CN111548620B - Environment-friendly optical-grade polycarbonate and preparation method thereof - Google Patents
Environment-friendly optical-grade polycarbonate and preparation method thereof Download PDFInfo
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- CN111548620B CN111548620B CN202010373339.1A CN202010373339A CN111548620B CN 111548620 B CN111548620 B CN 111548620B CN 202010373339 A CN202010373339 A CN 202010373339A CN 111548620 B CN111548620 B CN 111548620B
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
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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
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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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention discloses an environment-friendly optical polycarbonate and a preparation method thereof, the environment-friendly optical polycarbonate comprises 100 parts of isosorbide type polycarbonate, 0.1-0.4 part of antioxidant, 10.05 parts of fluorescent brightener OB, 0.5-1.5 parts of light diffusant and 0.15 part of wetting agent; the preparation method comprises the following steps: putting isosorbide type polycarbonate, an antioxidant, a fluorescent whitening agent, liquid paraffin, an organic silicon light diffusant and an ultraviolet absorbent into a high-speed mixer, mixing for 5-10min at the speed of 900rpm to obtain a premix, and extruding, cooling, cutting and granulating by a double-screw extruder. The product of the invention can be used in the fields of lamp covers and the like, and has the advantages of high haze, good weather resistance and the like.
Description
Technical Field
The invention relates to the technical field of polymer modified materials, in particular to environment-friendly optical-grade polycarbonate and a preparation method thereof.
Background
Polycarbonate is a thermoplastic engineering plastic with excellent comprehensive performance, has outstanding impact resistance, good creep resistance and dimensional stability, higher heat resistance and cold resistance, excellent electrical performance, low water absorption and good light transmittance, is the only product with good transparency in five engineering plastics, and is also a universal engineering plastic with the fastest growth speed in recent years. In the development of polycarbonate synthesis technology, many synthetic methods have appeared, such as low-temperature solution polycondensation, high-temperature solution polycondensation, interfacial polycondensation, melt transesterification, and the like. Because bisphenol A with biotoxicity is required to be used in the preparation process of polycarbonate, and phosgene and methylene dichloride involved in part of the synthesis process do not meet the requirement of green environmental protection, the environmental protection awareness is strengthened, and the research on environment-friendly bio-based polycarbonate is trending.
Isosorbide is a rigid molecule, and the bio-based diol prepared by glucose hydrogenation and dehydration has a chiral structure and high thermal stability. In addition, because isosorbide is a biomass product, the secondary carbon carbonyl group of isosorbide is less active than the phenol carbonyl group of bisphenol A, so that isosorbide is more prone to be broken by the action of microorganisms or degrading enzymes in the product after polymerization reaction, and is a promising polycondensation bio-based monomer which is proved to be used for replacing petroleum-based bisphenol A with slow toxicity to synthesize isosorbide type polycarbonate.
Chinese patent publication No. CN105218802B discloses a process for synthesizing polycarbonate, which comprises adding isosorbide and carbonic acid diester into a mixing tank, mixing them uniformly, adding the mixed raw materials into an ester exchange reactor, removing the released hydroxyaryl reaction product, after esterification, adding the reaction product into a kettle-type prepolycondensation reactor, generating prepolymerization product therein, continuously removing the released hydroxyaryl reaction product, finally adding the prepolycondensation reaction product into a horizontal disc polycondensation reactor with hydraulic drive, and subjecting the prepolycondensation reaction product to microwave treatment to polycondense it into polycarbonate melt, thereby preparing isosorbide-type polycarbonate. The process has the advantages of high reaction rate and high conversion rate.
Although isosorbide polycarbonate has high hardness and certain scratch resistance, thermal-oxidative aging and photo-oxidative aging are easy to occur if the isosorbide polycarbonate is used outdoors for a long time, and the isosorbide polycarbonate can react with oxygen in the air to degrade at a certain temperature to cause internal defects, thereby affecting the optical performance; in addition, under the action of light, free radicals are generated in the matrix, and under the aerobic condition, the free radicals induce the oxidation reaction of the high molecular chain segment, so that the matrix is yellowed, and the optical performance of the matrix is influenced.
Disclosure of Invention
In view of the disadvantages of the prior art, the first object of the present invention is to provide an environmentally friendly optical grade polycarbonate which has the advantage of stable optical properties.
The second purpose of the invention is to provide a preparation method of the environment-friendly optical-grade polycarbonate.
