Sulfone polymer composition and preparation method and application thereof

Abstract

The invention discloses a sulfone polymer composition and a preparation method and application thereof, the sulfone polymer composition comprises at least one sulfone polymer and a compound N-methylacetamide, based on the total weight of the sulfone polymer composition, the content of N-methylacetamide is 1t; and the total weight is 100 ppm. The sulfone polymer composition product with the N-methylacetamide content lower than 100 ppm can be obtained, the haze of the sulfone polymer product is remarkably reduced, and the light transmission performance is improved. The low-haze and high-heat-resistance product disclosed by the invention is more suitable for being applied to high-end fields, such as the fields of optical materials, medical apparatuses and instruments and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer material synthesis, and particularly relates to a composition of a sulfone polymer, a preparation method and application thereof. BACKGROUND

[0002] In the field of polymer synthesis, sulfone polymer is an important thermoplastic engineering plastic, which has excellent heat resistance, chemical stability and mechanical properties, mainly including three types of polysulfone PSU, polyether sulfone PES and polyphenyl sulfone PPSU, and is widely used in the fields of aerospace, electronics and electrical appliances, medical treatment and the like. Especially in the high-temperature field and the optical field, the requirements for the thermal performance and optical performance of the sulfone polymer are higher and higher.

[0003] In the preparation process of the sulfone polymer resin, cyclobutan sulfone or N,N-dimethylacetamide (DMAc) is often used as a solvent. However, the inventors of the present application accidentally found in the research that, in the solvent system of DMAc, the degradation reaction of DMAc is prone to occur at high temperature, and N-methyl acetamide and other by-products are generated. N-methyl acetamide has a high boiling point, which is higher than 200℃, and is difficult to be completely removed.

[0004] Patent CN102888003B discloses a polymer material precipitation method and an industrialized production method of polysulfone resin. The patent adopts a flash evaporation precipitation method, and under the action of high negative pressure and bidirectional stirring, the solvent is rapidly evaporated and condensed for recovery, and the precipitated material becomes powdery, which is beneficial to the next step processing. However, the patent cannot effectively remove the high-boiling-point N-methyl acetamide residues in the polymer. SUMMARY

[0005] The inventors of the present application further found that the presence of N-methyl acetamide can seriously affect the performance of the polysulfone resin, especially the thermal performance and optical performance. When the content of N-methyl acetamide is high, the thermal decomposition temperature of the polysulfone resin is reduced, the optical haze is increased, and the like, thereby limiting the application thereof in the high-temperature field and the optical field. Based on the foregoing finding, the present application provides a composition of a sulfone polymer with controllable content of N-methyl acetamide, so as to ensure the excellent performance of the polysulfone resin, thereby completing the present application.

[0006] In order to solve the above problems, the technical scheme adopted by the present application is as follows:

[0007] A composition of a sulfone polymer, comprising:

[0008] (a) at least one sulfone polymer;

[0009] (b) N-methyl acetamide;

[0010] The content of N-methyl acetamide is less than 100 ppm, and the content of N-methyl acetamide is not 0, based on the total weight of the sulfone polymer composition;

[0011] The sulfone polymer is obtained by performing a salt polymerization reaction of monomer one containing a bisphenol structure and monomer two of 4,4'-dichlorodiphenyl sulfone under the condition that N,N-dimethylacetamide is used as a reaction solvent.

[0012] The present application surprisingly finds that, by controlling the content of N-methyl acetamide in the sulfone polymer composition to be within 100 ppm, the thermal performance and optical performance of the sulfone polymer resin can be effectively improved, the 5% thermal weight loss temperature of the sulfone polymer is not less than 505 DEG C, and the haze is less than 6, effectively avoiding the problems of reduced thermal decomposition temperature and increased haze, thereby expanding the application range of the sulfone polymer resin.

[0013] In one specific embodiment, the weight average molecular weight of the sulfone polymer is between 50,000 and 150,000 g / mol, and the molecular weight distribution is less than 2.0.

[0014] In one specific embodiment, the 5% thermal weight loss temperature of the sulfone polymer is not less than 505 DEG C, and the haze is less than 6.

