. The polycarbonate alloy material according to any one of claims 1 to 7, wherein the acrylonitrile-styrene-butadiene is prepared by a bulk method, and has a butadiene content of 10 to 30% by mass, an acrylonitrile content of 15 to 35% by mass, and a styrene content of 50 to 70% by mass.
9. The polycarbonate alloy material according to any one of claims 1-7, wherein the fluorinated siloxane polymer backbone is a compliant silicone chain, the side chains are organofluorine chains, and the structural formula is represented by formula (1):
wherein R is1And R2Is a hydrogen atom, or a hydrocarbon group of carbon number 1 to 18, or a fluorocarbon group of carbon number 1 to 18, and R1And R2At least one of which is a fluorocarbon group, n is 1 to 200; the mass content of fluorine in the fluorinated siloxane polymer is 10-50%.
10. The polycarbonate alloy material of claim 9, wherein n is 10-160.
11. The polycarbonate alloy material of claim 9, wherein the fluorinated siloxane polymer is one or more of hydroxyfluorosilicone oil, polytrifluoropropylmethylsiloxane, polymethylnonafluorohexylsiloxane, trifluoropropylmethylcyclotrisiloxane, and vinyl fluorosilicone oil.
12. The polycarbonate alloy material of any of claims 1-7, wherein 0.1-15 parts of other additives are optionally added; the auxiliary agent is selected from one or more of flame retardant, toughening agent, compatibilizer, antioxidant, lubricant, ultraviolet absorbent, infrared absorbent, heat stabilizer, metal deactivator, colorant, coupling agent, foaming agent, hydrolysis-resistant agent, chain extender, flow modifier, delustering agent, antistatic agent, reinforcing agent, filler, light diffusant, metal pigment and pearl powder.
13. The polycarbonate alloy material as defined in any one of claims 1-7, wherein the screw rotation speed is 800-950 rpm.
14. The method of making the polycarbonate alloy material of any of claims 1-13, comprising the steps of:
(1) premixing: adding polycarbonate, acrylonitrile-styrene-butadiene, fluorinated siloxane polymer and optional auxiliary agent into a mixer according to the proportion and stirring to obtain premix;
(2) extruding: and granulating the obtained premix by using a double-screw extruder, wherein the screw rotating speed of the extruder is 700-1000 revolutions per minute, and obtaining the low-odor polycarbonate alloy material granules.
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| CN105566834B (en) * | 2014-11-10 | 2018-11-23 | 合肥杰事杰新材料股份有限公司 | A kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell and preparation method |
| WO2017141779A1 (en) * | 2016-02-18 | 2017-08-24 | スターライト工業株式会社 | Nanofiber dispersion, method for producing nanofiber dispersion, powdery nanofibers obtained from dispersion, resin composition including said powdery nanofibers, and molding material for 3d printer in which said resin composition is used |
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