CN112457617A - High-transparency low-dielectric-loss toughened cyclic polyolefin material and preparation method thereof - Google Patents
High-transparency low-dielectric-loss toughened cyclic polyolefin material and preparation method thereof Download PDFInfo
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- CN112457617A CN112457617A CN202011325146.5A CN202011325146A CN112457617A CN 112457617 A CN112457617 A CN 112457617A CN 202011325146 A CN202011325146 A CN 202011325146A CN 112457617 A CN112457617 A CN 112457617A
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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
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
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- 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
- C08L2205/03—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
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Abstract
The invention discloses a high-transparency low-dielectric-loss toughened cyclic polyolefin material which comprises the following components in parts by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of compatilizer; the elastomer is at least one of a styrene-butadiene-styrene block copolymer and a styrene-ethylene-butadiene-styrene block copolymer. The cyclic polyolefin material has high impact and notch impact performance>13KJ/m2Can satisfy communicationBasic impact requirements and light transmission requirements of the electronic and household appliance industries. Meanwhile, the invention also discloses a preparation method of the cyclic polyolefin material.
Description
Technical Field
The invention relates to the field of modification of high polymer materials, in particular to a high-transparency low-dielectric-loss toughened cyclic polyolefin material and a preparation method thereof.
Background
The existing cyclic polyolefin material has low dielectric constant and loss, but has low impact strength, and cannot meet the requirements on the comprehensive properties of the material. Although the prior art can improve the impact strength, the transparency is lost, and the dielectric loss and the dielectric constant are also improved.
Disclosure of Invention
Based on the above, the present invention aims to overcome the defects of the prior art and provide a high-transparency low-dielectric-loss toughened cyclic polyolefin material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a high-transparency low-dielectric-loss toughened cyclic polyolefin material comprises the following components in parts by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of compatilizer; the elastomer is at least one of styrene-butadiene-styrene block copolymer (SBS elastomer) and styrene-ethylene-butadiene-styrene block copolymer (SEBS elastomer).
The material provided by the invention is mainly used for improving the impact strength of the cyclic polyolefin material on the basis of ensuring the low dielectric loss performance and high transparency of the cyclic polyolefin material. The impact strength of the material is improved through the specific elastomer, and the lower dielectric constant, the dielectric loss and the higher transparency of the cyclic polyolefin are kept through the specific elastomer.
Because the cyclic polyolefin is a non-polar amorphous material, the elastomer is a polar material, and the compatibility of the cyclic polyolefin and the elastomer is poor, in order to adjust the size of a disperse phase of the elastomer in the cyclic polyolefin to achieve the balance of transparency and toughening at the same time, the compatilizer is adopted in the invention, so that the light transmittance and the impact toughness of the material are effectively improved.
Preferably, in the styrene-ethylene-butadiene-styrene block copolymer, the mass percentage of PS is 28-33%, and the weight average molecular weight of the styrene-ethylene-butadiene-styrene block copolymer is 5-8 ten thousand.
Preferably, the styrene-butadiene-styrene block copolymer is a linear structure; in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 10-15%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 7-8 ten thousand; when the mass percentage of PS in the styrene-butadiene-styrene block copolymer is 28-33%, the molecular weight of the styrene-butadiene-styrene block copolymer is 11-12 ten thousand.
Preferably, the light transmittance of the COC resin is greater than 90%; the light transmittance test standard is GB/T2410-2008; the COC resin is an injection molding-grade COC material; the COC resin has a melt flow rate of more than 15g/10min at 260 ℃ and 2.16 Kg.
Preferably, the compatilizer is at least one of maleic anhydride grafted polyethylene (PE-g-MAH) and maleic anhydride grafted cyclic polyolefin copolymer (COC-g-MAH); in the compatilizer, the grafting rate of maleic anhydride is 1-2%.
