阅读说明：本技术 一种芳族砜聚合物及其制备方法和应用 (Aromatic sulfone polymer and preparation method and application thereof ) 是由 高红军 王道波 张登 黄险波 叶南飚 孙学科 陈锐斌 杨硕 姜苏俊 曹民 于 2020-12-23 设计创作，主要内容包括：本发明涉及一种芳族砜聚合物及其制备方法和应用。该芳族砜聚合物的酚端基含量为30～80mol/t,Fe元素含量不高于40ppm。本发明通过调控芳族砜聚合物的酚端基含量和Fe元素含量,得到的芳族砜聚合物热稳定性好,着色性能优异,对制备颜色鲜艳、高亮度的芳族砜组合物有实际指导意义。(The invention relates to an aromatic sulfone polymer and a preparation method and application thereof. The aromatic sulfone polymer has a phenolic end group content of 30-80 mol/t and an Fe element content of not higher than 40 ppm. According to the invention, by regulating the content of the phenolic terminal group and the content of the Fe element in the aromatic sulfone polymer, the obtained aromatic sulfone polymer has good thermal stability and excellent coloring performance, and has practical guiding significance for preparing aromatic sulfone compositions with bright colors and high brightness.)

1. An aromatic sulfone polymer, characterized in that the aromatic sulfone polymer has a phenolic terminal group content of 30 to 80mol/t and an Fe element content of not more than 40 ppm.

2. The aromatic sulfone polymer of claim 1, wherein the aromatic sulfone polymer has a phenolic terminal group content of 40 to 60 mol/t.

3. The aromatic sulfone polymer according to claim 1, wherein the aromatic sulfone polymer has an Fe element content of 10 to 20 ppm.

4. The aromatic sulfone polymer of claim 1, wherein the aromatic sulfone polymer is one or more of polyphenylsulfone, polyethersulfone, polysulfone, or polyetherethersulfone.

5. The aromatic sulfone polymer of claim 1, wherein the phenolic end groups comprise a phenolic hydroxyl end group and a phenolate end group.

6. A process for producing an aromatic sulfone polymer as described in any one of claims 1 to 5, which comprises the steps of:

s1, salt forming reaction: mixing a phenol monomer, a sulfone monomer, a salt forming agent, an entrainer and a solvent, and carrying out a salt forming reaction at 180-220 ℃;

s2, polymerization: heating the system subjected to the salt forming reaction of S1 to 230-240 ℃ for polymerization reaction, adding a monohalogenated compound for continuous reaction until the polymerization reaction is finished, and performing post-treatment to obtain the aromatic sulfone polymer;

the total content of Fe element in the phenolic monomer and the sulfone monomer is not higher than 40 ppm.

7. The method according to claim 6, wherein the phenolic monomer in S1 is 4, 4' -bis

One or more of hydroxy diphenyl sulfone, biphenol or 2, 2' -bis (4-hydroxyphenyl) propane;

the sulfone monomer is one or more of 4,4 '-dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone or bis- (4-chlorobenzenesulfonyl) biphenyl;

the salt forming agent is one or more of sodium carbonate or potassium carbonate;

the entrainer is one or more of toluene, xylene or trimethylbenzene.

8. The method according to claim 6, wherein the monohalogenated compound in S2 is one or more selected from methyl chloride, ethyl chloride, 4-fluoro diphenyl sulfone, 4-chloro diphenyl sulfone and 4-bromo diphenyl sulfone.

9. The method according to claim 6, wherein the molar ratio of the monohalogenated compound to the phenolic monomer in S2 is 0.03-0.08: 1.

10. Use of an aromatic sulfone polymer as claimed in any one of claims 1 to 5 in the preparation of an aromatic sulfone composition.

Technical Field

The invention belongs to the technical field of high molecular materials, and particularly relates to an aromatic sulfone polymer and a preparation method and application thereof.