[0015] On the other hand, a preparation method of a sulfone polymer composition includes the following steps:

[0016] (1) dissolving monomer one, monomer two and a salt forming agent in a reaction solvent, then heating and refluxing to react, completely removing water in the reaction kettle, and starting the polymerization reaction by increasing the temperature;

[0017] (2) after the polymerization reaction, reducing the stirring speed, then adding a capping agent to cap, and then filtering, crushing, washing and drying the reaction solution to obtain the sulfone polymer.

[0018] In one specific embodiment, the monomer one is one or more of bisphenol A, bisphenol S and diphenylolpropane, and the monomer two is 4,4'-dichlorodiphenyl sulfone.

[0019] In one specific embodiment, the reaction solvent is N,N-dimethylacetamide.

[0020] In one specific embodiment, the capping agent is chloromethane, and the capping temperature is 120-160 DEG C.

[0021] In one specific embodiment, the salt forming agent is sodium carbonate or potassium carbonate, and the salt forming stage is heated to 150-160 DEG C to reflux for 2-6 h.

[0022] In one embodiment, the powder obtained by polymerization and pulverization is washed with 10wt% to 30wt% aqueous N,N-dimethylacetamide solution, and the washing temperature is 90 to 110°C.

[0023] In another aspect, the use of the aforementioned sulfone polymer composition or the sulfone polymer composition prepared by the aforementioned preparation method in high-end optical materials and medical devices.

[0024] Compared with the prior art, the beneficial effects of the technical scheme of the present application are as follows:

[0025] 1) Improve the thermal stability of the product: by optimizing the post-treatment process, the content of N-methylacetamide is controlled below 100 ppm, and it is found that the thermal stability of the product can be improved, for example, the 5% thermal weight loss temperature of polysulfone can be increased from 396°C to 405°C, and the thermal weight loss temperature of polyether sulfone can be increased from 513°C to 528°C, thereby effectively expanding the application field of sulfone polymers.

[0026] 2) Improve the optical performance of the product: it is also found that reducing the content of N-methylacetamide to below 100 ppm can reduce the haze of the sulfone polymer product and increase the light transmission performance. For example, when the content of N-methylacetamide is 45 ppm, the haze of polysulfone is 11.27, and when the content of N-methylacetamide is 8 ppm, the haze of polysulfone is 5.05. DETAILED DESCRIPTION

[0027] The preferred embodiments of the present application will be described in more detail below. Although the preferred embodiments of the present application are described below, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein.

[0028] A sulfone polymer composition of the present application comprises:

[0029] (a) at least one sulfone polymer;

[0030] (b) N-methylacetamide;

[0031] wherein the content of N-methylacetamide is less than 100 ppm, for example, less than 99 ppm, less than 95 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 25 ppm, less than 20 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 5 ppm, etc., based on the total weight of the sulfone polymer composition, and the content of N-methylacetamide is not 0;

[0032] The sulfone polymer is obtained by performing a salt polymerization reaction of monomer one containing a bisphenol structure and monomer two of 4,4'-dichlorodiphenyl sulfone under a condition of using N,N-dimethylacetamide as a reaction solvent.

[0033] The present application surprisingly finds that the content of N-methyl acetamide in the sulfone polymer composition has a significant influence on the thermal and optical properties of the sulfone polymer resin, and that the thermal and optical properties of the sulfone polymer resin can be effectively improved by controlling the content of N-methyl acetamide in the sulfone polymer composition to be less than 100 ppm, the 5% thermal weight loss temperature of the sulfone polymer is not less than 505°C, and the haze is less than 6, effectively avoiding the problems of reduced thermal decomposition temperature and increased haze, thereby expanding the application range of the sulfone polymer resin.

[0034] In the present application, the weight average molecular weight of the sulfone polymer is between 50000 and 150000 g / mol, for example, the weight average molecular weight is 50000 g / mol, 60000 g / mol, 70000 g / mol, 80000 g / mol, 90000 g / mol, 100000 g / mol, 110000 g / mol, 120000 g / mol, 130000 g / mol, 140000 g / mol, 150000 g / mol, etc., preferably between 60000 and 100000 g / mol; at the same time, the molecular weight distribution is less than 2.0, for example, 1.9, 1.8, 1.7, 1.6, 1.5, etc., preferably 1.5 to 1.9.