Preferably, the high-transparency low-dielectric-loss toughened cyclic polyolefin material further comprises the following components in parts by weight: 0.1-0.3 part of antioxidant and 0.1-0.2 part of lubricant.
More preferably, the antioxidant is a hindered amine antioxidant, and the lubricant is ethylene bis stearamide.
Meanwhile, the invention also provides a preparation method of the high-transparency low-dielectric-loss toughened cyclic polyolefin material, which comprises the following steps: mixing the components, adding the mixture into a main feeding system of an extruder, and mixing, extruding and granulating the mixture by the extruder to obtain the high-transparency low-dielectric-loss toughened annular polyolefin material.
In addition, the invention also discloses application of the high-transparency low-dielectric-loss toughened cyclic polyolefin material in the fields of communication, radar, aerospace, intelligent wearing, imaging and global positioning.
Compared with the prior art, the invention has the beneficial effects that:
1. high impact, notched impact performance>8KJ/m2Can meet the basic impact requirements of communication, electronics and household appliance industries;
2. the dielectric property is 2.4-2.6 at 2.5GHz, the dielectric constant is as low as 0.001-0.008, the electric field loss is extremely low, and the modern communication requirements are met;
3. the high transparency, the light transmittance is more than 70 percent, and the basic light transmittance requirement of the communication, electronic and household appliance industries can be met;
4. the invention is thermoplastic resin, can be processed by adopting a common injection molding process, and has convenient molding and high production efficiency.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. The following examples are merely exemplary of the present invention, and the scope of the present invention is not limited thereto.
The main representative materials used in the examples and comparative examples are as follows:
COC resin 1 #: the light transmittance of the COC resin is more than 90%; the COC resin is an injection molding-grade COC material; the melt flow rate of the COC resin under the conditions of 260 ℃ and 2.16Kg is more than 15g/10min (manufacturer: Mitsui chemical APEL 6015);
SBS elastomer 1 #: the mass percentage content of PS is 10-15%, and the weight average molecular weight is 7-8 ten thousand (the tomb petrifaction YH-796);
SBS elastomer 2 #: the mass percentage content of PS is 28-33%, and the weight average molecular weight is 11-12 ten thousand; (ba ling petrochemical YH-791);
the SBS elastomer 3# comprises 35-40% of PS by mass, and has a weight average molecular weight of 14-15 ten thousand (Basil petrifaction YH-792);
SEBS elastomer 1 #: the mass percentage content of PS is 28-33%, and the weight average molecular weight is 5-8 ten thousand; (Kraton G1652);
SEBS elastomer 2 #: the mass percentage content of PS is 35-40%, and the weight average molecular weight is 9-10 ten thousand; (Kraton G1654);
POE elastomer: dow chemical, POE ENGAGE 7467, melt flow rate of about 2g/10min at 190 deg.C and 2.16 Kg;
COC-g-MAH: the grafting rate of maleic anhydride is 1 percent; jinfa science and technology, Inc.;
PE-g-MAH: the grafting rate of maleic anhydride is 1 percent; koeis W1H;
PP-g-MAH (PP grafted maleic anhydride): the grafting rate of maleic anhydride is 1 percent, and Nanhai cypress is PC-1;
antioxidant: linaloon RIANOX 1010 and RIANOX 168;
lubricant: EBS lubricant, guangzhou jingyang chemical B50;
the relevant performance test criteria or methods are as follows:
light transmittance: reference GB/T2410-2008;
notched impact strength: ISO 180: 2000;
dielectric strength and dielectric loss: IPC-TM-6502.5.5.13-2007;
the preparation method of the high-transparency low-dielectric-loss toughened cyclic polyolefin material comprises the following steps:
mixing the components, adding the mixture into a main feeding system of an extruder, and mixing, extruding and granulating the mixture by the extruder to obtain the high-transparency low-dielectric-loss toughened annular polyolefin material; the temperature of the first zone to the second zone of the double-screw extruder is 200 ℃ to 220 ℃, the temperature of the third zone to the fifth zone is 220 ℃ to 240 ℃, the temperature of the fifth zone to the tenth zone is 240 ℃ to 260 ℃, and the rotating speed of the screw is 300rpm to 600 rpm.
