CN112646340A - High-temperature oil-resistant flame-retardant bio-based polycarbonate material and preparation method thereof - Google Patents
High-temperature oil-resistant flame-retardant bio-based polycarbonate material and preparation method thereof Download PDFInfo
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- CN112646340A CN112646340A CN202011032971.6A CN202011032971A CN112646340A CN 112646340 A CN112646340 A CN 112646340A CN 202011032971 A CN202011032971 A CN 202011032971A CN 112646340 A CN112646340 A CN 112646340A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
The invention relates to a high-temperature oil-resistant flame-retardant bio-based polycarbonate material and a preparation method thereof, wherein the material is prepared from the following components in percentage by weight: 83-90% of common PC resin; 5-10% of bio-based PC resin; 1.5 to 2 percent of brominated flame retardant; 2-3% of a toughening agent; 1.5 to 2 percent of auxiliary agent. The invention has the beneficial effects that the common PC resin is taken as the main component, the bio-based PC resin with high fluidity is added, and a proper amount of toughening agent and auxiliary agent are added, so that the prepared polycarbonate material has good high-temperature oil resistance, and after the polycarbonate material is soaked in R134a halogenated hydrocarbon oil at the high temperature of 70 ℃ for 48 hours, the polycarbonate material can be prevented from cracking after being stressed for 5 hours.
Description
Technical Field
The invention relates to the field of materials for compressor electric appliance shells, in particular to a high-temperature oil-resistant flame-retardant bio-based polycarbonate material and a preparation method thereof.
Background
Polycarbonate (PC) is a polymer containing carbonate groups in molecular chains, generally refers to bisphenol A type aromatic PC, and two preparation methods, namely a phosgene interface method and a molten ester exchange method (indirect phosgene and complete non-phosgene), are mainly adopted at present, and the Ningbo Zhejiang iron galenic company has marketed PC products, namely the green and environment-friendly complete non-phosgene molten ester exchange method is adopted. The bio-based PC is aliphatic PC with isosorbide replacing bisphenol A, and is called DURABIO by chemical commercial product name of Mitsubishi Japan. The common PC has ductility and toughness, and is widely used in various safety lampshades, signal lamps, transparent protective plates of stadiums and stadiums, lighting glass, high-rise building glass, CD discs, motorcycle driving safety helmets and the like. The areas where the largest amount of PC is used are computers, office supplies, automobiles, replacement glass and sheets. The bio-based PC is mainly used for automobile instrument panels at present, and is bright black and scratch-resistant. Ordinary PC is now cheap, 12 yuan per kg, while bio-based PC 90 yuan per kg.
Common PC is transparent and nontoxic, has good heat resistance and cold resistance, and is easy to generate stress cracking, because a benzene ring rigid group exists on a PC molecular chain, the steric effect is large, the high-temperature injection molding fluidity is general, the benzene ring molecular chain is difficult to be subjected to disorientation, the local stress of a workpiece is concentrated, and the workpiece can crack after the stress is released along with the time lapse. But the bio-based PC is completely different from the bio-based PC, does not contain benzene ring rigid groups, has very good fluidity and is the same as polypropylene resin, so the risk of stress concentration problem of a product is reduced by 80-90%. The best method for solving the problem of PC stress cracking is alloying, and the method comprises PC + toughening agent, PC + ABS, PC + PBT, PC + AS, PC + PET or ternary blend, and is applied in large batch in the market. At present, the focus of the modified PC is oil resistance, stress cracking resistance is focused before, and compared with the latter, the oil resistance difficulty is higher, namely, the modified PC can pass through the stress resistance through oil-resistant materials, and the requirement is higher. In the American group of the year, vegetable oil-resistant flame-retardant PC resin is required, wherein the vegetable oil comprises blend oil, peanut oil and corn oil, and the flame-retardant PC of a shell of a compressor electric appliance requires engine oil-resistant oil, wherein the blend oil comprises R134a, 600A, antirust oil and oil-resistant paint for an automobile door handle, so that the requirements of customers in the market prompt research and development personnel to find a solution hard to find, and a patent CN201510485848.2 discloses an oil-resistant flame-retardant polycarbonate material and a preparation method thereof, and the oil-resistant flame-retardant polycarbonate material is mainly used for kitchen wall switches (basically used at normal temperature); patent CN201180063799.3 improves the chemical resistance of PC materials by adding siloxane polycarbonate, and patent ZL201710419341.6 granted by this unit solves the high temperature oil resistance problem of PC, also alloyed and copolymerized PC.
