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Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin

A technology with high thermal stability and biphenyl structure, applied in the field of polymer materials, can solve the problems of wide molecular distribution, adding more solvent, depolymerization, etc., achieving narrow molecular weight distribution, reducing post-processing difficulty and reducing production costs Effect

Active Publication Date: 2015-04-01
JIANGMEN YOUJU NEW MATERIALS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] By changing the aromatic ring structure in the main chain structure of polyaryletherketone, the melting point of the polymer can be improved, and the application range of polyaryletherketone can be expanded, such as patent EP 0327984 (A 2 ), US4687833(A), but the viscosity of polyaryletherketone containing biphenyl structure they synthesized is all low
Chinese patents CN 971027080 and CN 971011680 utilize ternary copolymerization to synthesize high-viscosity polyether ether ketone and polyetherether ketone ketone containing biphenyl structure, but the salt-forming agent is mixed carbonate, and relatively expensive strontium carbonate is added. Moreover, the solid content of the reaction is 20%, and more solvents are added, and the cost is higher
Another example is the Chinese patent CN 2006100168898, using sulfolane as a solvent, potassium carbonate and sodium carbonate mixed salt system to prepare polyether ether ketone and polyetherether ketone ketone containing biphenyl structure. It can be seen from the experimental results that the glass transition temperature decreases, The viscosity of the synthesized copolymer becomes larger and the viscosity is higher, so its mechanical properties are lower than those of the previous two patents
Chinese patent 200810000647.9 uses sodium carbonate alone as the condensing agent and adds hydroquinone step by step to synthesize polyether ether ketone containing biphenyl structure. However, the chain growth of this method is relatively fast in the later stage of the reaction, and the process is unstable and uncontrollable. , difficult to industrialize, and the synthetic molecular distribution range is wide
The end-capping agents that these technologies adopt have the following defects in actual production: (1) adopt 4,4'-difluorobenzophenone as the end-capping agent, and 4,4'-difluorobenzophenone can be When adding in excess at one time, it can also be added in the later stage of the reaction
The existing end-capping agents have defects, which will cause depolymerization, and additional LiCl should be added

Method used

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  • Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin
  • Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin
  • Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] In a 200-liter stainless steel reaction kettle equipped with a nitrogen pipe and a high-efficiency stirrer, first add 90.00KG diphenyl sulfone, 30.000KG 4,4'-difluorobenzophenone, 12.54KG biphenol and 16.000KG sodium carbonate Then start to heat up to 130-140°C. After the monomers are completely dissolved, add 7.420KG hydroquinone to the system, continue to stir evenly, then raise the temperature to 180°C-220°C, react for 1-2 hours, and then heat up to 240°C ~260°C, react for 0.5~2 hours, raise the temperature to 270°C~280°C, react for 0.5~2 hours, then raise the temperature to 310°C~320°C and polymerize for 1~4 hours, add 283.7g 3,4'-difluorodiphenyl Methanone, continue to react for 10-30 minutes to obtain polymerized mucus; water-cooled and crushed polymerized mucus into powder or directly form a film on a stainless steel belt cooler and then pulverize, then add the filtered powder to ethanol and reflux to boil for 1 hour, repeat this for 10 Once again, boil it with n...

Embodiment 2

[0044] Same as Example 1, except that the amount of 3,4'-difluorobenzophenone is added to 340.3 g, other conditions are the same.

[0045] Gained biphenyl structure-containing PEEK resin melt index:

[0046] MI=20.7g / 10min (400.0°C, 5KG, 5 minutes);

[0047] MI=20.0g / 10min (400.0°C, 5KG, 30 minutes).

Embodiment 3

[0049] Same as Example 1, except that the amount of 3,4'-difluorobenzophenone is increased to 397.3g, other conditions are the same.

[0050] Gained biphenyl structure-containing PEEK resin melt index:

[0051] MI=30.4g / 10min (400.0°C, 5KG, 5 minutes);

[0052] MI=30.0g / 10min (400.0°C, 5KG, 30 minutes).

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PUM

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Abstract

The invention discloses an industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin. The industrial synthesis method of the high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin comprises the following steps: carrying out polymerization reaction based on paradioxybenzene, biphenol and 4,4'-difluoro diphenyl ketone or 4,4'-difluoro triphenyl diketone as reaction monomers, a high boiling point organic solvent as a solvent, alkali carbonate as a salt-forming agent and asymmetric aromatic ketone-based derivative as a blocking agent, so as to obtain polymerization mucosal fluid; cooling the polymerization mucosal fluid and smashing the cooled polymerization mucosal fluid into powder, filtering and boiling and washing with an organic solvent and deionized water for removing the solvent and byproduct salt, and drying, thus obtaining the binphenyl-structure-containing polyaryletherketone resin. The industrial synthesis method of the high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin has the advantages that sodium carbonate alkali metal is individually adopted as a catalyst, and a good blocking effect is realized after the blocking agent is added; besides, no polymerization phenomenon is caused in a system, and the obtained blocked binphenyl-structure-containing polyaryletherketone resin has high temperature thermal stability.

Description

technical field [0001] The invention belongs to the technical field of macromolecular materials, and in particular relates to an industrial synthesis method of polyaryl ether ketone resin with high thermal stability and capped polyaryl ether ketone resin containing biphenyl structure. Background technique [0002] Polyaryletherketone is a kind of high-performance engineering plastics. Now commercialized mainly include polyetherketone (PEK), polyetheretherketone (PEEK), polyetheretherketoneketone (PEEKK), because of their heat resistance, Excellent comprehensive properties such as hot water resistance, abrasion resistance, fatigue resistance, radiation resistance, peel resistance, creep resistance, dimensional stability, impact resistance, chemical resistance, non-toxic, flame retardant, etc. Therefore, it has been widely used in the fields of electronics, electrical appliances, machinery, automobiles, medical appliances, aviation industry, food processing and non-stick coati...

Claims

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Application Information

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IPC IPC(8): C08G8/02C08G65/40
Inventor 王贤文黎昱江友飞
Owner JIANGMEN YOUJU NEW MATERIALS
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