[0035] In the present application, the 5% thermal weight loss temperature of the sulfone polymer is not less than 505°C, for example, 508°C, 510°C, 512°C, 515°C, 520°C, 525°C, 530°C, 535°C, 540°C, 550°C, etc., and the haze is less than 6, for example, 5.9, 5.8, 5.7, 5.6, 5.5, 5.4, 5.3, 5.2, 5.1, 5.0, 4.9, 4.8, 4.7, 4.6, 4.5, etc.

[0036] The following provides an exemplary preparation method of the above-mentioned sulfone polymer composition, but does not constitute any limitation. The preparation method of the sulfone polymer composition comprises the following steps:

[0037] The monomer one, the monomer two and the salt forming agent are dissolved in the reaction solvent, and then heated to reflux reaction, the water in the reaction kettle is completely removed, and the polymerization reaction is started; after the polymerization reaction, the stirring speed is reduced, and then the end-capping agent is added for end-capping, and then the reaction liquid is filtered, broken, washed with water and vacuum dried to obtain the sulfone polymer.

[0038] The monomer one is one or more of bisphenol A, bisphenol S, and diphenol, and the monomer two is 4,4'-dichlorodiphenyl sulfone; and a polysulfone, polyethersulfone, or polyphenylsulfone is prepared.

[0039] The salt forming agent is sodium carbonate or potassium carbonate, the reaction solvent is N,N-dimethylacetamide, and the capping agent is chloromethane.

[0040] In the salt forming stage, the reaction is refluxed at 150-160 DEG C for 2-6 hours, for example, the reflux temperature is 150 DEG C, 151 DEG C, 153 DEG C, 155 DEG C, 158 DEG C, 160 DEG C, etc., and the reflux time is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.

[0041] In the polymerization stage, the reaction is carried out at 155-165 DEG C for 2-48 hours, for example, the polymerization temperature is 155 DEG C, 158 DEG C, 160 DEG C, 162 DEG C, 164 DEG C, 165 DEG C, etc., and the polymerization time is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 10 hours, 16 hours, 20 hours, 25 hours, 30 hours, 36 hours, 40 hours, 45 hours, 48 hours, etc.

[0042] In the present application, the amount of each reaction material is not particularly limited, for example, taking bisphenol S and dichlorodiphenyl sulfone as the reaction materials, the molar ratio of bisphenol S to dichlorodiphenyl sulfone is 1:1.0-1:1.03, the amount of the salt forming agent is 1.05-1.3 times the amount of bisphenol S, the amount of the reaction solvent is determined according to the solid content of the reaction system, which is 20%-50%, the amount of the water-carrying agent is 10-50% of the mass of the reaction solvent, or no water-carrying agent is added, and the amount of the capping agent is 2%-10% of the molar amount of bisphenol S.

[0043] To control the content of N-methylacetamide to be less than 20 ppm, the present application mainly adopts the following technical means: selecting a specific washing liquid (N,N-dimethylacetamide aqueous solution) and a specific washing temperature to achieve a high washing effect.

[0044] The post-processing process of the present application comprises: after the polymerization reaction is completed, the product needs to be post-processed, the crushed powder is washed with 10wt%-30wt% N,N-dimethylacetamide aqueous solution, the washing temperature is 90-110 DEG C, so as to obtain the required aromatic sulfone polymer product.

[0045] In addition, the preparation process of the present application also includes necessary performance detection: the obtained aromatic sulfone polymer product is detected for performance, including heat resistance, product haze and other indexes, so as to evaluate the product quality, and adjust and optimize according to the need, and the specific test method is described below.

[0046] The reaction conditions of the present application are all under nitrogen atmosphere, the reaction vessel is dried by baking, and the nitrogen is filled after vacuumizing for many times. The steps not specially described in the present application can refer to the prior art, for example, the reaction liquid pressure filter, crushing, washing, vacuum drying and other processes, which can be realized by using the conventional technical means in the art.

[0047] Through the above steps, the sulfone polymer composition product with N-methyl acetamide content less than 100ppm can be obtained, and the product with low haze and high heat resistance is more suitable for high-end application fields such as optical materials, medical devices and the like.

[0048] The present application is further explained by more specific examples below, but does not constitute any limitation.

[0049] The test method and test conditions used in the following examples are as follows:

[0050] The sulfone polymer molecular weight is determined by using permeation gel chromatography (GPC), DMF containing 20mmol lithium bromide is used as the mobile phase, PMMA is used as the standard sample, the chromatographic column is Agilent MIXD C, MIXD D, MIXD E in series, and the flow rate is 1.0mL / min.

