CN103087494A - Polymethyl ethylene carbonate modification method, modified material and application thereof - Google Patents
Polymethyl ethylene carbonate modification method, modified material and application thereof Download PDFInfo
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- CN103087494A CN103087494A CN2013100293281A CN201310029328A CN103087494A CN 103087494 A CN103087494 A CN 103087494A CN 2013100293281 A CN2013100293281 A CN 2013100293281A CN 201310029328 A CN201310029328 A CN 201310029328A CN 103087494 A CN103087494 A CN 103087494A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a polymethyl ethylene carbonate modification method, a modified material and application thereof. The modification method comprises the following steps of: mixing polymethyl ethylene carbonate with a modifying agent; and fusing and melting at 110-140 DEG C to obtain a modified material of the polymethyl ethylene carbonate, wherein the modifying agent comprises one or more of polyethylene, a polyolefin plastomer, a polyolefin elastomer, an ethylene-vinyl acetate copolymer, an ethylene acrylic acid copolymer, a maleic anhydride grafted polyethylene and a maleic anhydride grafted ethylene-octylene copolymer. The polymethyl ethylene carbonate modification method provided by the invention is simple in process, easy to control and low in cost; the modified material is free of peculiar smell, can be used as a middle partition layer with excellent performance, can be used for preparing a cosmetic hose, is capable of greatly broadening the application of a carbon dioxide-based copolymer, high in partition performance and biodegradable. Besides, the polymethyl ethylene carbonate modification method is safe and environmentally-friendly; the partition performance and bonding performance of the modified material are excellent; and the product performance can be controlled.
Description
Technical field
The present invention relates to makeup hose material field, relate in particular to a kind of lined polymethyl ethylene carbonate method of modifying, material and application.
Background technology
Due to the coextrusion composite hose (being the makeup flexible pipes) that is used for the product such as makeup, to resistance oxygen, block water, the barrier property such as choke has very high requirement, so generally all adopt the material of better performances as the industrial raw material of makeup flexible pipe.Ethylene-vinyl alcohol copolymer (EVOH) becomes barrier material the most frequently used in industrial production due to its outstanding gas barrier property, good oil resistant and organic solvent resistance.But the EVOH price is higher, wet sensitive is strong, and after moisture absorption, barrier property descends, and reclaims difficulty, and its waste can bring serious pollution to environment.A kind of barrier property is better, over-all properties is more excellent, the barrier material of low-carbon environment-friendly substitutes so demand urgently seeking.
Lined polymethyl ethylene carbonate (PPC) is a kind of have good choke block-water performance and biodegradable carbonic acid gas base co-polymer.PPC adopts carbonic acid gas and propylene oxide monomer to synthesize preparation by polyreaction, and efficiently stabilizing carbon dioxide, significantly reduce the industrial carbon dioxide exhaust gas emission, and protection of the environment is expected to become the novel environment friendly barrier material that substitutes EVOH.But PPC is existent defect also: because PPC is a kind of amorphous polymer, its second-order transition temperature is lower, mechanical property and thermal stability are relatively poor, barrier property has much room for improvement, can't use separately, and the PPC raw material smell of domestic supply is heavier, has greatly limited its application in high-end used for cosmetic coextrusion composite hose.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of lined polymethyl ethylene carbonate method of modifying, material and application, be intended to solve existing polymethyl ethylene carbonate material mechanical property and poor heat stability, peculiar smell is heavy, barrier property is not high problem.
Technical scheme of the present invention is as follows:
A kind of lined polymethyl ethylene carbonate method of modifying, wherein, comprise step: lined polymethyl ethylene carbonate is mixed with properties-correcting agent, and carrying out the material modified of melting mixing acquisition lined polymethyl ethylene carbonate under 110 ~ 140 ℃ of conditions, described properties-correcting agent comprises one or more in polyethylene, polyolefin plastomers, polyolefin elastomer, ethylene-vinyl acetate copolymer, ethylene acrylic acid co polymer, maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-octene copolymer.