The present application sets forth examples 1-12 and comparative examples 1-3, and the content of each component and the performance data of examples 1-5 and comparative examples 1-3 are shown in table 1; the contents of the respective components and the performance data in examples 6 to 12 are shown in Table 2.
TABLE 1 ingredients, contents, Performance data in examples 1-5 and comparative examples 1-3
TABLE 2 Components, contents, Performance data in examples 6 to 12
Comparing examples 1 to 5 with comparative example 2, it can be seen that the elastomer in comparative example 2 is not a styrene-butadiene-styrene block copolymer or a styrene-ethylene-butadiene-styrene block copolymer, and has a lower transmittance and a lower notched impact strength than examples 1 to 5 and a higher dielectric loss than examples 1 to 5 under the same other conditions.
Comparing examples 1 to 3, it can be seen that when the mass percent of PS in the SBS elastomer of examples 1 to 2 is 10% to 15%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 7 to 8 ten thousand; or in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 28-33%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 11-12 ten thousand; the SBS elastomer in the embodiment 3 is not in the above range, the transmittance and the notch impact strength in the embodiment 3 are lower than those in the embodiments 1 to 2, and the dielectric loss is higher than those in the embodiments 1 to 2.
Comparing example 4 with example 5, it can be seen that the SEBS elastomer in example 4 has a PS content of 33% by mass and a weight average molecular weight of 5-8 ten thousand; the SEBS elastomer in example 5 was out of the above range, and the transmittance and notched impact strength in example 5 were lower than those in example 4, and the dielectric loss was higher than that in example 4.
Comparing examples 10, 11 and 12, it can be seen that the compatibilizer in example 12 is not PE-g-MAH or COC-g-MAH, the transmittance and notched impact strength of example 12 are lower than those of examples 10 to 11, and the dielectric loss is higher than those of examples 10 to 11.
Comparing example 1 with comparative example 3, it can be seen that the content of elastomer in comparative example 3 is out of the range of the present application, the transmittance is significantly lower than that of example 1, and the dielectric loss is significantly higher than that of example 1.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A high-transparency low-dielectric-loss toughened cyclic polyolefin material is characterized by comprising the following components in parts by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of compatilizer; the elastomer is at least one of a styrene-butadiene-styrene block copolymer and a styrene-ethylene-butadiene-styrene block copolymer.
2. The high-transparency low-dielectric-loss toughened cyclic polyolefin material according to claim 1, wherein the mass percentage of PS in the styrene-ethylene-butadiene-styrene block copolymer is 28-33%, and the weight average molecular weight of the styrene-ethylene-butadiene-styrene block copolymer is 5-8 ten thousand.
3. The high transparent low dielectric loss toughened cyclic polyolefin material of claim 1, wherein the styrene-butadiene-styrene block copolymer is of a linear structure; in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 10-15%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 7-8 ten thousand; when the mass percentage of PS in the styrene-butadiene-styrene block copolymer is 28-33%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 11-12 ten thousand.
4. The high-transparency low-dielectric-loss toughened cyclic polyolefin material as claimed in claim 1, wherein the transmittance of the COC resin is greater than 90%, and the transmittance test standard is GB/T2410-2008; the COC resin is an injection molding-grade COC material; the COC resin has a melt flow rate of more than 15g/10min at 260 ℃ and 2.16 Kg.
5. The high transparent low dielectric loss toughened cyclic polyolefin material of claim 1, wherein the compatibilizer is at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted cyclic polyolefin copolymer; in the compatilizer, the grafting rate of maleic anhydride is 1-2%.
