CN111808426A - A kind of aromatic sulfone composition and its preparation method and application - Google Patents

Abstract

The invention relates to an aromatic sulfone composition, a preparation method and application thereof. The aromatic sulfone composition comprises an aromatic sulfone polymer and a tert-butyl aromatic phenol compound; the aromatic sulfone composition contains a tert-butyl aromatic phenol compound in an amount of 15 to 1000 ppm. The aromatic sulfone composition provided by the invention improves the performance of the aromatic sulfone polymer by adding the tert-butyl aromatic phenol compound with relatively smaller molecular weight, and the tert-butyl aromatic phenol compound can keep high light transmittance of the composition and improve the fluidity of the composition at a certain content, has certain oxidation resistance, can reduce the color of the composition and parts thereof in the product processing process, and gives consideration to the fluidity and color grade of the composition. Especially in the process of processing transparent products such as milk bottles and the like, compared with pure resin, the processing temperature can be reduced, the color grade of the products can be improved on the premise of ensuring high light transmittance of the products, low-cost and high-transparency light-color products can be obtained, and the method has great practical application significance.

Description

A kind of aromatic sulfone composition and its preparation method and application

technical field

The invention belongs to the technical field of polymer materials, and in particular relates to an aromatic sulfone composition and a preparation method and application thereof.

Background technique

Aromatic sulfone polymers are high temperature resistant and highly transparent polymer materials. They also have excellent properties such as chemical corrosion resistance, excellent electrical properties, and dimensional stability. They are widely used in aerospace, medical, food and other fields. The existence of polar sulfone groups makes the intermolecular cohesive energy larger, which leads to the high viscosity of the hot processing melt, poor fluidity, high processing temperature, and prone to yellowing and other product defects. In order to improve the fluidity of aromatic sulfone polymers, aromatic sulfone polymers are usually mixed with other resins or flow modifiers with high fluidity to obtain high fluidity and good heat resistance by physical blending or chemical copolymerization. properties and mechanical properties of materials. CN109504089 discloses a low-cost polysulfone alloy prepared by blending polysulfone resin, polycarbonate resin and other corresponding additives, which can reduce the cost while maintaining the advantages of high temperature resistance and mechanical properties of polysulfone resin, and at the same time significantly reduce the cost of polysulfone resin. processing temperature and maintains good melt flow at relatively low temperatures. CN101743272 discloses a thermoplastic molding composition composed of polyethersulfone, polysulfone, stearic acid and other additives and auxiliaries, which has improved flowability, surface quality and notched impact strength, and can be used in the manufacture of automotive headlights. CN104387587 adopts the copolymerization of semi-aromatic dihalogenated diamide, 4,4'-dichlorodiphenyl sulfone and diphenol to prepare high fluidity polyethersulfone/amide copolymer, which is suitable for preparing special thin-walled parts.

Researchers in this field have done a lot of work on the fluidity of aromatic sulfone polymers, mainly focusing on the improvement of the fluidity of composite or copolymer molding compositions. Few studies have been reported to improve its fluidity and improve the color of the product under the premise of rapidity. In some specific fields and products, in addition to higher requirements for fluidity, there are also higher requirements for their light transmittance and color. For example, transparent products (such as milk bottles) have higher light transmittance requirements and higher requirements for product color grades.

Therefore, it is of great research significance and application value to develop an aromatic sulfone polymer material that can take into account both fluidity and high transparency.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects or deficiencies of the prior art that aromatic sulfone polymers are difficult to take into account both fluidity and high transparency, and to provide an aromatic sulfone composition. The aromatic sulfone composition provided by the present invention improves the performance of the aromatic sulfone polymer by adding a tert-butyl aromatic phenol compound with a relatively small molecular weight. The tert-butyl aromatic phenol compound can not only maintain a high light transmittance of the composition under a certain content, but also improve the performance of the aromatic sulfone polymer. At the same time, the fluidity of the composition can be improved, and it has a certain anti-oxidation property, which can reduce the color and luster of the composition and its parts during product processing, taking into account the fluidity and color grade of the composition. Especially in the processing of transparent products such as milk bottles, compared with pure resin, the processing temperature can be reduced, the color grade of the product can be improved on the premise of ensuring the high light transmittance of the product, and the low-cost, high-transparency light-colored product can be obtained great practical application.

Another object of the present invention is to provide a method for preparing the above-mentioned aromatic sulfone composition.

Another object of the present invention is to provide the application of the above-mentioned aromatic sulfone composition in the preparation of transparent articles.

For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

An aromatic sulfone composition includes an aromatic sulfone polymer and a t-butyl aromatic phenol compound; the content of the t-butyl aromatic phenol compound in the aromatic sulfone composition is 15-1000 ppm.