Described lined polymethyl ethylene carbonate method of modifying, wherein, by mass percentage, described lined polymethyl ethylene carbonate accounts for 60% ~ 95%, and properties-correcting agent accounts for 5% ~ 40%.
Described lined polymethyl ethylene carbonate method of modifying, wherein, by mass percentage, described lined polymethyl ethylene carbonate accounts for 65 ~ 80%, and properties-correcting agent accounts for 20 ~ 35%.
A kind of lined polymethyl ethylene carbonate is material modified, wherein, adopts the method for claim 1 to prepare.
The material modified application of a kind of described lined polymethyl ethylene carbonate, wherein, with the raw material in the material modified obstruct middle layer as preparation makeup flexible pipe of described lined polymethyl ethylene carbonate.
The application that described lined polymethyl ethylene carbonate is material modified, wherein, the pipe shaft of described makeup flexible pipe comprises five layers from outside to inside successively: outer, outer bonding coat, obstruct middle layer, interior bonding coat and internal layer, the thickness of described pipe shaft is 0.5 ~ 1.0mm, outer field thickness is greater than 0.2mm, the thickness in described obstruct middle layer is greater than 0.1mm, and described outer field thickness is greater than 0.15mm.
The application that described lined polymethyl ethylene carbonate is material modified, wherein, the raw materials of described outer bonding coat and interior bonding coat is the anhydride modified linear low-density polyethylene polymer of process.
The application that described lined polymethyl ethylene carbonate is material modified, wherein, the raw materials of described skin and internal layer is polypropylene or polyethylene or polypropylene and poly blend.
The application that described lined polymethyl ethylene carbonate is material modified, wherein, the preparation process of the pipe shaft of described makeup flexible pipe comprises: the raw materials of each layer is carried out melting treatment from corresponding screw extrusion press, melt after melting treatment is confluxed mix rear coextrusion to the multilayer co-extruding machine head, after stretched, cooling, Vacuum shaping, thermal treatment, traction, fixed length cutting, make described pipe shaft.
The application that described lined polymethyl ethylene carbonate is material modified, wherein, the vacuum pressure of Vacuum shaping is controlled at 0.003 ~-0.001MPa.
Beneficial effect: lined polymethyl ethylene carbonate method of modifying technique provided by the invention is simple, easy-regulating, cost are low, material modified free from extraneous odour, can be used as the obstruct middle layer of excellent property, for the preparation of the makeup flexible pipe, greatly widened the carbon dioxide-base Application of copolymer, barrier property is high, and biodegradable, the material barrier property after safety and environmental protection of the present invention, modification and bond properties is good, product performance are controlled.
Description of drawings
Fig. 1 is the structural representation of the cross section of the makeup flexible pipe for preparing of the present invention.
Fig. 2 is the structural representation of the production unit of makeup flexible pipe of the present invention.
Fig. 3 is the Photomicrograph of the longitudinal cross-section of the makeup flexible pipe of preparation in the embodiment of the present invention 1.
Fig. 4 is the Photomicrograph of the longitudinal cross-section of the makeup flexible pipe of preparation in the embodiment of the present invention 2.
Fig. 5 is the Photomicrograph of the longitudinal cross-section of the makeup flexible pipe of preparation in the embodiment of the present invention 3.
Embodiment
The invention provides a kind of lined polymethyl ethylene carbonate method of modifying, material and application, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Lined polymethyl ethylene carbonate method of modifying provided by the invention, comprise step: lined polymethyl ethylene carbonate is mixed with properties-correcting agent, and carrying out the material modified of melting mixing acquisition lined polymethyl ethylene carbonate under 110 ~ 140 ℃ of conditions, described properties-correcting agent comprises one or more in polyethylene, polyolefin plastomers, polyolefin elastomer, ethylene-vinyl acetate copolymer, ethylene acrylic acid co polymer, maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-octene copolymer.