6. The high-transparency low-dielectric-loss toughened cyclic polyolefin material of claim 1, further comprising the following components in parts by weight: 0.1-0.3 part of antioxidant and 0.1-0.2 part of lubricant.
7. The high transparent low dielectric loss toughened cyclic polyolefin material of claim 6, wherein the antioxidant is a hindered amine antioxidant and the lubricant is ethylene bis stearamide.
8. The method for preparing the high-transparency low-dielectric-loss toughened cyclic polyolefin material according to any one of claims 1 to 7, wherein the method comprises the following steps: mixing the components, adding the mixture into a main feeding system of an extruder, and mixing, extruding and granulating the mixture by the extruder to obtain the high-transparency low-dielectric-loss toughened annular polyolefin material.
9. The use of the high transparent low dielectric loss toughened cyclic polyolefin material of any one of claims 1 to 7 in the fields of communication, radar, aerospace, smart wear, imaging, global positioning.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011325146.5A CN112457617B (en) | 2020-11-23 | 2020-11-23 | High-transparency low-dielectric-loss toughened cyclic polyolefin material and preparation method thereof |
| PCT/CN2021/092787 WO2022105149A1 (en) | 2020-11-23 | 2021-05-10 | Toughened cyclic polyolefin material with high transparency and low dielectric loss and preparation method therefor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956596A (en) * | 2021-10-18 | 2022-01-21 | 金旸（厦门）新材料科技有限公司 | Low-dielectric high-toughness COP/LDPE alloy material and preparation method thereof |
| WO2022105149A1 (en) * | 2020-11-23 | 2022-05-27 | 金发科技股份有限公司 | Toughened cyclic polyolefin material with high transparency and low dielectric loss and preparation method therefor |
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| CN115746488B (en) * | 2022-11-28 | 2023-11-21 | 金发科技股份有限公司 | Polyolefin composition and preparation method and application thereof |
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| CN108912578A (en) * | 2018-06-13 | 2018-11-30 | 金发科技股份有限公司 | A kind of modified cyclic polyolefin material and its application |
| WO2019028201A1 (en) * | 2017-08-03 | 2019-02-07 | Polyone Corporation | Translucent coc polymer compounds for 3d printing |
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| CA2168927A1 (en) * | 1995-02-07 | 1996-08-08 | Toshiyuki Hirose | Cycloolefin resin composition |
| JP3856875B2 (en) * | 1996-09-26 | 2006-12-13 | 三井化学株式会社 | Norbornene resin composition and use thereof |
| JPH1121413A (en) * | 1997-07-02 | 1999-01-26 | Kanegafuchi Chem Ind Co Ltd | Cycloolefin-based copolymer resin composition and its production |
| CN101501126A (en) * | 2006-08-04 | 2009-08-05 | 埃克森美孚化学专利公司 | Polymer compositions comprising cyclic olefin polymers, polyolefin modifiers, and fillers |
| CN112457617B (en) * | 2020-11-23 | 2022-09-13 | 金发科技股份有限公司 | High-transparency low-dielectric-loss toughened cyclic polyolefin material and preparation method thereof |
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| WO2019028201A1 (en) * | 2017-08-03 | 2019-02-07 | Polyone Corporation | Translucent coc polymer compounds for 3d printing |
| CN108912578A (en) * | 2018-06-13 | 2018-11-30 | 金发科技股份有限公司 | A kind of modified cyclic polyolefin material and its application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022105149A1 (en) * | 2020-11-23 | 2022-05-27 | 金发科技股份有限公司 | Toughened cyclic polyolefin material with high transparency and low dielectric loss and preparation method therefor |
| CN113956596A (en) * | 2021-10-18 | 2022-01-21 | 金旸（厦门）新材料科技有限公司 | Low-dielectric high-toughness COP/LDPE alloy material and preparation method thereof |
| CN113956596B (en) * | 2021-10-18 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | Low-dielectric high-toughness COP/LDPE alloy material and preparation method thereof |
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