Composition for synthesizing polyether-ether-ketone, synthesis method of polyether-ether-ketone and polyether-ether-ketone

文档序号：251733 发布日期：2021-11-16 浏览：9次中文

阅读说明：本技术 用于合成聚醚醚酮的组合物、聚醚醚酮的合成方法及聚醚醚酮 (Composition for synthesizing polyether-ether-ketone, synthesis method of polyether-ether-ketone and polyether-ether-ketone ) 是由谢怀杰平仕衡于 2021-08-16 设计创作，主要内容包括：本发明公开了用于合成聚醚醚酮的组合物、聚醚醚酮的合成方法及聚醚醚酮。本发明组合物,至少由第一聚合单体和第一碱金属碳酸盐混合而成；第一聚合单体为4,4’-二氟二苯甲酮、2,4’-二氟二苯甲酮、4-氟二苯甲酮、4-氯二苯甲酮、4-氟-4’-氯-二苯甲酮、2-氟-4’-氯-二苯甲酮、2-氯-4’-氟-二苯甲酮、二苯醚、4,4’-二苯氧基二苯甲酮、对苯二甲酰氯和间苯二甲酰氯中的任一种。本发明利用第一聚合单体与碱金属碳酸盐的组合物即低纯度的聚合单体来制备聚醚醚酮,制备得到的聚醚醚酮具有较宽的分子量分布特征,具有低熔融指数和低粘度,在聚醚醚酮板材和管材等型材的加工领域具有广阔的应用前景。(The invention discloses a composition for synthesizing polyether-ether-ketone, a synthesis method of polyether-ether-ketone and polyether-ether-ketone. The composition of the invention is prepared by mixing at least a first polymerization monomer and a first alkali carbonate; the first polymerization monomer is any one of 4,4' -difluorobenzophenone, 2, 4' -difluorobenzophenone, 4-fluorobenzophenone, 4-chlorobenzophenone, 4-fluoro-4 ' -chlorobenzophenone, 2-chloro-4 ' -fluorobenzophenone, diphenyl ether, 4' -diphenoxybenzophenone, terephthaloyl chloride and isophthaloyl chloride. The polyether-ether-ketone is prepared from the composition of the first polymeric monomer and the alkali carbonate, namely the low-purity polymeric monomer, and the prepared polyether-ether-ketone has the characteristics of wide molecular weight distribution, low melt index and low viscosity, and has wide application prospects in the processing field of section bars such as polyether-ether-ketone plates, tubes and the like.)

1. A composition for synthesizing polyetheretherketone, formed by mixing at least a first polymeric monomer and a first alkali metal carbonate;

the first polymerization monomer is any one of 4,4' -difluorobenzophenone, 2, 4' -difluorobenzophenone, 4-fluorobenzophenone, 4-chlorobenzophenone, 4-fluoro-4 ' -chlorobenzophenone, 2-chloro-4 ' -fluorobenzophenone, diphenyl ether, 4' -diphenoxybenzophenone, terephthaloyl chloride and isophthaloyl chloride.

2. The composition of claim 1, wherein: the mass percentage content of the first polymerization monomer in the composition is 63-68%;

the first alkali metal carbonate is sodium carbonate and/or potassium carbonate.

3. A process for preparing a composition according to claim 1 or 2, comprising the steps of: and uniformly mixing the first polymerization monomer and the first alkali metal carbonate in a molten state to obtain the composition.

4. The production method according to claim 3, characterized in that: the mixing is carried out under the condition of heating and heat preservation, the heating temperature is 105-160 ℃, and the heat preservation time is 10-20 min;

the mixing is carried out under the stirring condition, and the rotating speed is 140-170 rpm;

the mixing is carried out under an inert atmosphere.

5. Use of a composition according to claim 1 or 2 for the preparation of polyetheretherketone.

6. A synthetic method of polyether-ether-ketone comprises the following steps: adding a second polymeric monomer, a second alkali metal carbonate and the composition of claim 1 or 2 in an inert aprotic solvent, and carrying out affinity polycondensation to obtain polyetheretherketone;

the second polymerization monomer is any one of hydroquinone, biphenol, 4' -dihydroxy benzophenone, 2-bis (4-hydroxyphenyl) propane, 1, 3-bis- (p-hydroxybenzoyl) benzene, 1, 4-bis- (p-hydroxybenzoyl) benzene, alpha-naphthol and beta-naphthol.