The inventors of the present invention have found through many studies that the tert-butyl aromatic phenol compound with relatively small molecular weight can not only improve the defect of poor fluidity of the aromatic sulfone polymer, but also maintain the high light transmittance of the composition; It has certain oxidation resistance, and can reduce the color of the composition and its parts during the processing of the product, taking into account the fluidity and color grade of the composition.

Especially in the processing of milk bottles or other transparent products, compared with pure resin, the processing temperature can be reduced, the color grade of the product can be improved under the premise of ensuring the high light transmittance of the product, and low-cost, high-transparency light-colored products can be obtained. greater practical significance.

The amount of the tert-butyl aromatic phenolic compound has a great influence on the properties of the composition. If the dosage is too small, the performance improvement effect is not good; if the dosage is too large, bubbles may be generated during processing. By optimizing its dosage, aromatic sulfone compositions with excellent performance can be obtained.

Preferably, the content of the tert-butyl aromatic phenol compound in the aromatic sulfone composition is 35-820 ppm.

More preferably, the content of the tert-butyl aromatic phenol compound in the aromatic sulfone composition is 200-710 ppm.

Preferably, the molecular weight of the tert-butyl aromatic phenol compound is 100-500 g/mol.

More preferably, the tert-butyl aromatic phenol compound is 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol One or more of butylphenol, 2,4,6-tri-tert-butylphenol, p-tert-butylcatechol or 4,6-di-tert-butylresorcinol.

Aromatic sulfone polymers conventional in the art can be used in the present invention.

Preferably, the aromatic sulfone polymer is one or more of polyphenylene sulfone, polyether sulfone, polysulfone, polyether ether sulfone, polyether sulfone ketone or polyphenylene sulfide sulfone.

Aromatic sulfone polymers can be obtained by conventional polymerization.

More preferably, the aromatic sulfone polymer is obtained by polymerizing an aromatic sulfone monomer; the monomer can be 4,4'-dichlorodiphenylsulfone, 4,4'-biphenol, 2,4'-dichlorodiphenylsulfone, One or more of 2'-bis(4-hydroxyphenyl)propane or 4,4'-dihydroxydiphenylsulfone.

Specifically, the aromatic sulfone polymer of the present application can be obtained by the following solution polycondensation process:

(1) Salt-forming reaction: quantitatively add solvent (such as sulfolane, N-methylpyrrolidone, etc.), reaction monomer, salt-forming agent (sodium carbonate, potassium carbonate, etc.), azeotrope (toluene, xylene, etc.) in the reactor , trimethylbenzene, etc.), adopt the solution polycondensation method, react between 180～220 ℃, in the reaction process, continuously remove the reaction water by the azeotrope azeotrope, until the water is removed, the salt-forming reaction ends, steam the azeotrope ;

(2) Polymerization reaction: after steaming out the azeotroping agent, the temperature is further increased, the reaction system is stabilized to 230～240° C., kept for 2～3h, and the reaction is continued until the end of the polymerization reaction;

(3) Post-polymerization treatment: stop stirring and heating, precipitate the polymer material into strips in water, and pulverize it with a crusher to obtain powdery material, boil with deionized water, centrifugally filter, and repeat several times to remove by-products The aromatic sulfone polymer is obtained by removing the moisture from the purified polymer under vacuum drying.

The preparation method of the above-mentioned aromatic sulfone composition includes the following steps: mixing the aromatic sulfone polymer and the tert-butyl aromatic phenol compound uniformly, then melting and kneading, and extruding and granulating to obtain the aromatic sulfone composition.

Preferably, the temperature of the melt-kneading is 280-350°C.

Specifically, the aromatic sulfone composition is prepared through the following process: the aromatic sulfone polymer and the tert-butyl aromatic phenol compound are uniformly mixed and then added to a twin-screw extruder, and melt-kneaded at an extrusion temperature of 280-350°C, Extrusion and granulation to obtain the aromatic sulfone composition.

The application of the above-mentioned aromatic sulfone composition in the preparation of transparent products, especially milk bottles, also falls within the protection scope of the present invention.

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

The aromatic sulfone composition provided by the present invention improves the performance of the aromatic sulfone polymer by adding a tert-butyl aromatic phenol compound with a relatively small molecular weight. The tert-butyl aromatic phenol compound can not only maintain a high light transmittance of the composition under a certain content, but also improve the performance of the aromatic sulfone polymer. At the same time, the fluidity of the composition can be improved, and it has a certain anti-oxidation property, which can reduce the color and luster of the composition and its parts during product processing, taking into account the fluidity and color grade of the composition. Especially in the processing of transparent products such as milk bottles, compared with pure resin, the processing temperature can be reduced, the color grade of the product can be improved on the premise of ensuring the high light transmittance of the product, and the low-cost, high-transparency light-colored product can be obtained great practical application.