In order to achieve the first object, the invention provides the following technical scheme:
the environment-friendly optical-grade polycarbonate is characterized by comprising the following components in parts by weight:
isosorbide type polycarbonate 100 parts
0.1 to 0.4 portion of antioxidant
Fluorescent brightener OB-10.05 parts
0.5 to 1.5 portions of light diffusant
0.15 part of wetting agent
0.5 part of ultraviolet absorber.
By adopting the technical scheme, the light diffusant is added into the isosorbide type polycarbonate, and due to the difference of the refractive indexes of the light diffusant and the isosorbide type polycarbonate, the light advancing path can be changed, the purposes of light uniformization and light transmission are achieved, and the haze of the product is improved.
In addition, the fluorescent whitening agent OB-1 is added on the basis, and the capability of the matrix for reflecting visible light can be enhanced by the fluorescent whitening agent OB-1, so that the white brightness of the product is improved; the antioxidant is added to improve the oxidation resistance of the isosorbide type polycarbonate;
furthermore, the addition of an ultraviolet absorber can absorb ultraviolet rays and reduce the degradation of isosorbide-type polycarbonate by ultraviolet rays, the fluorescent whitening agent OB-1 contains a carbon-carbon double bond, and the ultraviolet absorber can also reduce the damage of the fluorescent whitening agent OB-1 by ultraviolet rays and improve the stability of the fluorescent whitening agent OB-1 in a matrix.
Further, the ultraviolet absorbent is one or two of ultraviolet absorbents UV-P, UV-329.
By adopting the technical scheme, the ultraviolet absorbers UV-P, UV-329 belong to benzotriazole ultraviolet absorbers, have high absorption strength and good ultraviolet absorption effect.
Further, the mass ratio of the ultraviolet absorbent UV-P, UV-329 is 1.5: 1.
by adopting the technical scheme, the ultraviolet absorbent UV-P, UV-329 is used together, so that the ultraviolet absorbent has good synergistic effect, further improves the effect of absorbing ultraviolet rays, and improves the stability of the medium carbon-carbon double bond of the fluorescent whitening agent OB-1.
Further, the antioxidant is one or two of an antioxidant 1076 and an antioxidant 168.
By adopting the technical scheme, the antioxidant 1076 is the main antioxidant, can capture free radicals generated in the aging process of an organism, and the antioxidant 168 can decompose polymers generated by thermal-oxidative aging of a matrix, and can play a role in reducing yellowing of the matrix.
Further, the mass ratio of the antioxidant 1076 to the antioxidant 168 is 1: 1.
by adopting the technical scheme, the antioxidant 1076 and the antioxidant 168 are jointly used, so that free radicals in a matrix can be reduced, the occurrence of thermal oxidation aging is reduced, and the antioxidant performance of the isosorbide type polycarbonate can be obviously improved.
Further, the light diffusing agent is an organic silicon light diffusing agent KMP-590.
By adopting the technical scheme, the organic silicon light diffusant is a transparent spherical body, has lower refractive index, and can refract a light source penetrating through the organic silicon light diffusant, so that the haze of the substrate is improved.
Further, the wetting agent is one of liquid paraffin and pentaerythritol stearate.
By adopting the technical scheme, the liquid paraffin and the pentaerythritol stearate have good internal and external wettability, and the fluidity during processing can be improved.
In order to achieve the second object, the invention provides the following technical scheme:
drying isosorbide type polycarbonate at 100 ℃ for 8h to ensure that the water content is less than 0.02%;
putting isosorbide type polycarbonate, an antioxidant, a fluorescent whitening agent, liquid paraffin, a light diffusant and an ultraviolet absorbent into a high-speed mixer, and mixing for 5-10min at the speed of 900rpm to obtain a premix;
the method comprises the steps of adopting a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 30-36, the rotating speed of the double-screw extruder is 180-220rpm, the torque is 75 +/-3%, the temperature of a machine barrel is 40-60 ℃ in a first area, 270 +/-10 ℃ in a second area, 270 +/-10 ℃ in a third area, 260 +/-10 ℃ in the third area, 250 +/-10 ℃ in a fourth area, 250 +/-10 ℃ in a sixth area, 250 +/-10 ℃ in a seventh area, 250 +/-10 ℃ in an eighth area and 260 +/-10 ℃ in a ninth area, adding the premix into a hopper of the double-screw extruder, and carrying out extrusion, cooling, cutting and granulation to obtain the product.
In conclusion, the invention has the following beneficial effects:
first, the present invention can improve the haze of a substrate by adding a light diffuser to isosorbide-type polycarbonate, improve the whiteness of the substrate by adding a fluorescent whitening agent to the substrate, and improve the weatherability of the substrate and the weatherability of the fluorescent whitening agent by absorbing ultraviolet rays by adding an ultraviolet absorber.