Disclosure of Invention
The invention provides a high-temperature oil-resistant flame-retardant polycarbonate material and a preparation method thereof.
The technical scheme for solving the technical problems is as follows: a high-temperature oil-resistant flame-retardant polycarbonate material is prepared from the following components in percentage by weight:
on the basis of the technical scheme, the invention can further specifically select the following.
Specifically, the ordinary PC resin is a mixture of an aromatic polycarbonate with either or both of a low viscosity and a high viscosity at an arbitrary ratio. Zhejiang iron of China made in the strong wind with the brand name PC02-10 and kesi chuang low-viscosity PC 2405.
Specifically, the bio-based PC resin is D6350R manufactured by Mitsubishi chemical, melt index 12g/10min, 230 ℃ 2.16 kg.
Specifically, the brominated flame retardant is one of or a mixture of brominated triazine and tetrabromobisphenol A oligomer in any proportion. Compared with the conventional polybrominated diphenyl ether, the brominated flame retardant is safer due to no generation of toxic dibenzodithiane and polybrominated dibenzofuran during thermal cracking or combustion of high polymers.
Specifically, the toughening agent is an organic silicon toughening agent. The organic silicon toughening agent used in the invention takes acrylic acid and organic silicon as cores and methyl methacrylate or styrene-acrylonitrile (SAN) as shells, and has the capabilities of toughening, high temperature resistance, weather resistance, fire prevention assistance and the like.
Specifically, the auxiliary agent is prepared by mixing the following raw materials in parts by weight: 0.2-0.3 part of antioxidant; 0.3-1 part of ester exchange inhibitor; 0.4-0.6 part of high-temperature lubricant; 0.5-1 part of black master batch.
Specifically, the antioxidant is any one of or a mixture of two of a high-efficiency phosphite ester antioxidant S9228 and a thioether antioxidant 412S in any proportion.
Specifically, the high-temperature lubricant is pentaerythritol stearate (PETS), belongs to alkyd ester lubricants, has good internal and external lubricity, can improve the thermal stability of products, and is non-toxic.
Specifically, the black master batch is any one of or a mixture of polycarbonate-based black master batch and styrene-acrylonitrile-based black master batch in any proportion. The black master is one of color master batches, which is a plastic colorant formed by well dispersing a high proportion of pigment, additive and thermoplastic resin, namely, the thermoplastic resin is used as a carrier, and the preferred black master in the application takes polycarbonate or styrene-acrylonitrile as a carrier.
The invention also provides a method for preparing the high-temperature oil-resistant flame-retardant polycarbonate material, which comprises the following steps:
s1, processing and mixing raw materials: drying the PC resin until the water content is below 0.03%, and then adding the PC resin, the brominated flame retardant, the toughening agent and the auxiliary agent into a high-speed mixer according to corresponding weight percentages for fully mixing;
s2, melt extrusion: adding the mixed materials into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 245-270 ℃, and the screw rotating speed is 350 revolutions per minute;
s3, granulation and post-treatment: and cooling, air-drying, granulating, strongly magnetizing and packaging the extruded material in sequence to obtain the high-temperature oil-resistant flame-retardant polycarbonate material.
The invention has the beneficial effects that:
the modified PC material prepared by using common PC and bio-based PC as main components and adding a proper amount of toughening agent, auxiliary agent and the like has good high-temperature oil resistance, can ensure that the PC material does not crack after being soaked in R134a halogenated hydrocarbon oil (R134a, R600a and R134a in antirust oil SNR-2000S have the strongest permeability) for 48 hours at the high temperature of 70 ℃, overcomes the defects of partial compatibility and reduced flame retardance caused by PC alloying in the prior art, and does not need to add more flame retardants including anti-dripping agents, compatilizers and ester exchange inhibiting agents. The bio-based PC provides ultrahigh fluidity, is well compatible with common PC, and has coexisting aliphatic and aromatic structures, thereby fundamentally reducing the internal stress of a workpiece and stress cracking of the workpiece; in addition, the high-temperature oil-resistant flame-retardant polycarbonate material provided by the invention has the characteristics of simple formula and preparation process, high production efficiency and convenience for industrialization.