Further, by mass percentage, described lined polymethyl ethylene carbonate accounts for 60% ~ 95%, properties-correcting agent accounts for 5% ~ 40%, under this ratio, the material modified good flowing properties of lined polymethyl ethylene carbonate that generates, and high with the consistency of tackiness agent, thus solved the problem of lined polymethyl ethylene carbonate starting material and the easy layering of polyethylene compound tense.
Further, by mass percentage, described lined polymethyl ethylene carbonate accounts for 65 ~ 80%, and properties-correcting agent accounts for 20 ~ 35%.Under this ratio, the material modified performance of the lined polymethyl ethylene carbonate for preparing is better, and mechanical property and thermal stability significantly improve, and the barrier property performance is better, and peculiar smell is less.
Lined polymethyl ethylene carbonate modification procedure of the present invention is directly to realize in screw extrusion press, it is specially: at first be ready to lined polymethyl ethylene carbonate and properties-correcting agent, then after super-dry, weighing, premix, extrude the single screw extrusion machine that intercepts the middle layer and carry out melting mixing to make lined polymethyl ethylene carbonate material modified thereby lined polymethyl ethylene carbonate and properties-correcting agent are put into simultaneously, and material modified directly confluxing of lined polymethyl ethylene carbonate formed the obstruct middle layer of makeup flexible pipe to the multilayer co-extruding machine head.
as the material modified application of lined polymethyl ethylene carbonate of the present invention, makeup flexible pipe of the present invention comprises tube head and pipe shaft, wherein, pipe shaft is five layers of composite structure, as shown in Figure 1, these five layers of composite structures comprise from outside to inside successively: outer 15, bonding coat 14(claims again outer bonding coat 14), intercept middle layer 13, bonding coat 12(claims again interior bonding coat 12), internal layer 11, intercept the middle layer and adopt namely that aforesaid lined polymethyl ethylene carbonate is material modified to be made, the material of skin and internal layer is polypropylene or polyethylene or polypropylene and poly blend, the material of bonding coat is tackiness agent.
Tackiness agent in the present invention preferably adopts anhydride modified linear low-density polyethylene polymer, linear low-density polyethylene polymer (Linear Low Density Polyethylene, LLDPE), it is the multipolymer that ethene and a small amount of senior ɑ-alkene are polymerized under catalyzer exists, through after anhydride modified, can improve interface compatibility and the adhesiveproperties of linear low-density polyethylene polymer and other materials, and greatly improve the barrier property of matrix material.
In these five layers of composite structures, the material of adjacent layers is different, and improving composite effect, and tackiness agent is not arranged on internal layer or skin.
The pipe shaft thickness of makeup flexible pipe of the present invention is generally 0.5mm to 1.0mm, and wherein, the thickness of internal layer intercepts the thickness in middle layer greater than 0.1mm greater than 0.2mm, and outer field thickness is greater than 0.15mm.
The below illustrates and utilizes the technique that described lined polymethyl ethylene carbonate is material modified and other materials is produced the makeup flexible pipe.
As shown in Figure 2, Fig. 2 is the production unit structural representation of five layers of composite soft tube pipe shaft of the present invention, as shown in the figure, this production unit comprises four screw extrusion presss, a multi-layer co-extruded head 7 of cover, stretches cooling and vacuum sizing device (being 8 with stretching refrigerating unit and vacuum sizing device label in the lump), thermal treatment unit, towing mechanism 9 and fixed-length cutting device 10; Four above-mentioned screw extrusion presss are the first screw extrusion press 1, the second screw extrusion press 2, three-screw extruder 5, four screw extruder 6, and the position of the extruder head of each screw extrusion press sequence afterwards in the past is followed successively by: the first extruder head 3 of the extruder head of the first screw extrusion press, the second screw extrusion press, the extruder head of three-screw extruder, the second extruder head 4 of the second screw extrusion press, the extruder head of four screw extruder.