Secondly, the ultraviolet absorbers in the invention are preferably ultraviolet absorbers UV-P and UV-329, which can absorb ultraviolet light of 270-280nm and reduce the possibility of the carbon-carbon double bond on the optical brightener OB-1 being broken by the ultraviolet light.
According to the method of the present invention, isosorbide-type polycarbonate, an antioxidant, a fluorescent whitening agent, liquid paraffin, a silicone light diffusing agent and an ultraviolet absorber are mixed, and the mixture is extruded, cooled, cut and granulated by a twin-screw extruder, so that the prepared isosorbide-type polycarbonate has the effects of high haze and good weather resistance.
Detailed Description
The present invention will be described in further detail with reference to examples.
The liquid paraffin in the following examples is selected from Fuyu fine chemical Co., Ltd, Tianjin, and the isosorbide-type polycarbonate is selected from Durabio, Mitsubishi, model No. D5360R; the antioxidant 1076 and the antioxidant 168 are selected from Irganox 1076 and Irganox 168 from Pasteur Limited; the optical brightener OB-1 is selected from TINOPAL OB of BASF Limited; the organic silicon light diffusant KMP-590 is selected from Nippon shin-Etsu chemical industries Co., Ltd; the ultraviolet absorber is selected from Tinuvin P and Tinuvin 329 of Bassff Limited.
Examples
The environment-friendly optical-grade polycarbonate is prepared by the following method:
(1) drying isosorbide type polycarbonate at 100 ℃ for 8h to ensure that the water content is less than 0.02%;
(2) putting isosorbide type polycarbonate, an antioxidant, a fluorescent whitening agent, liquid paraffin, a light diffusant and an ultraviolet absorbent into a high-speed mixer, and mixing for 5-10min at the speed of 900rpm to obtain a premix;
(3) the method comprises the steps of adopting a double-screw extruder, wherein the length-diameter ratio of the double-screw extruder is 30-36, the rotating speed of the double-screw extruder is 180-220rpm, the torque is 75 +/-3%, the temperature of a machine barrel is 40-60 ℃ in a first area, 270 +/-10 ℃ in a second area, 270 +/-10 ℃ in a third area, 260 +/-10 ℃ in the third area, 250 +/-10 ℃ in a fourth area, 250 +/-10 ℃ in a sixth area, 250 +/-10 ℃ in a seventh area, 250 +/-10 ℃ in an eighth area and 260 +/-10 ℃ in a ninth area, adding the premix into a hopper of the double-screw extruder, and carrying out extrusion, cooling, cutting and granulation to obtain the product.
Examples 1-3 and comparative examples 1-4 environmentally friendly optical grade polycarbonates were prepared using the above process, with the raw material amounts shown in table 1.
TABLE 1 raw material usage tables for examples 1-3 and comparative examples 1-4
Examples 4 to 6 and comparative examples 5 to 9 environmental friendly optical grade polycarbonate was prepared by the above method, and the amounts of the raw materials used are shown in table 2.
TABLE 2 tables for raw materials used in examples 4 to 6 and comparative examples 5 to 9
Performance detection
The environmentally friendly optical grade polycarbonates prepared in examples 1 to 6 and comparative examples 1 to 9 were injection molded into test bars according to standard sizes, and the test results were shown in Table 4 according to the test methods in Table 3.
TABLE 3 Performance test methods
| Performance index | Test method |
| Light transmittance test | ISO 13468-1 |
| Haze test | ISO 14782 |
| Xenon lamp aging | ISO 4892.2-2013 |
| Blue light whiteness test | GB/T 17749-2008 |
| Thermo-oxidative ageing (90 ℃, 5d) | GB/T 7141-2008 |
| Melt index determination | GB/T3682-2000 |
TABLE 4 Property test Table for polycarbonates in examples 1 to 6 and comparative examples 1 to 9
As can be seen from table 4: as can be seen by comparing example 2 with comparative examples 1 and 2, the weight ratio of antioxidant 1076 to antioxidant 168 was 1: 1, the substrate has better thermal oxidation resistance, and the substrate is not easy to age and turn yellow in the thermal oxidation aging process, so that the retention rate of the light transmittance is higher. As can be seen by comparing example 2 with comparative examples 3 and 4, the weight ratio of the ultraviolet absorber UV-P to the ultraviolet absorber UV-329 is 1: 1, the substrate has better ultraviolet resistance, and after xenon lamp aging, the color difference value of the substrate in the example 2 is smaller, which indicates that the color change is smaller.