7. The method of claim 6, wherein:

the ratio of the number of moles a of the second polymeric monomer, the number of moles b of the first polymeric monomer, and the sum c of the number of moles of the second alkali metal carbonate and the first alkali metal carbonate a: b: c is 1: (1-1.2): (1.15-1.35);

the second alkali metal carbonate is sodium carbonate and/or potassium carbonate;

the molar ratio of the inert aprotic solvent to the second polymeric monomer is (3.5-4): 1;

the inert aprotic solvent is any one of sulfolane, diphenyl sulfone, glycerol, dimethylacetamide and methylpyrrolidone.

8. The method according to claim 6 or 7, characterized in that: the temperature of the nucleophilic polycondensation reaction is 200-305 ℃, and the time is 4-6 hours; preferably, the temperature is firstly increased to 200 ℃ and kept constant for 1h, then increased to 280 ℃ and kept constant for 1h, and finally increased to 305 ℃ and kept constant for 2 h.

9. Polyetheretherketone synthesized by the method of any one of claims 6 to 8.

10. Use of a polyetheretherketone according to claim 9 in the preparation of a polyetheretherketone profile.

Technical Field

The invention relates to a composition for synthesizing polyether-ether-ketone, a synthesis method of polyether-ether-ketone and polyether-ether-ketone, and belongs to the technical field of high polymer materials.

Background

Polyaryletherketones are high-end products among special engineering plastics, and are typically Polyetheretherketones (PEEK), which are high-performance special engineering plastics developed in 1978 by the british empire chemical industry (ICI corporation), and PEEK of the ICI corporation has been transferred to VICTREX corporation of the british. In China, PEEK is regarded as a strategic national defense and military material due to the excellent performance of PEEK, and the research thereof is always listed in the seventy-five national key science and technology project and the '863 plan'. Polyetheretherketone is generally synthesized by stepwise polymerization of alkylated bisphenolates. The reaction is typically carried out using high purity 4,4' -difluorobenzophenone and disodium hydroquinone (disodium hydroquinone is formed by reacting hydroquinone with sodium carbonate) in an aprotic solvent, such as diphenylsulfone, at about 300 degrees. The polyether ether ketone prepared by the method has a narrow molecular weight distribution, and the polyether ether ketone with the narrow molecular weight distribution has higher melt viscosity mainly under the condition of lower melt index in the aspect of performance.

At present, the production of PEEK plates and pipe products has a large market, the domestic market has the scale of thousands of tons per year, but the extrusion of the plates and the pipes not only needs the PEEK products with lower melt index, but also requires the PEEK to have lower melt viscosity, and the PEEK prepared by the traditional method can not meet the requirement of preparing the PEEK of the plates and the pipes, so the preparation of the PEEK with low melt index and low melt viscosity has wide prospect.

Disclosure of Invention

In order to solve the above technical problems, an object of the present invention is to provide a composition for synthesizing polyetheretherketone, a method for synthesizing polyetheretherketone, and polyetheretherketone, wherein the polyetheretherketone prepared by the method has a wide molecular weight distribution characteristic, a low melt index, and a low viscosity.

It is a first object of the present invention to provide a composition for synthesizing polyetheretherketone, formed by mixing a first polymeric monomer and a first alkali metal carbonate;

In the composition, the mass percentage of the first polymerized monomer in the composition may be 63% to 68%, specifically 67.31%, 64.16%, 64.02%, 63.88% or 63.74%. The first polymerization monomer is a pure product, such as a pure product with the purity of more than or equal to 99.9%.

Preferably, the first alkali metal carbonate may be sodium carbonate and/or potassium carbonate, and a light alkali metal carbonate or a nano-sized alkali metal carbonate may be used.

The invention further provides a preparation method of the composition, which comprises the following steps: and uniformly mixing the first polymerization monomer and the first alkali metal carbonate in a molten state to obtain the composition.

In the preparation method, the mixing can be carried out under the condition of heating and heat preservation, and the heating temperature can be 105-160 ℃, such as 140 ℃; the heat preservation time can be 10-20 min, such as 15 min.

In the above preparation method, the mixing may be performed under stirring; preferably, the rotation speed of the stirring is 140-170 rpm, such as 160 rpm.

In the above-mentioned production method, the method may be carried out under an inert atmosphere, such as a nitrogen atmosphere.