Internal layer is extruded by screw extrusion press 1, bonding coat by screw extrusion press 2 extrude rear material shunt again respectively from the first extruder head 3 and the second extruder head 4 extrude form in bonding coat and outer bonding coat, intercepting the middle layer extrudes from three-screw extruder 5, skin is extruded by screw extrusion press 6, five layer materials conflux to multilayer co-extruding machine head 7, realize the sizing of pipe shaft after the processing of the cooling and vacuum sizing device 8 of drawn, after thermal treatment, through the traction of towing mechanism 9 and the fixed length cutting of fixed-length cutting device 10, make the pipe shaft of makeup flexible pipe.Namely get makeup flexible pipe finished product after the operations such as process head, printing, post-treatment, packing again through the flexible pipe pipe shaft that aforesaid method makes.
In above-mentioned steps, the vacuum pressure that vacuum sizing device is controlled remain on 0.003MPa ~-0.001MPa between, in addition, thermal treatment is to adopt 20 ~ 40 ℃ of warm water to heat.Adopt above-mentioned vacuum-treat and heat treatment process, can be good at solving the problem of peculiar smell residual in the lined polymethyl ethylene carbonate starting material, thereby expanded the range of application of this makeup flexible pipe in the field of assurance.And above-mentioned technological process safety, environmental protection, removed the gas that peculiar smell is arranged, the course of processing is simple, processing parameter is easily controlled, during in Screw Extrusion, the microtexture of matrix material under the melting mixing effect can directly be retained in product, thereby realization realizes the controllability of product performance by the control of morphological structure.
The present invention is owing to adopting lined polymethyl ethylene carbonate material modified as intercepting the middle layer, and unconventional petroleum base EVOH, due to the material modified effectively stabilizing carbon dioxide of lined polymethyl ethylene carbonate, thereby significantly reduce the discharging of CO 2 waste gas, reduce the Greenhouse effect of carbon dioxide generating to the impact of environment.
The below does the present invention with specific embodiment and illustrates.
Embodiment 1
After super-dry, metering, by mass percentage, with lined polymethyl ethylene carbonate and polyolefin plastomers (melting index is 1.0) the ratio premix with 70:30, and drop in three-screw extruder 5 hoppers, form blend through melting mixing, coextrusion forms and intercepts the middle layer.Wherein, three-screw extruder 5 diameter 35mm, length-to-diameter ratio 26.Also internal layer and outer field raw materials are put into respectively simultaneously in the first screw extrusion press 1 in four screw extruder 6, the raw materials of bonding coat is put in the second screw extrusion press 2, wherein, internal layer and outer field raw materials are the blend of Low Density Polyethylene and linear low density polyethylene, the melting index of Low Density Polyethylene is 1.84 ~ 2.5, the melting index of linear low density polyethylene is 2.0 ± 0.3, and the raw materials of bonding coat is that melting index is 1.8 acid anhydride-grafted linear low density polyethylene.
The first screw extrusion press 1 wherein and the barrel zone temperature of four screw extruder 6 are set to 145 ~ 155 ℃, the barrel zone temperature of the second screw extrusion press 2 is set to 150 ~ 180 ℃, the barrel zone temperature of three-screw extruder 5 is set to 110 ~ 130 ℃, the vacuum pressure of Vacuum shaping is 0.003 ~-0.001MPa, 20 ~ 40 ℃ of warm water are adopted in thermal treatment, and multi-layer co-extruded head 7 Temperature Settings are between 150 ~ 180 ℃.
The cosmetic QC for preparing according to the method described above, intercept middle layer and internal layer and outer bond effect better, its result can be as can be seen from Figure 3, interface between each layer and thickness distribution, flow interface is stable, and thickness distribution is even, internal layer thickness is 0.22 mm, intermediate layer thickness is 0.13 mm, and outer layer thickness is 0.17 mm, satisfies the requirement of used for cosmetic makeup flexible pipe.