As can be seen from comparison among examples 1, 2 and 3, as the content of the antioxidant increases, the thermo-oxidative aging resistance of the matrix increases, and the retention rate of the light transmittance gradually increases. As can be seen from comparison among examples 2, 4 and 5 and comparative example 8, the haze of the matrix is increased with the addition of the content of the silicone light diffuser KMP-590, which shows that the silicone light diffuser KMP-590 can refract light to achieve the effect of improving the haze, and the haze of the matrix is greatly reduced without the addition of the silicone light diffuser KMP-590 in comparative example 8.
As can be seen from the comparison between example 5 and comparative examples 6 and 7, the increase of the fluorescent whitening agent OB-1 can improve the whiteness of the substrate, the ultraviolet absorbent can improve the light aging resistance of the substrate, the color difference value of the substrate after xenon lamp aging reaches 11.6 in the absence of the ultraviolet absorbent, and the color difference value is only 6.2 in example 5, which shows that the ultraviolet absorbent can protect the substrate and the fluorescent whitening agent OB-1. As can be seen from comparison of examples 5 and 6 with comparative example 9, both of liquid paraffin and pentaerythritol stearate act to improve the processing fluidity, and the melt index is greatly reduced and the fluidity is deteriorated without the addition of a wetting agent.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (6)
1. The environment-friendly optical-grade polycarbonate is characterized by comprising the following components in parts by weight:
isosorbide type polycarbonate 100 parts
0.1 to 0.4 portion of antioxidant
Fluorescent brightener OB-10.05 parts
0.5 to 1.5 portions of light diffusant
0.15 portion of wetting agent
0.5 part of ultraviolet absorber;
the ultraviolet absorbent is ultraviolet absorbent UV-P and UV-329.
2. The environmentally friendly optical grade polycarbonate of claim 1, wherein the weight ratio of the UV absorber UV-P, UV-329 is 1.5: 1.
3. the environmentally friendly optical grade polycarbonate of claim 1, wherein the antioxidant is one or both of antioxidant 1076 and antioxidant 168.
4. The environmentally friendly optical grade polycarbonate of claim 3, wherein the mass ratio of the antioxidant 1076 to the antioxidant 168 is 1: 1.
5. the environment-friendly optical grade polycarbonate of claim 1, wherein the light diffuser is a silicone light diffuser KMP-590.
6. The environmentally friendly optical grade polycarbonate of claim 1, wherein the wetting agent is one of liquid paraffin and pentaerythritol stearate.
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| CN113563708B (en) * | 2021-07-16 | 2023-05-05 | 上海品诚控股集团有限公司 | Polycarbonate solid plate applied to outdoors and preparation method thereof |
| CN114539754B (en) * | 2021-12-16 | 2023-11-14 | 上海长伟锦磁工程塑料有限公司 | Weather-resistant halogen-free flame-retardant bio-based polycarbonate material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105385133A (en) * | 2015-11-02 | 2016-03-09 | 中广核俊尔新材料有限公司 | Halogen-free flame retardant PC reinforcing material, preparing method of halogen-free flame retardant PC reinforcing material and application in preparing electric meter shell |
| CN107245233A (en) * | 2016-04-26 | 2017-10-13 | 宁波浙铁大风化工有限公司 | LED illumination uses up diffusion flame-retardant polycarbonate material and preparation method thereof |
| CN109749389A (en) * | 2018-12-27 | 2019-05-14 | 浙江普利特新材料有限公司 | A kind of isobide type polycarbonate of weatherability and ABS resin alloy material and preparation method thereof |
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| JP7237592B2 (en) * | 2016-04-14 | 2023-03-13 | コベストロ、ドイチュラント、アクチエンゲゼルシャフト | Polycarbonate composition containing isosorbide diester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385133A (en) * | 2015-11-02 | 2016-03-09 | 中广核俊尔新材料有限公司 | Halogen-free flame retardant PC reinforcing material, preparing method of halogen-free flame retardant PC reinforcing material and application in preparing electric meter shell |
| CN107245233A (en) * | 2016-04-26 | 2017-10-13 | 宁波浙铁大风化工有限公司 | LED illumination uses up diffusion flame-retardant polycarbonate material and preparation method thereof |
| CN109749389A (en) * | 2018-12-27 | 2019-05-14 | 浙江普利特新材料有限公司 | A kind of isobide type polycarbonate of weatherability and ABS resin alloy material and preparation method thereof |
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