Background

The aromatic sulfone polymer belongs to a high-temperature-resistant and high-transparency high polymer material, has excellent characteristics of chemical corrosion resistance, excellent electrical property, stable size and the like, is widely applied to the fields of aerospace, medical treatment, food and the like, but has large intermolecular cohesive energy due to the existence of strong polar sulfone groups in molecular chains, so that the problems of large melt viscosity and poor flowability of hot processing, high processing temperature, easy yellowing and other product defects are caused. In the process of preparing the color matching composition, high-temperature-resistant toner is required to be selected due to high processing temperature, the optional range is narrow, and the color matching process at high temperature is difficult to prepare the aromatic sulfone color matching composition with bright color and high brightness due to poor interaction between a polymer and the toner or adverse effects caused by metal elements, particularly Fe elements. Aromatic sulfone polymers or compositions having high brightness and excellent coloring properties have been reported. Researchers often add a proper amount of additives to improve the coloring performance, for example, CN111448256A adds a phosphorous compound to a polyarylether polymer to prepare a polyarylether resin composition with excellent coloring performance, and the whiteness index is effectively improved.

Therefore, the development of an aromatic sulfone polymer or composition having excellent coloring properties has important research significance and application value.

Disclosure of Invention

The invention aims to overcome the defects or shortcomings of high brightness and excellent coloring performance of the prior art in lack of aromatic sulfone polymers and provide an aromatic sulfone polymer. According to the invention, by regulating the content of the phenolic terminal group and the content of the Fe element in the aromatic sulfone polymer, the obtained aromatic sulfone polymer has good thermal stability and excellent coloring performance, and has practical guiding significance for preparing aromatic sulfone compositions with bright colors and high brightness.

It is another object of the present invention to provide a method for preparing the above aromatic sulfone polymer.

It is another object of the present invention to provide use of the above aromatic sulfone polymer in preparation of an aromatic sulfone composition.

In order to achieve the purpose, the invention adopts the following technical scheme:

an aromatic sulfone polymer having a phenolic terminal group content of 30 to 80mol/t and an Fe element content of not more than 40 ppm.

The inventors of the present invention have repeatedly found that, in addition to Fe element affecting the coloring properties of the aromatic sulfone polymer, its phenol end group content also has a critical influence on its coloring properties.

Wherein, at a specific phenolic end group content, the aromatic sulfone polymer can maintain excellent thermal stability; meanwhile, because of the existence of a certain content of phenolic end groups, compared with the aromatic sulfone polymer with lower content of phenolic end groups, the aromatic sulfone polymer has stronger polarity, has certain enhancement with the acting force of additives such as titanium dioxide and other toner or other additive components, and can effectively improve the brightness of the composition. If the content of the phenolic terminal group is too low, the coloring property is not good; if the content of the phenolic terminal group is too high, the resin has poor thermal stability, can be degraded in the high-temperature processing process, and has the defects of reduced resin molecular weight, yellowing color, reduced brightness and influence on the coloring performance.

The content of the Fe element is in a certain lower range, so that the adverse degradation of the Fe element to the resin, the interaction or adverse chemical reaction of the Fe element and the toner can be reduced, and the reduction of the resin brightness caused by the degradation or the possible interaction or chemical reaction of the resin and the toner can be avoided.

According to the invention, by regulating the content of the phenolic terminal group and the content of the Fe element, the obtained aromatic sulfone polymer has good thermal stability, high brightness and excellent coloring performance.

Preferably, the aromatic sulfone polymer has a phenolic end group content of 40 to 60 mol/t.

Preferably, the content of Fe element in the aromatic sulfone polymer is 10-20 ppm.

The content of the phenolic terminal group and the content of the Fe element can be regulated and controlled on the prior conventional aromatic sulfone polymer so as to endow the aromatic sulfone polymer with better thermal stability, high brightness and excellent coloring performance.

Preferably, the aromatic sulfone polymer is one or more of polyphenylsulfone, polyethersulfone, polysulfone or polyether ether sulfone.

Preferably, the phenolic end groups comprise a phenolic hydroxyl end group and a phenolate end group.

The preparation method of the aromatic sulfone polymer comprises the following steps:

s1, salt forming reaction: mixing a phenol monomer, a sulfone monomer, a salt forming agent, an entrainer and a solvent, and carrying out a salt forming reaction at 180-220 ℃;

s2, polymerization: and heating the system subjected to the salt forming reaction of S1 to 230-240 ℃ for polymerization reaction, adding a monohalogenated compound for continuous reaction until the polymerization reaction is finished, and performing post-treatment to obtain the aromatic sulfone polymer.