The invention further provides application of the composition in preparation of polyether-ether-ketone.

The invention also provides a synthesis method of the polyether-ether-ketone, which comprises the following steps: adding a second polymeric monomer, a second alkali metal carbonate and the composition into an inert aprotic solvent, and carrying out affinity polycondensation reaction to obtain polyether-ether-ketone;

In the above synthesis method, the composition may be fed directly in a molten state or may be fed after cooling.

In the above synthesis method, the ratio of the number of moles a of the second polymeric monomer, the number of moles b of the first polymeric monomer, and the sum c of the number of moles of the second alkali metal carbonate and the first alkali metal carbonate a: b: c is 1: (1-1.2): (1.15-1.35), specifically 1: 1: (1.28-1.35), 1: 1: 1.28, 1: 1: 1.29, 1: 1: 1.32 or 1: 1: 1.35.

in the above synthesis method, the second alkali metal carbonate may be sodium carbonate and/or potassium carbonate, and a light alkali metal carbonate or a nano alkali metal carbonate may be used.

In the above synthesis method, the mole ratio of the inert aprotic solvent to the second polymeric monomer is (3.5-4): 1, specifically 3.6: 1;

the inert aprotic solvent may be any one of sulfolane, diphenyl sulfone, glycerol, dimethylacetamide and methylpyrrolidone.

In the synthesis method, the temperature of the nucleophilic polycondensation reaction can be 200-305 ℃, the time can be 4-6 hours, and specifically, the temperature can be first raised to 200 ℃ and then kept constant for 1 hour, then raised to 280 ℃ and kept constant for 1 hour, and finally raised to 305 ℃ and kept constant for 2 hours.

Polyetheretherketone synthesized by the method of any of the above, is also within the scope of the present invention.

The molecular weight distribution width PD of the polyether-ether-ketone is more than or equal to 2.10 through GPC test;

the value of the melt viscosity/melt mass flow rate of the polyether-ether-ketone is less than or equal to 50, wherein the unit of the melt viscosity is g/10min, and the unit of the melt mass flow rate is Pa.S.

The invention also provides application of the polyether-ether-ketone in preparation of polyether-ether-ketone profiles.

The profile may be any one of a pipe, a plate, a sheet and a bar.

In the present invention, "first" and "second" in the first polymerized monomer, the second polymerized monomer, the first alkali metal carbonate and the second alkali metal carbonate do not indicate any order, amount or importance, but are merely used for distinction.

The invention has the following beneficial effects:

the composition for synthesizing the polyether-ether-ketone is prepared by mixing 4,4' -difluorobenzophenone or other polymeric monomers with alkali carbonate, and the polyether-ether-ketone prepared by using the composition has the characteristics of wider molecular weight distribution, low melt index and low viscosity, and has wide application prospect in the processing field of section bars such as polyether-ether-ketone plates, pipes and the like.

Drawings

FIG. 1 shows the results of molecular weight distribution of a sample of PEEK prepared in example 1 by PL-220 gel chromatography (GPC).

FIG. 2 shows the results of molecular weight distribution of a sample of PEEK prepared in example 2 by PL-220 gel chromatography (GPC).

FIG. 3 shows the results of molecular weight distribution of a sample of PEEK prepared in example 3 by PL-220 gel chromatography (GPC).

FIG. 4 shows the results of molecular weight distribution of a sample of PEEK prepared in example 4 by PL-220 gel chromatography (GPC).

FIG. 5 shows the results of molecular weight distribution of a sample of PEEK prepared in example 5 by PL-220 gel chromatography (GPC).

FIG. 6 shows the results of molecular weight distribution of a sample of PEEK prepared in example 6, measured by PL-220 gel chromatography (GPC).

FIG. 7 shows the results of molecular weight distribution of a sample of PEEK prepared in example 7 by PL-220 gel chromatography (GPC).

FIG. 8 is the results of molecular weight distribution of a sample of PEEK prepared in example 8 by PL-220 gel chromatography (GPC).

FIG. 9 shows the results of molecular weight distribution of a sample of PEEK prepared in example 9 by PL-220 gel chromatography (GPC).

FIG. 10 shows the results of molecular weight distribution of a sample of PEEK prepared in example 10, as measured by PL-220 gel chromatography (GPC).

FIG. 11 shows the results of molecular weight distribution of a sample of PEEK prepared in example 11, as measured by PL-220 gel chromatography (GPC).