Drawings
FIG. 1 is a schematic view of a sample strip inserted into a fixture when the invention is used for testing the cracking time of the sample strip;
FIG. 2 is a schematic view of a preparation process of a high-temperature oil-resistant flame-retardant polycarbonate material.
In the drawings, the components represented by the respective reference numerals are listed below:
1. a jig; 2. a spline.
Detailed Description
The principles and features of this invention are described in connection with the drawings and the detailed description of the invention, which are set forth below as examples to illustrate the invention and not to limit the scope of the invention.
The invention provides a method for preparing a high-temperature oil-resistant flame-retardant polycarbonate material, which comprises the following steps:
s1, processing and mixing raw materials: drying the PC resin until the water content is below 0.03%, and then adding the PC resin, the brominated flame retardant, the toughening agent and the auxiliary agent into a high-speed mixer according to the weight percentage in the following table for fully mixing, wherein the auxiliary agent is prepared by mixing the following raw materials in parts by weight: the antioxidant, the high-temperature lubricant and the black master batch are mixed;
s2, melt extrusion: adding the mixed materials into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 245-270 ℃, and the screw rotating speed is 350 revolutions per minute;
s3, granulation and post-treatment: and (2) sequentially cooling, air-drying, granulating, strongly magnetizing and packaging the extruded material to obtain the high-temperature oil-resistant flame-retardant polycarbonate material, and in brief, after drying pretreatment of PC, mixing the components in a high-speed mixer for 1-2 minutes, and then putting the mixture into a double-screw extruder for extrusion and granulation to obtain the high-temperature oil-resistant flame-retardant polycarbonate material.
In the following examples, aromatic PC resin was Zhejiang iron Dafeng PC02-10, bio-based PC resin was Mitsubishi chemical D53 5360R, toughening agent was Mitsubishi yang SX-006, brominated flame retardant was Mitsubishi Gemini BC-58, antioxidant was Dover S9228, lubricant was Longsha PETS, and black masterbatch was Guangzhou Runfeng RF-5030C.
The examples and the components thereof, the weight percentages of the components are as follows:
| components | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Aromatic PC (02-10) | 90.3 | 87.5 | 83.7 | 95.3 | 93.7 | 84.7 |
| Aliphatic PC (D5360R) | 5 | 7.8 | 10 | 0 | 0 | 10 |
| Toughening agent (SX-006) | 2 | 2 | 3 | 2 | 3 | 2 |
| Brominated flame retardant (BC-58) | 1.5 | 1.5 | 2 | 1.5 | 2 | 2 |
| Antioxidant (S9228) | 0.2 | 0.2 | 0.3 | 0.2 | 0.3 | 0.3 |
| High temperature lubricant (PETS) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Black masterbatch (RF5030C) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The flame-retardant polycarbonate materials obtained in examples 1 to 5 and comparative examples 1 to 2 were subjected to the performance test, and the test results are shown in the following table:
the criteria and conditions for the performance test are as follows:
bending test GB/T9341-2008, speed 2mm/min, span 64 mm; notched impact strength test GB/T1843-2008; the melt index test GB/T3682-2000, the temperature is 300 ℃, and the weight is 1.2 kg; flame resistance test UL94, 2 mm; glow wire test GB/T5169-2006, 2 mm; CTI test GB/T4207-; high temperature oil resistance test: oil resistance 1, sample size 58 x 12.6 x 1.6mm, oil resistance 2, sample size 70 x 12.6 x 1.6mm, placing the samples in a high-low temperature box to soak R134a halogenated hydrocarbon oil at 70 ℃ for 48 hours before testing, taking out and cooling, bending the samples 2 into a bow shape to clamp the samples into a jig 1 with a span of 55mm (as shown in figure 1), adjusting the stress size through different sample sizes, wherein the cracking time is the time from the moment that the samples 2 are bent into the bow shape to clamp the samples into the jig until the samples crack, the span of the jig is 55mm, the corresponding size of the samples is 58mm or 70mm, and the samples are clamped into the jig in the bow shape.
As can be seen from the performance test data in the table above, the high-temperature oil-resistant flame-retardant bio-based polycarbonate provided by the invention has the average stress cracking time of more than 5 hours after being soaked in R134a halogenated hydrocarbon with the strongest penetration capacity at the temperature of 70 ℃ for 48 hours, and completely meets the requirements of the shell material of the compressor and the electric appliance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The high-temperature oil-resistant flame-retardant polycarbonate material is characterized by being prepared from the following components in percentage by weight:
2. the polycarbonate material as claimed in claim 1, wherein the ordinary PC resin is an aromatic polycarbonate with viscosity average molecular weight of 16000 and 28000.