Aromatic sulfone polymers are generally polymerized by a phenolic monomer (containing a phenolic end group) and a sulfone monomer (containing a chlorine end group) in excess, the end group being predominantly a chlorine end group at the end of the polymerization reaction. However, since it is difficult to completely and sufficiently conduct the polymerization reaction, a certain amount of phenol terminal groups still remain. According to the invention, the monohalogenated compound is added in the synthesis process of the aromatic sulfone polymer to realize effective regulation and control of the phenolic end group of the polymer, specifically, the monohalogenated compound can react with the unreacted phenolic end group, so that the content of the phenolic end group is reduced, and the regulation and control of the content of the phenolic end group can be realized by regulating and controlling the dosage of the monohalogenated compound.

In addition, the Fe element content in the raw materials (phenolic monomers and sulfone monomers) and conveying pipelines (such as a stainless steel reaction kettle, a purification process conveying pipeline and the like) of a reaction container and a polymerization post-treatment material are main sources of the Fe element in the preparation process of the aromatic sulfone polymer, and the Fe element content in the aromatic sulfone polymer can be effectively controlled by controlling the Fe element content and the stainless steel reaction kettle and the purification process conveying pipeline.

Monomers, salt-forming agents, entrainers, solvents and the like conventionally used in the art for the synthesis of aromatic sulfone polymers may be used in the present invention, and the amount thereof is also controlled in the conventional amount.

Preferably, the phenolic monomer in S1 is one or more of 4,4 '-dihydroxydiphenyl sulfone, biphenol, and 2, 2' -bis (4-hydroxyphenyl) propane.

Preferably, the sulfone monomer is one or more of 4,4 '-dichlorodiphenyl sulfone, 4' -difluorodiphenyl sulfone or bis- (4-chlorobenzenesulfonyl) biphenyl.

Preferably, the salt forming agent is one or both of sodium carbonate and potassium carbonate.

Preferably, the entrainer is one or more of toluene, xylene or trimethylbenzene.

Preferably, the solvent is one or both of sulfolane and N-methylpyrrolidone.

Preferably, the molar ratio of the sulfone monomer to the phenol monomer is 1.01-1.05: 1.

Preferably, the molar ratio of the salt forming agent to the phenolic monomer is 1.01-1.20: 1.

Preferably, the mass molar ratio of the entrainer to the phenolic monomer is 20-200 g/mol.

Preferably, the monohalogenated compound in S2 is one or more of methyl chloride, ethyl chloride, 4-fluoro diphenyl sulfone, 4-chloro diphenyl sulfone or 4-bromo diphenyl sulfone.

Preferably, the mole ratio of the monohalogenated compound to the phenolic monomer in S2 is 0.03-0.08: 1.

Better regulation and control of the content of the phenol end group can be realized under the dosage range.

Specifically, the preparation method of the aromatic sulfone polymer comprises the following steps:

(1) salt forming reaction: quantitatively adding a solvent (such as sulfolane, N-methyl pyrrolidone and the like), a reaction monomer (wherein the mole number of sulfone monomers is slightly higher than that of sulfone monomers), a salt forming agent (such as sodium carbonate, potassium carbonate and the like), an entrainer (such as toluene, xylene, trimethylbenzene and the like) into a reaction kettle, reacting at 180-220 ℃ by adopting a solution polycondensation method, continuously removing reaction water by azeotropic distillation of the entrainer in the reaction process until no water is removed, finishing a salt forming reaction, and distilling out the entrainer;

(2) polymerization reaction: after the entrainer is evaporated, further heating, stabilizing the reaction system to 230-240 ℃, keeping for 1-2 h, adding the monohalogenated compound, and continuing to react for 1-2 h until the polymerization reaction is finished;

(3) post-polymerization treatment (purification and drying): stopping stirring and heating, precipitating the polymer material in water to form strips, crushing by a crusher to obtain powdery material, boiling with deionized water, centrifugally filtering, repeating for several times until the byproduct salt is removed, and removing water from the purified polymer under vacuum drying to obtain the aromatic sulfone polymer.

The polymerization post-treatment pipeline is made of stainless steel and lined with polytetrafluoroethylene.

The use of the above aromatic sulfone polymers in the preparation of aromatic sulfone compositions is also within the scope of the present invention.

In particular, aromatic sulfone compositions have wide applications in the fields of electronics and electrical (e.g., electrical connectors), medical (e.g., medical sterilization trays, respirators), industrial use (e.g., chip trays), aerospace (e.g., aircraft interiors), and the like.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, by regulating the content of the phenolic terminal group and the content of the Fe element in the aromatic sulfone polymer, the obtained aromatic sulfone polymer has good thermal stability and excellent coloring performance, and has practical guiding significance for preparing aromatic sulfone compositions with bright colors and high brightness.