Detailed Description

The composition for synthesizing the polyether-ether-ketone is prepared by mixing a first polymerization monomer and a first alkali carbonate;

the first polymeric monomer is selected from any one of 4,4' -difluorobenzophenone, 2, 4' -difluorobenzophenone, 4-fluorobenzophenone, 4-chlorobenzophenone, 4-fluoro-4 ' -chlorobenzophenone, 2-chloro-4 ' -fluorobenzophenone, diphenyl ether, 4' -diphenoxybenzophenone, terephthaloyl chloride and isophthaloyl chloride.

The invention provides a synthesis method of polyether-ether-ketone, which comprises the following steps: adding a second polymeric monomer, a second alkali metal carbonate and the composition into an inert aprotic solvent, and carrying out affinity polycondensation reaction to obtain polyether-ether-ketone;

the second polymeric monomer is selected from any one of hydroquinone, biphenol, 4' -dihydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, 1, 3-bis- (p-hydroxybenzoyl) benzene, 1, 4-bis- (p-hydroxybenzoyl) benzene, alpha-naphthol, and beta-naphthol.

The present invention will be described in detail below with reference to an example of synthesizing polyether ether ketone by nucleophilic polycondensation of hydroquinone using low-purity 4,4 '-difluorobenzophenone obtained by mixing 4,4' -difluorobenzophenone and an alkali metal carbonate as a raw material. The result shows that the polyether-ether-ketone prepared by using the low-purity 4,4' -difluorobenzophenone has a wider molecular weight distribution characteristic, a low melting index and low viscosity.

The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.

The experimental procedures in the following examples, unless otherwise indicated, are conventional and are carried out according to the techniques or conditions described in the literature in the field or according to the instructions of the products. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The sodium carbonate used in the following examples is light sodium carbonate, and meets all indexes of the national standard industrial sodium carbonate GB 210-92 of the people's republic of China, and the light potassium carbonate meets all indexes of GB/T1587-2000.

Example 1 of the present invention is a comparative example of a conventional synthesis method, and examples 2 to 11 provide a method for preparing polyetheretherketone using 4,4 '-difluorobenzophenone of low purity, and provide results of measuring molecular weight distribution, melt flow rate, viscosity, etc. of polyetheretherketone prepared using 4,4' -difluorobenzophenone of different low purity, and comparative analysis of the results, thereby obtaining examples of the widest molecular weight distribution.

The melt flow rate is measured by using a melt flow rate meter, according to the test standard of ISO 1133, under the condition of 380 ℃, a weight with the load of 5000g is used, the diameter of a melt flow rate meter neck mold is 2mm +/-0.095 mm, the melt Mass Flow Rate (MFR) is taken as the test result, and the average value is taken after three times of tests; the viscosity is measured by a Dynisco LCR7001 capillary rheometer, the load is 10KN at the temperature of 400 ℃, and the shear flow rate is 1000 (1/S); molecular weight distribution was measured using Agilent Technologies PL-GPC220 High Temperature chromatography (Agilent PL-GPC220 High Temperature gel chromatography) using α -chloronaphthalene as the solvent and 1,2, 4-trichlorobenzene as the diluent. The temperature of the chromatographic column is 115 ℃, the mobile phase adopts a mixture of alpha-chloronaphthalene and 1,2, 4-trichlorobenzene, and the mass ratio of the alpha-chloronaphthalene to the 1,2, 4-trichlorobenzene is as follows: 1,2, 4-trichlorobenzene is 1:2.2, and the test parameters are that K is 14.1 and alpha is 0.7.

Example 1:

a3000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle opening, one side opening is connected with a tee joint for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 240.02g of 4,4' -difluorobenzophenone, 121.11g of hydroquinone and 150.01g of Na after the diphenyl sulfone is molten₂CO₃After all the materials are melted, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h,heating to 280 deg.C, holding the temperature for 1h, heating to 305 deg.C, holding the temperature for 2h, and pouring into cold distilled water to obtain loose lump.

Crushing the block loose objects, putting 100g of the sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, adding 500ml of pure water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample.

Melt mass flow rate test (MFR): testing according to the test standard of GB/T3682.1-2018 (ISO 1133).

Measurement of melt viscosity: according to the GB/T25278-.

