WO2022105149A1 - Toughened cyclic polyolefin material with high transparency and low dielectric loss and preparation method therefor - Google Patents

Abstract

Disclosed is a toughened cyclic polyolefin material with a high transparency and a low dielectric loss, comprising the following components in parts by weight: 70-85 parts of a COC resin, 10-20 parts of an elastomer and 5-10 parts of a compatilizer, wherein 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 a high impact property and a notched impact property of >13 KJ/m2, which can meet the basic impact requirements and light transmission requirements of the communication, electronics and household appliances industries. Also disclosed is a preparation method of the cyclic polyolefin material.

Description

A kind of high transparency and low dielectric loss toughened cyclic polyolefin material and preparation method thereof technical field

The invention relates to the field of polymer material modification, in particular to a toughened cyclic polyolefin material with high transparency and low dielectric loss and a preparation method thereof.

Background technique

Existing cyclic polyolefin materials, although low in dielectric constant and loss, have low impact strength and cannot meet the requirements for comprehensive properties of the material. Although the prior art can improve the impact strength, it loses transparency and increases the dielectric loss and dielectric constant at the same time.

SUMMARY OF THE INVENTION

Based on this, the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a toughened cyclic polyolefin material with high transparency and low dielectric loss.

In order to achieve the above purpose, the technical solution adopted in the present invention is: a high-transparency and low-dielectric loss toughened cyclic polyolefin material, comprising the following components by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of a compatibilizer; the elastomer is a styrene-butadiene-styrene block copolymer (SBS elastomer), a styrene-ethylene-butadiene-styrene block copolymer ( SEBS elastomer) at least one.

The material involved in the invention mainly improves the impact strength on the basis of ensuring the low dielectric loss performance and high transparency of the cyclic polyolefin material. Through the specific elastomer, the impact strength of the material is improved on the one hand, and the low dielectric constant, dielectric loss and high transparency of the cyclic polyolefin are maintained on the other hand.

Since the cyclic polyolefin is a non-polar amorphous material and the elastomer is a polar material, the compatibility between the two is not good. In order to adjust the size of the dispersed phase of the elastomer in the cyclic polyolefin to achieve simultaneous transparency and toughness The present invention adopts a compatibilizer, which effectively improves the light transmittance and impact toughness of the material.

Preferably, in the styrene-ethylene-butadiene-styrene block copolymer, the mass percentage of PS is 28%-33%, and the styrene-ethylene-butadiene-styrene The weight average molecular weight of the block copolymer is 50,000 to 80,000.

Preferably, the styrene-butadiene-styrene block copolymer has 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 70,000 to 80,000; when the styrene-butadiene-styrene block copolymer, when PS When the mass percentage of the styrene-butadiene-styrene block copolymer is 28%-33%, the molecular weight of the styrene-butadiene-styrene block copolymer is 110,000-120,000.

Preferably, the light transmittance of the COC resin is greater than 90%; the light transmittance test standard is GB/T 2410-2008; the COC resin is an injection molding grade COC material; the COC resin is 260°C, 2.16Kg The melt flow rate under the condition is greater than 15g/10min.

Preferably, the compatibilizer is at least one of maleic anhydride grafted polyethylene (PE-g-MAH) and maleic anhydride grafted cyclic polyolefin copolymer (COC-g-MAH); the In the compatibilizer, the graft ratio of maleic anhydride is 1% to 2%.

Preferably, the high transparency and low dielectric loss toughened cyclic polyolefin material further comprises the following components 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-stearic acid amide.

At the same time, the present invention also provides the preparation method of the high-transparency low-dielectric loss toughened cyclic polyolefin material. The method is as follows: mixing the components, adding them to the main feeding system of the extruder, and passing the extruder through the extruder. Mixing, extruding and granulating to obtain the high-transparency and low-dielectric-loss toughened cyclic polyolefin material.

In addition, the present invention also discloses the application of the high transparent and low dielectric loss toughened cyclic polyolefin material in the fields of communication, radar, aerospace, smart wear, imaging and global positioning.

Compared with the prior art, the beneficial effects of the present invention are:

1. High impact, notched impact performance >8KJ/m ² , which can meet the basic impact requirements of communications, electronics, and home appliance industries;

2. Dielectric properties, at 2.5GHz, the dielectric constant is 2.4-2.6, the dielectric loss is as low as 0.001-0.008, the electric field loss is extremely low, and it meets the requirements of modern communication;

3. High transparency, light transmittance > 70%, which can meet the basic light transmittance requirements of communication, electronics and home appliance industries;

4. The present invention is a thermoplastic resin, which can be processed by common injection molding process, with convenient molding and high production efficiency.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments. The following embodiments are only typical examples of the present invention, and the protection 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 greater than 90%; the COC resin is an injection molding grade COC material; the melt flow rate of the COC resin at 260°C and 2.16Kg is greater than 15g/10min (manufacturer : Mitsui Chemicals APEL6015);

SBS Elastomer 1#: The mass percentage of PS is 10%-15%, and the weight average molecular weight is 70,000-80,000 (Baling Petrochemical YH-796);

SBS Elastomer 2#: The mass percentage of PS is 28%-33%, and the weight average molecular weight is 110,000-120,000; (Baling Petrochemical YH-791);

SBS Elastomer 3#: The mass percentage of PS is 35%-40%, and the weight-average molecular weight is 140,000-150,000 (Baling Petrochemical YH-792);

SEBS Elastomer 1#: The mass percentage of PS is 28-33%, and the weight average molecular weight is 50,000-80,000; (Kraton G1652);

SEBS Elastomer 2#: The mass percentage of PS is 35-40%, and the weight average molecular weight is 90,000-100,000; (Kraton G1654);