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.

Some of the reagents selected in the examples and comparative examples of the present invention are described below:

sulfolane: solvent, Liaoyang Guanghua chemical industry Co., Ltd., purity > 99.8%;

4, 4' -dichlorodiphenyl sulfone: the reaction monomer, Taiwan Liu and chemical industry Co., Ltd, has the purity of more than 99.5%;

4, 4' -difluorodiphenyl sulfone: the reaction monomer, Taiwan Liu and chemical industry Co., Ltd, has the purity of more than 99.5%;

4, 4' -biphenol: the reaction monomer, Taiwan Liu and chemical industry Co., Ltd, has the purity of more than 99.5%;

4, 4' -dihydroxydiphenyl sulfone: the reaction monomer, Jiangsu Aolandao scientific and technical actual company, the purity is more than 99.5%;

sodium carbonate: salt forming agent, Shandong Haihai chemical group Limited company, purity > 99.5%;

xylene: entrainer, isomerization grade, petrochemical company, ltd, china.

The properties of the aromatic sulfone polymers of the examples of the present invention and the comparative examples were measured according to the following test methods.

(1) Testing the content of the phenolic end group: dissolving a polymer to be detected in dimethyl sulfoxide (DMSO), preparing a solution to be detected with a proper concentration (5-20 mg/mL), adding hydrochloric acid and a p-hydroxybenzoic acid (PHBA) internal standard substance, titrating with a tetrabutylammonium hydroxide solution in methanol, and determining an end point by a potential to obtain the total amount M of the phenolic end groups of the polymer solution. Weighing the same hydrochloric acid and PHBA, preparing a blank solution, testing the blank phenolic hydroxyl quantity M by potentiometric titration, and obtaining the phenolic end group content of the polymer by the difference (M-M) between the two.

(2) And (4) testing the content of Fe: placing 0.1g of solid to be detected in a digestion device, adding a digestion reagent (8mL of analytically pure HNO)₃2mL of analytically pure H₂O₂) Digestion was carried out using a microwave digestion apparatus (220 ℃, 1.5h), and the digestion solution was quantitatively taken out by weighing as a measurement solution. And (3) measuring the solution to be measured by using an inductively coupled plasma emission spectrometer (ICP-OES) through a calibration curve method, and performing qualitative and quantitative analysis.

(3) And (3) shear viscosity test: obtained by testing with a capillary rheometer at 380 deg.C and a shear rate of 1000S^-1The shear viscosity and the shear viscosity change rate at different times were measured using a die having an inner diameter of 1mm and a length of 40 mm. The shear viscosity change rate is the ratio of the measured shear viscosity difference value at two time points of 1h and 10min to the shear viscosity at the time point of 10 min. The smaller the absolute value of the shear viscosity change rate is, the better the thermal stability of the resin is, and in the present invention, the absolute value of the shear viscosity change rate is required to be less than 3.0%.

(4) And (3) carrying out injection molding test on a color plate: aromatic sulfone polymers and compositions thereof are injection molded at 360 ℃ to give standard plaques having a thickness of 2mm and the L, a, b values of the plaques are determined by means of a colorimeter according to the standard ASTM E1164, the higher the L value the higher the brightness and for white plaques the higher the L value the higher the whiteness index and the whiter the color. The L value is a value indicating the coordinate axis of the inherent color, and ranges from 0 to 100. Closer to 0 the resin indicates a darker color, closer to 100 the value indicates a whiter color.

(5) And (3) testing the coloring performance: 98 parts of an aromatic sulfone polymer and 2 parts of titanium dioxide (commercially available) were uniformly mixed, and then the mixture was fed into a twin-screw extruder set at 280 to 350 ℃ and extruded to prepare pellets. And then, carrying out injection molding on the granules in an injection molding machine at 350-370 ℃ to prepare a standard color plate with the thickness of 2 mm. The higher the L value of the injection molded color plate of the aromatic sulfone composition is, the higher the brightness of the composition is, the better the coloring performance of the reflected polymer is, and the L value is required to be not lower than 85 in the invention.