Measurement of molecular weight distribution: placing a 20mg PEEK sample into a 10ml penicillin bottle, adding 3.15ml Alpha-chloronaphthalene by using a pipette, placing the mixture into an oscillator at 150 ℃ to shake for 1.5h, completely dissolving the sample into the Alpha-chloronaphthalene, cooling, adding 4.20ml 1,2, 4-trichlorobenzene into a Xilin bottle to shake uniformly, taking 2ml of the sample from the penicillin bottle by using a filter pipette, adding the sample into an An-cut bottle, sealing the An-cut bottle by using an aluminum cover, placing the An-cut bottle on a PL-220 gel chromatograph (GPC) sample tray, and measuring the molecular weight distribution of the sample as shown in figure 1 under the conditions of column temperature of 115 ℃ and 1ml/min of mobile phase, wherein the sample feeding amount is 200 mu l, the k value is 14.1 and the Alpha value is 0.7.

Example 2:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating sleeve, putting 436.4g (2mol) of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking off the spherical condenser tube, putting 211.98g (1.93mol) of Na into the bottle from a side opening₂CO₃Connecting the spherical condenser tube to the side opening again, accelerating the stirring speed to 160rpm, heating to 140 ℃, keeping the temperature for 15min, quickly pouring the reactants in the three-mouth bottle into a metal plate made of 022Cr17Ni12Mo2 material, and naturally cooling to room temperature to obtain the productA mixture of 4,4 '-difluorobenzophenone and sodium carbonate in bulk form, wherein the purity of 4,4' -difluorobenzophenone is 67.31%, and grinding for later use.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g (4mol) of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g (1.1mol) of hydroquinone after the diphenyl sulfone is molten, and adding 33.01g (0.31mol) of Na after the hydroquinone is molten₂CO₃Keeping the temperature at 140 ℃, adding 356.61g of the mixture of the 4,4 '-difluorobenzophenone (1.1mol) with the purity of 67.31% and sodium carbonate (1.1mol), starting stirring to 100rpm after the 4,4' -difluorobenzophenone is melted, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain the blocky loose object.

Testing of melt mass flow rate, melt viscosity and molecular weight distribution: the test conditions were the same as described in example 1, and the molecular weight distribution of the sample was determined as shown in FIG. 2.

Example 3:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating jacket, adding 436.4g of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking down the spherical condenser tube, adding 243.78g of Na from a side opening₂CO₃The edge opening is connected with the spherical condenser tube again, the stirring speed is increased to 160rpm, and the temperature is raised toKeeping the temperature at 140 ℃ for 15min, quickly pouring reactants in a three-necked flask into a metal disc made of 022Cr17Ni12Mo2 to obtain a mixture of blocky 4,4 '-difluorobenzophenone and sodium carbonate, wherein the purity of the 4,4' -difluorobenzophenone is 64.16%, and crushing for later use.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g (4mol) of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g (1.1mol) of hydroquinone after the diphenyl sulfone is molten, and adding 15.90g (0.15mol) of Na after the hydroquinone is molten₂CO₃Keeping the temperature at 140 ℃, adding 374.10g of a mixture of 64.16% purity 4,4 '-difluorobenzophenone (1.1mol) and sodium carbonate (1.27mol), starting stirring to 100rpm after 4,4' -difluorobenzophenone is melted, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

Example 4:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating jacket, adding 436.4g of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking down the spherical condenser tube, adding 238.90g of the spherical condenser tube from a side openingNa of (2)₂CO₃And 6.36g of K₂CO₃And (3) connecting a spherical condenser pipe again at the edge opening, accelerating the stirring speed to 160rpm, heating to 140 ℃, keeping the temperature for 15min, quickly pouring reactants in a three-opening bottle into a metal disc made of 022Cr17Ni12Mo2 material to obtain a mixture of blocky 4,4 '-difluorobenzophenone, sodium carbonate and potassium carbonate, wherein the purity of the 4,4' -difluorobenzophenone is 64.02%, and crushing for later use.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 15.20g of Na after the hydroquinone is molten₂CO₃Keeping the temperature at 140 ℃, adding 374.91g of the mixture of the 4,4 '-difluorobenzophenone with the purity of 64.02% and sodium carbonate potassium carbonate, stirring to 100rpm after the 4,4' -difluorobenzophenone is melted, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain the blocky loose object.