Embodiment 2
The coextrusion process process is substantially the same manner as Example 1, and difference is that to intercept the material in middle layer different.In the present embodiment, the blend ratio of lined polymethyl ethylene carbonate and polyolefin plastomers is 80:20, and other layers of materials are identical with embodiment 1.
Moulding process is used for extruding the second screw extrusion press temperature that intercepts the middle layer and is controlled at 105 ~ 125 ℃, and other processing parameters are identical.
Can find from Fig. 4, lined polymethyl ethylene carbonate content increases, when polyolefin plastomers content reduces, intercepting middle layer and interior and outer bond effect does not weaken, flow interface is stable, thickness distribution slightly changes, and internal layer thickness is 0.24 mm, and intermediate layer thickness is 0.11 mm, outer layer thickness is 0.17 mm, still can satisfy the requirement of makeup flexible pipe.
The coextrusion process process is substantially the same manner as Example 1, and difference is that to intercept the material in middle layer different.In the present embodiment, properties-correcting agent is selected ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene, the blend ratio of lined polymethyl ethylene carbonate, ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene is 70:20:10, and other layers of materials are identical with embodiment 1.
Moulding process is used for extruding the second screw extrusion press temperature that intercepts the middle layer and is controlled at 110 ~ 130 ℃, and other processing parameters are identical.
Can find from Fig. 5, ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene are extruded stable as properties-correcting agent, good with the lined polymethyl ethylene carbonate consistency, the flexible pipe thickness distribution is even, and internal layer thickness is 0.25 mm, intermediate layer thickness is 0.10mm, and outer layer thickness is 0.16 mm.
In sum, lined polymethyl ethylene carbonate method of modifying technique provided by the invention is simple, easy-regulating, cost are low, material modified free from extraneous odour, can be used as the obstruct middle layer of excellent property, for the preparation of the makeup flexible pipe, greatly widened the carbon dioxide-base Application of copolymer, barrier property is high, and biodegradable, the material barrier property after safety and environmental protection of the present invention, modification and bond properties is good, product performance are controlled.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or conversion, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1. lined polymethyl ethylene carbonate method of modifying, it is characterized in that, comprise step: lined polymethyl ethylene carbonate is mixed with properties-correcting agent, and carrying out the material modified of melting mixing acquisition lined polymethyl ethylene carbonate under 110 ~ 140 ℃ of conditions, described properties-correcting agent comprises one or more in polyethylene, polyolefin plastomers, polyolefin elastomer, ethylene-vinyl acetate copolymer, ethylene acrylic acid co polymer, maleic anhydride grafted polyethylene, maleic anhydride grafted ethene-octene copolymer.
2. lined polymethyl ethylene carbonate method of modifying according to claim 1, is characterized in that, by mass percentage, described lined polymethyl ethylene carbonate accounts for 95% ~ 60%, and properties-correcting agent accounts for 5% ~ 40%.
3. lined polymethyl ethylene carbonate method of modifying according to claim 2, is characterized in that, by mass percentage, described lined polymethyl ethylene carbonate accounts for 65 ~ 80%, and properties-correcting agent accounts for 20 ~ 35%.
4. a lined polymethyl ethylene carbonate is material modified, it is characterized in that, adopts the method for claim 1 to prepare.
5. the material modified application of lined polymethyl ethylene carbonate as claimed in claim 4, is characterized in that, with the raw material in the material modified obstruct middle layer as preparation makeup flexible pipe of described lined polymethyl ethylene carbonate.
6. the material modified application of lined polymethyl ethylene carbonate according to claim 5, it is characterized in that, the pipe shaft of described makeup flexible pipe comprises five layers from outside to inside successively: outer, outer bonding coat, obstruct middle layer, interior bonding coat and internal layer, the thickness of described pipe shaft is 0.5 ~ 1.0mm, outer field thickness is greater than 0.2mm, the thickness in described obstruct middle layer is greater than 0.1mm, and described outer field thickness is greater than 0.15mm.
