Cycloolefin copolymer with polar group and preparation method thereof

A cyclic olefin copolymer and polar group technology, applied in the field of C08F, can solve the problems of lack of physical properties of cyclic olefin copolymer, loss of performance advantages of cyclic olefin copolymer, insufficient comonomer insertion rate, etc., to avoid crystallinity. Effects of segment generation, compatibility promotion, and enhancement of optical properties

Pending Publication Date: 2022-04-26
广东新华粤石化集团股份公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above catalysts have low polymerization activity, low polymer molecular weight, and insufficient comonomer insertion rate, resulting in the lack of necessary physical properties of the obtained cycloolefin copolymer, and the application is limited.
[0005] Chinese patent CN202010066897 discloses a method for preparing a copolymer containing polar norbornene to obtain a high-molecular-weight polymer. However, the copolymer prepared by this method has a low glass transition temperature and is elastic at room temperature. It maintains a high hardness structure above room temperature, so its application is greatly limited
Chinese patent CN202110078800 discloses a method for preparing ethylene and copolymerization of norbornene monomers with bipolar groups, which can obtain polymers with a glass transition temperature higher than room temperature. However, the copolymers obtained by this method have an obvious melting point (Tm). In some examples, the melting point even reaches 102.1°C, indicating that there are crystalline segments in the polymer. The existence of crystalline regions will significantly reduce the light transmittance of the polymer, and the performance advantages of cycloolefin copolymers will be lost and the application will be limited.

Method used

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  • Cycloolefin copolymer with polar group and preparation method thereof
  • Cycloolefin copolymer with polar group and preparation method thereof
  • Cycloolefin copolymer with polar group and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066]Embodiment 1 provides the preparation method of cycloolefin copolymer and the prepared copolymer thereof, including: adding solvent toluene, and a certain amount of norbornene monomer (b) and 5-hydroxy- 2-norbornene monomer (c), the concentrations of monomers (b) and (c) were 2.0 mol / L and 0.5 mol / L, respectively, and the total volume was kept at 200 mL. Start stirring, set the rotation speed at 500r / min, then feed ethylene monomer (a), raise the pressure to 0.5MPa, and equilibrate at 70°C for 30 minutes. Then, 2 mL of catalyst containing 5 μmol (Ar 1 and Ar 2 C respectively 6 h 5 , 2-{(2’,6’-(CH 3 O) 2 (C 6 h 3 )}C 6 h 4 , R 10 , R 11 Respectively CH 3 , H) dichloromethane solution, start the polymerization reaction, keep the system temperature and pressure constant during the polymerization process. After the reaction was carried out for 1 hour, the stirring was stopped, the temperature of the reactor was lowered to room temperature, the pressure was relea...

Embodiment 15

[0077] Embodiments 15-18 provide the preparation method of cycloolefin copolymer and the prepared copolymer. The polymerization conditions are respectively that monomer a is ethylene; monomer b is norbornene, concentration: 2mol / L; monomer c is 5 -Hydroxy-2-norbornene (Example 16-18), concentration: 0.5mol / L; Monomer d, concentration is 0.2mol / L (Example 16-18); Polymerization temperature: 70°C, polymerization pressure: 0.5MPa, polymerization time: 1h, catalyst dosage: 5μmol. Its specific implementation is the same as Example 1, and the difference is as shown in table 3. In addition, the polymer weight that embodiment 15-18 obtains, polymer glass transition temperature, the content of monomer b / c in the polymer, and Polymer melt index is listed in the following table 3, wherein the DSC collection of illustrative plates of embodiment 15 is as Figure 4 As shown, a Tg peak can be observed without a crystalline peak.

[0078] table 3

[0079]

[0080] Embodiments 19-22 pr...

Embodiment 23

[0085] Embodiments 23-26 provide the preparation method of cycloolefin copolymer and the prepared copolymer. The polymerization conditions are respectively that monomer a is ethylene; monomer b is norbornene, concentration: 1mol / L; monomer c is 5 -Hydroxy-2-norbornene, concentration: 0.2mol / L; polymerization temperature: 70°C, polymerization pressure: 0.5MPa, polymerization time: 1h, catalyst dosage: 5μmol. Its specific embodiment is the same as Example 1, and difference is as shown in table 5, in addition, the polymer weight that embodiment 8-14 obtains, polymer glass transition temperature, the content of monomer b / c in the polymer, and Polymer melt index is listed in the following table 5, wherein the DSC collection of illustrative plates of embodiment 23 is as Image 6 As shown, a Tg peak can be observed without a crystalline peak.

[0086] table 5

[0087]

[0088]

[0089] According to the performance tests of the copolymers prepared by different monomers a, b, c...

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Abstract

The invention relates to C08F, in particular to a cycloolefin copolymer with polar groups and a preparation method of the cycloolefin copolymer. Structural units of the cycloolefin copolymer comprise a vinyl unit A, a non-polar unit B and a polar unit. According to the cycloolefin copolymer provided by the invention, the polar cyclic unit is introduced, so that the compatibility and cohesiveness of the material in the use process can be promoted, and meanwhile, the structure of the non-polar unit and the polar unit can be controlled, so that the cycloolefin copolymer has high light transmission and provides high optical performance under different vinyl chain unit copolymers. By adjusting the use amount of a polar unit and a non-polar unit relative to a vinyl unit, the inventor finds that the polar copolymer is controlled to have a wide-range adjustable glass transition temperature, the formation of an amorphous structure can be promoted, the generation of a crystalline chain segment is avoided, and the improvement of optical characteristics is further promoted; the copolymer application range is expanded.

Description

technical field [0001] The present invention relates to C08F, more specifically, the present invention relates to a kind of cyclic olefin copolymer with polar group and preparation method. Background technique [0002] Polyolefin materials have been widely used in daily life. Among them, cyclic olefin copolymer (COC) is widely used in the fields of optics, packaging, medical treatment, and electronic products due to its excellent optical properties, good heat resistance, low dielectric constant, and good barrier properties. However, cyclic olefin copolymers composed only of carbon and hydrogen atoms have non-polar characteristics, which lead to disadvantages such as poor adhesion, poor printing effect, and insufficient compatibility with other polymer materials during application. Introducing polar groups into polymers is an effective method to solve the shortcomings of cycloolefin copolymers, improve their physical and chemical properties, and broaden their application ran...

Claims

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Application Information

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IPC IPC(8): C08F210/02C08F210/06C08F210/14C08F232/08C08F4/80
CPCC08F210/02C08F210/14C08F210/06C08F232/08C08F4/80
Inventor 廖恒左洪亮刘阳陈鹏州黄杰
Owner 广东新华粤石化集团股份公司
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