Example 5:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating jacket, adding 436.4g of 4,4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening the cooling water of a spherical condenser tube, and startingHeating, after 4,4' -difluorobenzophenone was completely melted, stirring to 60rpm, removing the spherical condenser tube, and charging 246.76g of Na through the edge₂CO₃And (3) connecting a spherical condenser pipe with the edge opening again, accelerating the stirring speed to 160rpm, heating to 140 ℃, keeping the temperature for 15min, quickly pouring reactants in the three-mouth bottle into a metal disc made of 022Cr17Ni12Mo2 material to obtain blocky 4,4 '-difluorobenzophenone and sodium carbonate, wherein the purity of the 4,4' -difluorobenzophenone is 63.88%, and crushing for later use.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 14.30g of Na after the hydroquinone is molten₂CO₃Keeping the temperature at 140 ℃, adding 375.76g of a mixture of 63.88% purity 4,4 '-difluorobenzophenone and sodium carbonate, starting stirring to 100rpm after 4,4' -difluorobenzophenone is molten, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain the blocky loose object.

Example 6:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Placing the three-necked bottle in an electric heating jacket, adding 436.4g of 4,4' -difluorobenzophenone into the bottle, and introducing the solution with a flow rate of 60ml/minHigh purity nitrogen, opening cooling water of spherical condenser tube, heating, stirring to 60rpm after 4,4' -difluorobenzophenone is completely melted, taking off spherical condenser tube, and adding 248.25g Na from edge₂CO₃And (3) connecting a spherical condenser pipe again at the edge opening, accelerating the stirring speed to 160rpm, heating to 140 ℃, keeping the temperature for 15min, quickly pouring reactants in a three-opening bottle into a metal disc made of 022Cr17Ni12Mo2 material to obtain a mixture of blocky 4,4 '-difluorobenzophenone and sodium carbonate, wherein the purity of the 4,4' -difluorobenzophenone is 63.74%, and crushing for later use.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 13.50g of Na after the hydroquinone is molten₂CO₃Keeping the temperature at 140 ℃, adding 376.56g of the mixture of the 4,4 '-difluorobenzophenone with the purity of 63.74% and the sodium carbonate, stirring to 100rpm after the 4,4' -difluorobenzophenone is melted, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain the lump loose object.

Example 7:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Placing the three-mouth bottle in an electric heating sleeve and placing the three-mouth bottle in the bottle240.02g of 4,4 '-difluorobenzophenone is added, high-purity nitrogen with the flow rate of 60ml/min is introduced, cooling water of a spherical condenser pipe is opened, heating is started, stirring is started to 60rpm after the 4,4' -difluorobenzophenone is completely melted, the spherical condenser pipe is taken down, 116.59g of Na is added from a side opening₂CO₃And the edge opening is connected with a spherical condenser tube again, the stirring speed is increased to 160rpm, the temperature is increased to 140 ℃, the temperature is kept for 15min, and the purity of the 4,4' -difluorobenzophenone is 63.74%.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 33.40g of Na after the hydroquinone is molten₂CO₃And keeping the temperature constant to 140 ℃. Pouring the mixture of the 4,4' -difluorobenzophenone with the purity of 63.74% and the sodium carbonate with the temperature of 140 ℃ into a 3000ml three-necked bottle while the mixture is hot, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

Example 8:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Placing the three-neck bottle in an electric heating jacket, adding 240.02g of 4,4' -difluorobenzophenone, introducing high-purity nitrogen gas with flow rate of 60ml/min, and opening the cooling of a spherical condenser tubeCooling water, heating, melting 4,4' -difluorobenzophenone, stirring to 60rpm, removing spherical condenser tube, and adding 134.08g Na₂CO₃And the edge opening is connected with a spherical condenser pipe again, the stirring speed is increased to 160rpm, the temperature is increased to 140 ℃, the temperature is kept for 15min, and the purity of the 4,4' -difluorobenzophenone is 64.16%.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 15.90g of Na after the hydroquinone is molten₂CO₃And keeping the temperature constant to 140 ℃. Pouring the mixture of the 4,4' -difluorobenzophenone with the purity of 64.16% and the sodium carbonate at 140 ℃ into a 3000ml three-necked bottle while the mixture is hot, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