7. the material modified application of lined polymethyl ethylene carbonate according to claim 6, is characterized in that, the raw materials of described outer bonding coat and interior bonding coat is the anhydride modified linear low-density polyethylene polymer of process.
8. the material modified application of lined polymethyl ethylene carbonate according to claim 6, is characterized in that, the raw materials of described skin and internal layer is polypropylene or polyethylene or polypropylene and poly blend.
9. the material modified application of lined polymethyl ethylene carbonate according to claim 6, it is characterized in that, the preparation process of the pipe shaft of described makeup flexible pipe comprises: the raw materials of each layer is carried out melting treatment from corresponding screw extrusion press, melt after melting treatment is confluxed mix rear coextrusion to the multilayer co-extruding machine head, after stretched, cooling, Vacuum shaping, thermal treatment, traction, fixed length cutting, make described pipe shaft.
10. the material modified application of lined polymethyl ethylene carbonate according to claim 9, is characterized in that, the vacuum pressure of Vacuum shaping is controlled at 0.003 ~-0.001MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387737A (en) * | 2014-11-13 | 2015-03-04 | 中国科学院长春应用化学研究所 | Reinforced modified poly(propylene carbonate) composition and preparation method thereof |
| CN107650360A (en) * | 2017-09-27 | 2018-02-02 | 华南理工大学 | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108395559A (en) * | 2018-03-22 | 2018-08-14 | 常德市金润新材料科技有限公司 | A kind of high performance high barrier food Package film and preparation method thereof |
| CN109438954A (en) * | 2018-11-13 | 2019-03-08 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof |
| US11214044B2 (en) | 2016-03-08 | 2022-01-04 | Lg Chem, Ltd. | Multilayer film comprising polyalkylene carbonate and manufacturing method of the same |
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| WO2012051219A2 (en) * | 2010-10-11 | 2012-04-19 | Novomer, Inc. | Polymer blends |
| CN102431706A (en) * | 2011-10-10 | 2012-05-02 | 深圳市通产丽星股份有限公司 | Packing hose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012051219A2 (en) * | 2010-10-11 | 2012-04-19 | Novomer, Inc. | Polymer blends |
| CN102431706A (en) * | 2011-10-10 | 2012-05-02 | 深圳市通产丽星股份有限公司 | Packing hose |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387737A (en) * | 2014-11-13 | 2015-03-04 | 中国科学院长春应用化学研究所 | Reinforced modified poly(propylene carbonate) composition and preparation method thereof |
| US11214044B2 (en) | 2016-03-08 | 2022-01-04 | Lg Chem, Ltd. | Multilayer film comprising polyalkylene carbonate and manufacturing method of the same |
| CN107650360A (en) * | 2017-09-27 | 2018-02-02 | 华南理工大学 | A kind of degradable poly methyl ethylene carbonate base microbedding coextruding composite material and preparation method thereof |
| CN107868425A (en) * | 2017-10-12 | 2018-04-03 | 杭州师范大学 | A kind of high-performance polymethyl ethylene carbonate material and preparation method thereof |
| CN108395559A (en) * | 2018-03-22 | 2018-08-14 | 常德市金润新材料科技有限公司 | A kind of high performance high barrier food Package film and preparation method thereof |
| CN108395559B (en) * | 2018-03-22 | 2020-12-22 | 常德市金润新材料科技有限公司 | High-performance high-barrier food packaging film and preparation method thereof |
| CN109438954A (en) * | 2018-11-13 | 2019-03-08 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof |
| WO2020098497A1 (en) * | 2018-11-13 | 2020-05-22 | 金发科技股份有限公司 | Polycarbonate alloy and preparation method thereof |
| CN109438954B (en) * | 2018-11-13 | 2020-12-15 | 金发科技股份有限公司 | Polycarbonate alloy and preparation method thereof |
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