Examples 1 to 5 and comparative examples 1 to 4

The present example and comparative examples provide a series of aromatic sulfone polymers. The preparation processes of the examples 1 to 4 and the comparative examples 1 to 3 are as follows:

36kg of sulfolane, 8.787kg (30.6mol) of 4,4 '-dichlorodiphenyl sulfone and 5.586kg (30mol) of 4, 4' -biphenol are quantitatively added into a 100L reaction kettle protected by high-purity nitrogen, the temperature is raised by stirring, 33kg (31.1mol) of sodium carbonate and 3kg of xylene are added, and the total content of Fe elements in the added raw materials is 25 ppm. And (3) keeping the temperature of 180-220 ℃ for 5 hours by adopting a solution polycondensation method, continuously discharging reaction water by using xylene through azeotropy in the reaction process until no water is discharged, finishing the salt forming reaction, and distilling out the xylene. Then, the reaction system was heated to 235 ℃ and maintained for 2 hours. Adding 10kg of sulfolane into the system, keeping the temperature at 200 ℃, introducing methyl chloride gas at the flow rate of 2.0L/min, stopping introducing gas after 0.5h, and finishing polymerization. And precipitating the polymer material into strips in water, crushing the strips by a crusher to obtain a powdery material, boiling the powdery material for 1 hour by using deionized water, centrifugally filtering the powdery material, and repeating the step for 8 to 10 times until the filtrate does not become turbid when detected by using silver nitrate, namely the byproduct salt is washed out completely. And (3) removing water from the purified polymer under vacuum drying to obtain the polyphenylsulfone polymer. The polymerized post-treatment pipelines are all lined with polytetrafluoroethylene.

Specifically, the flow rates of the methyl chloride gas introduced in examples 1 to 4 were 2.0L/min, 1.8L/min, 1.5L/min, and 1.0L/min, respectively. The flow rate of the methyl chloride gas introduced in comparative example 1 was 0L/min (i.e., the methyl chloride gas was not introduced), the flow rate of the methyl chloride gas introduced in comparative example 2 was 0.5L/min, and the flow rate of the methyl chloride gas introduced in comparative example 3 was 2.5L/min.

In addition, iron oxide powder (iron oxide, Guangzhou chemical Co., Ltd.) was additionally added to the aromatic sulfone polymer obtained in example 1 so that the Fe element content of the aromatic sulfone polymer was 36ppm and 45ppm as example 5 and comparative example 4, respectively.

Example 6

This example provides an aromatic sulfone polymer which is 4,4 'dihydroxydiphenyl sulfone (7.508kg (30mol)) except that the phenolic monomer used is not 4, 4' -biphenol; the sulfone monomer was not 4,4 '-dichlorodiphenyl sulfone but 4, 4' -difluorodiphenyl sulfone (7.780kg (30.6mol)), except that the balance was the same as in example 1, wherein the total of Fe elements in the respective raw materials was 25 ppm.

The properties of the obtained aromatic sulfone polymer were measured in accordance with the above-mentioned methods, and the results are shown in Table 1.

TABLE 1 compounding ratio conditions and test results for examples 1 to 6 and comparative examples 1 to 4

From the test results of examples 1 to 4 and comparative examples 1 to 3 in Table 1, it can be seen that the content of Fe element in the aromatic sulfone polymer is kept substantially constant, the phenolic terminal group of the aromatic sulfone polymer shows a significant change with the difference in the amount of the introduced methyl chloride gas, the higher the amount of the aromatic sulfone polymer is, the lower the phenolic terminal group content is, and correspondingly, the more the amount of the aromatic sulfone polymer is, the smaller the absolute value of the change rate of the shear viscosity of the polymer is, the better the thermal stability is considered, and when the content of the phenolic terminal group is between 30 to 80mol/t, the coloring property L >85 shows excellent coloring property. Meanwhile, by controlling the content of Fe element in the aromatic sulfone polymer (example 14 and comparative example 4), it was found that the content of Fe element in the aromatic sulfone polymer can be significantly reduced, and that the content of Fe element in comparative examples 4 and 5 >40ppm, the coloring property of which is decreased, i.e., L <83, shows decreased brightness, while the viscosity and thermal stability are kept more consistent with those of the examples. Therefore, it is most advantageous that the phenolic terminal group content and the Fe element content of the aromatic sulfone polymer of the present invention are maintained within a certain range.

It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.