3. The high temperature oil resistant flame retardant polycarbonate material of claim 1, wherein the bio-based PC resin is isosorbide aliphatic polycarbonate.
4. The high-temperature oil-resistant flame-retardant polycarbonate material as claimed in claim 1, wherein the brominated flame retardant is one or a mixture of brominated triazine and tetrabromobisphenol A oligomer in any proportion.
5. The high-temperature oil-resistant flame-retardant polycarbonate material as claimed in claim 1, wherein the toughening agent is an organosilicon toughening agent.
6. The high-temperature oil-resistant flame-retardant polycarbonate material as claimed in any one of claims 1 to 5, wherein the assistant is prepared by mixing the following raw materials in parts by weight: 0.2-0.3 part of antioxidant; 0.4-0.6 part of high-temperature lubricant; 0.5-1 part of black master batch.
7. The high-temperature oil-resistant flame-retardant polycarbonate material as claimed in claim 6, wherein the antioxidant is any one or a mixture of two of high-efficiency phosphite antioxidant S9228 and thioether antioxidant 412S in any proportion.
8. The high temperature oil resistant flame retardant polycarbonate material of claim 6, wherein the high temperature lubricant is pentaerythritol stearate.
9. The high-temperature oil-resistant flame-retardant polycarbonate material as claimed in claim 6, wherein the black masterbatch is any one of or a mixture of polycarbonate-based black masterbatch and styrene-acrylonitrile-based black masterbatch in any proportion.
10. A method for preparing the high-temperature oil-resistant flame-retardant polycarbonate material as claimed in any one of claims 1 to 9, which comprises the following steps:
s1, processing and mixing raw materials: drying the PC resin until the water content is below 0.03%, and then adding the PC resin, the brominated flame retardant, the toughening agent and the auxiliary agent into a high-speed mixer according to corresponding weight percentages for fully mixing;
s2, melt extrusion: adding the mixed materials into a double-screw extruder for melt extrusion, wherein the extrusion temperature is 245-270 ℃, and the screw rotating speed is 350 revolutions per minute;
s3, granulation and post-treatment: and cooling, air-drying, granulating, strongly magnetizing and packaging the extruded material in sequence to obtain the high-temperature oil-resistant flame-retardant polycarbonate material.
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Citations (7)
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| CN102712804A (en) * | 2009-12-10 | 2012-10-03 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
| CN102712805A (en) * | 2009-12-10 | 2012-10-03 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
| CN104761878A (en) * | 2015-04-08 | 2015-07-08 | 中国科学院化学研究所 | Polycarbonate composite material and preparation method thereof |
| CN107141755A (en) * | 2017-05-26 | 2017-09-08 | 合肥会通新材料有限公司 | A kind of bloom exempts from sprayed on material and preparation method thereof |
| CN107849344A (en) * | 2015-07-31 | 2018-03-27 | 华东理工大学 | Polycarbonate resin compound |
| US20180163046A1 (en) * | 2015-05-27 | 2018-06-14 | Kingfa Sci. & Tech. Co., Ltd. | Polycarbonate composition and preparation method thereof |
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2020
- 2020-09-27 CN CN202011032971.6A patent/CN112646340A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110306712A1 (en) * | 2009-03-03 | 2011-12-15 | Sony Corporation | Aromatic polycarbonate resin composition and molded product of the same |
| CN102712804A (en) * | 2009-12-10 | 2012-10-03 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
| CN102712805A (en) * | 2009-12-10 | 2012-10-03 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
| CN104761878A (en) * | 2015-04-08 | 2015-07-08 | 中国科学院化学研究所 | Polycarbonate composite material and preparation method thereof |
| US20180163046A1 (en) * | 2015-05-27 | 2018-06-14 | Kingfa Sci. & Tech. Co., Ltd. | Polycarbonate composition and preparation method thereof |
| CN107849344A (en) * | 2015-07-31 | 2018-03-27 | 华东理工大学 | Polycarbonate resin compound |
| CN107141755A (en) * | 2017-05-26 | 2017-09-08 | 合肥会通新材料有限公司 | A kind of bloom exempts from sprayed on material and preparation method thereof |
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