POE elastomer: Dow Chemical, POE ENGAGE 7467, the melt flow rate is about 2g/10min at 190℃, 2.16Kg;

COC-g-MAH: maleic anhydride grafting rate of 1%; Kingfa Technology Co., Ltd.;

PE-g-MAH: maleic anhydride grafting rate 1%; Coace W1H;

PP-g-MAH (PP grafted maleic anhydride): maleic anhydride grafting rate of 1%, Nanhai Baichen PC-1;

Antioxidants: RIANOX 1010 and RIANOX 168;

Lubricant: EBS lubricant, Guangzhou Jinyang Chemical B50;

The relevant performance test standards or methods are as follows:

Light transmittance: refer to GB/T 2410-2008;

Notched impact strength: ISO 180:2000;

Dielectric strength and dielectric loss: IPC-TM-6502.5.5.13-2007;

The preparation method of the toughened cyclic polyolefin material with high transparency and low dielectric loss is as follows:

Mix the components, add them to the main feeding system of the extruder, and mix, extrude and granulate through the extruder to obtain the high-transparency and low-dielectric loss toughened cyclic polyolefin material; twin-screw extruder one to two The temperature of zone is 200℃～220℃, the temperature of zone three to five is 220℃～240℃, the temperature of zone five to ten is 240℃～260℃, and the screw speed is 300rpm～600rpm.

The application sets Examples 1 to 12 and Comparative Examples 1 to 3. The content and performance data of each component in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1; the content of each component in Examples 6 to 12, The performance data are shown in Table 2.

Table 1 Composition, content and performance data in Examples 1-5 and Comparative Examples 1-3

Table 2 Composition, content and performance data in Examples 6-12

Comparing Examples 1 to 5 with Comparative Example 2, it can be seen that under the same other conditions, the elastomer in Comparative Example 2 is not styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene The block copolymer of diene-styrene has lower light transmittance and notched impact strength than Examples 1-5, and higher dielectric loss than Examples 1-5.

Comparing Examples 1 to 3, it can be seen that in the SBS elastomers in Examples 1 to 2, when the mass percentage of PS is 10%-15%, the styrene-butadiene-styrene block copolymer has a The weight average molecular weight is 70,000-80,000; or in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 28%-33%, the styrene-butadiene - The weight average molecular weight of the styrene block copolymer is 110,000-120,000; the SBS elastomer in Example 3 is not within the above range, and the transmittance and notched impact strength in Example 3 are lower than those in Examples 1-2, and the intermediate The electrical loss is higher than that of Examples 1-2.

Comparing Example 4 with Example 5, it can be seen that the SEBS elastomer in Example 4 has a mass percentage content of PS of 33% and a weight-average molecular weight of 50,000 to 80,000; the SEBS elastomer in Example 5 is not in the above-mentioned range. 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, and the transmittance and notched impact strength of Example 12 are lower than those of Examples 10～ 11. The dielectric loss is higher than that of Examples 10-11.

Comparing Example 1 with Comparative Example 3, it can be seen that the content of elastomer in Comparative Example 3 is not within the scope of the present application, its 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 to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced 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, characterized in that it comprises the following components by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of compatibilizer; The elastomer is at least one of a styrene-butadiene-styrene block copolymer and a styrene-ethylene-butadiene-styrene block copolymer.
2. The toughened cyclic polyolefin material with high transparency and low dielectric loss according to claim 1, wherein, in the block copolymer of styrene-ethylene-butadiene-styrene, the mass percentage of PS is The content is 28%-33%, and the weight average molecular weight of the styrene-ethylene-butadiene-styrene block copolymer is 50,000-80,000.
3. The toughened cyclic polyolefin material with high transparency and low dielectric loss according to claim 1, wherein the styrene-butadiene-styrene block copolymer has a linear structure; the styrene- In the butadiene-styrene block copolymer, when the mass percentage content of PS is 10%-15%, the weight-average molecular weight of the styrene-butadiene-styrene block copolymer is 7-8 10,000; when in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 28%-33%, the styrene-butadiene-styrene block copolymer The weight average molecular weight is 11-12 million.
4. The high transparency and low dielectric loss toughened cyclic polyolefin material according to claim 1, wherein the light transmittance of the COC resin is greater than 90%, and the light transmittance test standard is GB/T 2410- 2008; the COC resin is an injection molding grade COC material; the melt flow rate of the COC resin at 260°C and 2.16Kg is greater than 15g/10min.
5. The toughened cyclic polyolefin material with high transparency and low dielectric loss according to claim 1, wherein the compatibilizer is maleic anhydride grafted polyethylene, maleic anhydride grafted cyclic polyolefin copolymer At least one of the compatibilizers; in the compatibilizer, the graft ratio of maleic anhydride is 1% to 2%.
6. The toughened cyclic polyolefin material with high transparency and low dielectric loss according to claim 1, further comprising the following components by weight: 0.1-0.3 part of antioxidant and 0.1-0.2 part of lubricant.
7. The high transparency and low dielectric loss toughened cyclic polyolefin material according to claim 6, wherein the antioxidant is a hindered amine antioxidant, and the lubricant is ethylene bis-stearic acid amide .
8. The method for preparing a high-transparency and 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 and adding them to the main feed of the extruder. The material system is mixed, extruded and pelletized by an extruder to obtain the high-transparency and low-dielectric loss toughened cyclic polyolefin material.
9. Application of the highly transparent and low dielectric loss toughened cyclic polyolefin material according to any one of claims 1 to 7 in the fields of communications, radar, aerospace, smart wear, imaging, and global positioning.