[0051] The N-dimethylacetamide content is tested by gas chromatography. The processing flow and testing method are as follows: the sample is completely dissolved in N-methylpyrrolidone, dispersed and treated with tetrahydrofuran, and settled and treated with methanol, the supernatant is filtered, and Agilent 7890B gas chromatography is used for analysis, and a hydrogen flame ionization detector (FID) is used for detection. The N-methylacetamide content in the sample is analyzed by an external standard method, the chromatographic column is HP-5 (the stationary phase is 5% phenyl-polymethylsiloxane), the specification is 60m x 0.25mm x 0.25um, the temperature rising program is: the initial temperature is 50℃, the temperature is raised to 80℃ at 5℃ / min, then the temperature is raised to 240℃ at 15℃ / min, and kept for 15min, the injection port temperature is 280℃, the FID detector temperature is 300℃, the split injection is used, the split ratio is 10:1, the injection amount is 1.0ul, the carrier gas flow rate (nitrogen) is 1ml / min, the hydrogen flow rate is 30ml / min, the air flow rate is 400ml / min, and the tail gas flow rate is 25ml / min.

[0052] 5% thermal weight loss temperature test method refers to ISO 11358, and the temperature rising rate is 10℃ / min.

[0053] The optical haze test method refers to ISO 13468-1, and the thickness of the optical sheet is 2mm.

[0054] Example 1

[0055] This example provides a method for preparing high-heat-resistant and low-haze polyether sulfone by reducing N-methylacetamide through washing. The specific steps are as follows:

[0056] Step one: polymerization reaction. 21271g (85mol) of bisphenol S, 24409g (85mol) of dichlorodiphenyl sulfone, and 9910g (93.5mol) of sodium carbonate are sequentially added to 19989g of N,N-dimethylacetamide, heated to 160℃ to reflux and remove water, and then polymerized at 165℃ for 32h after the water is completely removed.

[0057] Step two: end-capping reaction. When the polymerization reaction reaches the end point, the temperature is reduced to 150℃, and chloromethane is introduced for 60min.

[0058] Step three: post-treatment process. After the end-capping reaction is completed, the reaction liquid is subjected to settling, crushing and other operations, then washed with 10wt% N,N-dimethylacetamide aqueous solution, the washing temperature is 90℃, and finally dried at 160℃ to obtain the required polyether sulfone product.

[0059] Step four: performance test. The results show that the weight average molecular weight of the prepared polyether sulfone is 88570 g / mol, the molecular weight distribution is 1.72, the N-methyl acetamide content is 74 ppm, the 5% thermal weight loss temperature is 522°C, and the haze is 5.68.

[0060] Example 2

[0061] The difference from Example 1 is that 30% N,N-dimethylacetamide aqueous solution is used for washing, and the washing temperature is 110°C.

[0062] Performance evaluation: the results show that the weight average molecular weight of the prepared sulfone polymer is 94576 g / mol, the molecular weight distribution is 1.66, the N-methyl acetamide content is 41 ppm, the 5% thermal weight loss temperature is 528°C, and the haze is 5.05.

[0063] Example 3

[0064] The difference from Example 1 is that bisphenol S is replaced by 4,4'-diphenol, and the polymerization time is changed to 3.5h.

[0065] Performance evaluation: the results show that the weight average molecular weight of the prepared polyphenyl sulfone is 52355 g / mol, the molecular weight distribution is 1.69, the N-methyl acetamide content is 67 ppm, the 5% thermal weight loss temperature is 539°C, and the haze is 5.59.

[0066] Example 4

[0067] The difference from Example 2 is that bisphenol S is replaced by bisphenol A, and the polymerization time is changed to 4h.

[0068] Performance evaluation: the results show that the weight average molecular weight of the prepared poly sulfone is 82560 g / mol, the molecular weight distribution is 1.70, the N-methyl acetamide content is 28 ppm, the 5% thermal weight loss temperature is 505°C, and the haze is 4.78.

[0069] Example 5

[0070] The difference from Example 1 is that sodium carbonate is replaced by potassium carbonate.