Example 9:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating sleeve, adding 240.02g of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking off the spherical condenser tube134.89g of Na was poured in from the edge₂CO₃And the edge opening is connected with a spherical condenser pipe again, the stirring speed is increased to 160rpm, the temperature is increased to 140 ℃, the temperature is kept for 15min, and the purity of the 4,4' -difluorobenzophenone is 64.02%.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 18.60g of Na after the hydroquinone is molten₂CO₃And keeping the temperature constant to 140 ℃. Pouring the mixture of the 4,4' -difluorobenzophenone with the purity of 64.02% and the sodium carbonate at 140 ℃ into a 3000ml three-necked bottle while the mixture is hot, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

Example 10:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating jacket, adding 240.02g of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking down the spherical condenser tube, adding 135.72g of Na from a side opening₂CO₃The edge is connected with the spherical condenser tube again to accelerate the stirring speedHeating to 160rpm, heating to 140 deg.c and maintaining for 15min to reach 4,4' -difluorobenzophenone purity 63.88%.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 21.30g of Na after the hydroquinone is molten₂CO₃And keeping the temperature constant to 140 ℃. Pouring the mixture of the 4,4' -difluorobenzophenone with the purity of 63.88% and the sodium carbonate at 140 ℃ into a 3000ml three-necked bottle while the mixture is hot, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

Example 11:

a stirring paddle is inserted into the middle opening of a 1000ml three-mouth bottle, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe. Putting a three-mouth bottle in an electric heating jacket, adding 240.02g of 4,4 '-difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 60ml/min, opening cooling water of a spherical condenser tube, starting heating, starting stirring to 60rpm after the 4,4' -difluorobenzophenone is completely melted, taking down the spherical condenser tube, adding 136.54g of Na from a side opening₂CO₃And the edge opening is connected with a spherical condenser tube again, the stirring speed is increased to 160rpm, the temperature is increased to 140 ℃, the temperature is kept for 15min, and the purity of the 4,4' -difluorobenzophenone is 63.74%.

And another 3000ml three-mouth bottle is taken, a stirring paddle is inserted into the middle port, one side port is connected with a tee joint for placing a thermometer and a high-purity nitrogen gas inlet, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, adding 873.08g of diphenyl sulfone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 121.11g of hydroquinone after the diphenyl sulfone is molten, and adding 24.0g of Na after the hydroquinone is molten₂CO₃And keeping the temperature constant to 140 ℃. Pouring the mixture of the 4,4' -difluorobenzophenone with the purity of 63.74% and the sodium carbonate with the temperature of 140 ℃ into a 3000ml three-necked bottle while the mixture is hot, starting stirring to 100rpm, heating to 200 ℃, keeping the temperature for 1h, heating to 280 ℃, keeping the temperature for 1h, heating to 305 ℃, keeping the temperature for 2h, and pouring the materials into cold distilled water to obtain a blocky loose substance.

The results of comparison of examples 1-11 are shown in Table 1.

Table 1, comparative results of examples 1 to 11

(. short for fluoroketone 4,4' -difluorobenzophenone in this table)

According to the analysis of the table, the melt viscosity of the polyetheretherketone with the same melt mass flow rate can be effectively reduced by adopting the low-purity 4,4' -difluorobenzophenone, and the molecular weight distribution diagram shows that the polyetheretherketone with the same melt mass flow rate has lower melt viscosity only under the condition of wider molecular weight distribution; examples 2-5 comparative examples 6-10 show that 4,4' -difluorobenzophenone, which is also of low purity, has no effect on the final viscosity of the polyetheretherketone, whether fed directly or indirectly.

The embodiments of the present invention provide a method for reducing the purity of 4,4' -difluorobenzophenone by adding sodium carbonate or (and) potassium carbonate as a method for reducing the purity of 4,4' -difluorobenzophenone and a method for preparing polyetheretherketone using 4,4' -difluorobenzophenone of low purity, which is characterized by a remarkably broad molecular weight distribution, i.e., polyetheretherketone prepared using 4,4' -difluorobenzophenone of low purity has a lower melt viscosity under the same melt mass flow rate, and the present inventors found that polyetheretherketone prepared using 4,4' -difluorobenzophenone of low purity has a feature of melt viscosity (η)/melt Mass Flow Rate (MFR) of 50 or less. Any modification or simulation of the methods provided by the present invention is considered to infringe the rights of this patent.

The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. The use of some of the essential features is possible within the scope of the claims attached below.

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Composition for synthesizing polyether-ether-ketone, synthesis method of polyether-ether-ketone and polyether-ether-ketone

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