[0071] Performance evaluation: the results show that the weight average molecular weight of the prepared polyether sulfone is 89620 g / mol, the molecular weight distribution is 1.71, the N-methyl acetamide content is 82 ppm, the 5% thermal weight loss temperature is 521°C, and the haze is 5.79.

[0072] Comparative Example 1

[0073] The difference from Example 1 is that 30% N,N-dimethylacetamide aqueous solution is replaced by deionized water.

[0074] Performance evaluation: the results show that the weight average molecular weight of the prepared polyether sulfone is 87980 g / mol, the molecular weight distribution is 1.71, the N-methyl acetamide content is 172 ppm, the 5% thermal weight loss temperature is 513°C, and the haze is 11.27.

[0075] Comparative example 2

[0076] The difference from example 3 is that 30% aqueous N,N-dimethylacetamide solution is replaced by deionized water, and the washing temperature is 100°C.

[0077] Performance evaluation: the results show that the weight average molecular weight of the prepared polyether sulfone is 52480 g / mol, the molecular weight distribution is 1.69, the N-methyl acetamide content is 156 ppm, the 5% thermal weight loss temperature is 527°C, and the haze is 10.68.

[0078] Comparative example 3

[0079] The difference from example 4 is that 30% aqueous N,N-dimethylacetamide solution is replaced by 5% aqueous N,N-dimethylacetamide solution.

[0080] Performance evaluation: the results show that the weight average molecular weight of the prepared polyether sulfone is 83126 g / mol, the molecular weight distribution is 1.69, the N-methyl acetamide content is 108 ppm, the 5% thermal weight loss temperature is 496°C, and the haze is 8.92.

[0081] Those skilled in the art can understand that some modifications or adjustments can be made to the present application under the teaching of the present specification. These modifications or adjustments should also be within the scope defined by the claims of the present application.

Claims

1. A composition of a sulfone polymer, characterized by, Comprise: (a) at least one sulfone polymer; (b) N-methylacetamide; Wherein, the content of N-methylacetamide is less than 100 ppm, and the content of N-methylacetamide is not 0, based on the total weight of the sulfone polymer composition; The sulfone polymer is obtained by salt-forming polymerization reaction of monomer one containing bisphenol structure and monomer two of 4, 4'-dichlorodiphenyl sulfone, in the condition of using N, N-dimethylacetamide as reaction solvent.

2. The composition of sulfone polymers according to claim 1, characterized by, The weight average molecular weight of the sulfone polymer is between 50000-150000 g / mol, and the molecular weight distribution is less than 2.0, preferably 1.5-1.

9.

3. The composition of sulfone polymers according to claim 2, characterized in that, The 5% thermal weight loss temperature of the sulfone polymer is not less than 505℃, and the haze is less than 6.

4. Process for the preparation of a composition of a sulfone polymer according to any one of claims 1 to 3, characterized in that, Comprise the following steps: (1) Dissolve monomer one, monomer two and salt-forming agent in reaction solvent, then heat to reflux reaction, completely remove water in the reaction kettle, and start polymerization reaction by increasing temperature; (2) After polymerization reaction, reduce the stirring speed, then add capping agent for capping, then filter, crush, wash and dry the reaction liquid to obtain the sulfone polymer.

5. The method of preparing a composition of a sulfone polymer according to claim 4, characterized by, The monomer one is one or more of bisphenol A, bisphenol S and diphenylolpropane, and the monomer two is 4, 4'-dichlorodiphenyl sulfone.

6. The method of preparing a composition of a sulfone polymer according to claim 4, characterized by, The reaction solvent is N, N-dimethylacetamide.

7. The method of preparing a composition of a sulfone polymer according to claim 4, characterized by, The capping agent is chloromethane, and the capping temperature is 120-160℃.

8. The method of preparing a composition of a sulfone polymer according to claim 4, characterized by, The salt-forming agent is sodium carbonate or potassium carbonate, and the salt-forming stage is heated to 150-160℃ to reflux reaction for 2-6h.

9. The method of preparing a composition of a sulfone polymer according to claim 4, characterized by, The powder obtained by polymerization and crushing is washed with 10wt%-30wt% N, N-dimethylacetamide aqueous solution, and the washing temperature is 90-110℃.

10. The application of the sulfone polymer composition of any one of claims 1-3 or the sulfone polymer composition prepared by the preparation method of any one of claims 4-9 in high-end optical materials and medical devices.