Detailed ways

The present invention is further described below in conjunction with the examples. These examples are only intended to illustrate the present invention and not to limit the scope of the present invention. The experimental methods that do not specify specific conditions in the following examples are usually in accordance with the conventional conditions in the field or the conditions suggested by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are available from commercial channels such as conventional markets. The obtained raw materials and reagents. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed by the present invention.

Some of the reagents selected for each embodiment of the present invention and the comparative example are described as follows:

Sulfolane: solvent, purity >99.8%, Liaoning Yanghua Chemical Co., Ltd.;

4,4'-Dichlorodiphenylsulfone: reaction monomer, purity >99.5%, Taiwan Liuhe Chemical Co., Ltd.;

4,4'-Biquinol: reaction monomer, purity >99.5%, Taiwan Liuhe Chemical Co., Ltd.;

4,4'-Dihydroxydiphenylsulfone: reaction monomer, purity >99.5%, Jiangsu Aolunda Technology Industrial Co., Ltd.;

Xylene: azeotrope, isomeric grade, China Petroleum & Chemical Corporation.

The viscosity of the aromatic sulfone compositions of the examples and comparative examples of the present invention is obtained by capillary rheometer test, the test temperature is 380°C, the shear rate is 1000S ^-1 , and is measured by using a die with an inner diameter of 1mm and a length of 40mm. body viscosity. The lower the melt viscosity, the better the fluidity.

The aromatic sulfone compositions of the examples and comparative examples of the present invention were injected into an injection molding machine at 360° C. to obtain a standard color plate with a thickness of 2 mm, and the L, a, b values of the color plate were measured by a colorimeter according to the standard ASTM E1164 , and the b value is used to compare the color depth. The smaller the b value, the lighter the color and the higher the color grade. At the same time, according to GB/T 2410 standard, the light transmittance of the color plate sample was tested by a light transmittance haze tester.

The content of tert-butyl aromatic phenolic compounds in the aromatic sulfone composition is determined by GC-MS test after the composition is extracted, and the specific process is as follows:

1. Sample preparation: take 100±0.5g of the sample and place it in a Soxhlet extractor for extraction, select acetone as the extraction solvent, and perform reflux extraction at 80±5°C for 7 days to obtain an acetone extract, which is concentrated by low-temperature rotary evaporation and weighed.

2. GC-MS test: use Agilent's 7890B-5977A MSD GC-MS test equipment to test; chromatographic conditions: capillary column is HP-5MS, 30m╳2505M, 0.25m; After 200 °C, the temperature was kept constant, the carrier gas was He gas, and the split ratio was 50:1.

The standard working curve of tert-butyl aromatic phenol compounds in gas chromatography was established by using the internal standard method with ethyl acetate as the internal standard. A known concentration of ethyl acetate internal standard solution is quantitatively added to the acetone extract sample to be tested, the peak area of the tert-butyl aromatic phenol compound in the sample is determined, and the content of the tert-butyl aromatic phenol compound in the tested sample is calculated according to the standard working curve. , and inversely deduce the content of tert-butyl aromatic phenolic compounds in the composition.

Examples 1-6 and Comparative Examples 1-4

This example and comparative example provide a series of polyphenylsulfone compositions. Its preparation process is as follows:

(1) Preparation of polyphenylsulfone polymer

Quantitatively add 36kg sulfolane, 8.79kg 4,4'-dichlorodiphenyl sulfone and 5.59kg 4,4'-biphenol in a high-purity nitrogen-protected 100L reactor, stir and heat up and add 33kg sodium carbonate and 3kg diphenylsulfone Toluene was kept at 180-220°C for 5 hours by solution polycondensation. During the reaction, the xylene was continuously discharged from the reaction water by azeotropy, and the salt-forming reaction was completed after the anhydrous discharge, and the xylene was distilled off. After that, the reaction system was heated to 235°C and kept for 3h. Stop stirring and heating, precipitate the above polymer material into strips in water, and pulverize by a crusher to obtain powdery material, boil with deionized water for 1 hour, and centrifugally filter, repeat 8 to 10 times until the filtrate is detected by silver nitrate. Turbidity means that the by-product salts have been washed away. The purified polymer is dried under vacuum to remove moisture to obtain polyphenylsulfone polymer.

(2) Preparation of polyphenylsulfone composition

The polyphenylsulfone polymer obtained in step (1) and 4-tert-butylphenol are mixed uniformly and added to a twin-screw extruder, melt-kneaded at an extrusion temperature of 280-350° C., and extruded and pelletized to obtain Polyphenylsulfone composition.

The ratio of the 4-tert-butylphenol added in the step (2) to the total mass of the polyphenylsulfone polymer and the 4-tert-butylphenol varies from 0 to 3000 ppm (0 to 0.3%).

Specifically, as shown in Table 1, the ratio of the mass of the 4-tert-butylphenol added in the step (2) to the sum of the mass of the polyphenylsulfone polymer and the 4-tert-butylphenol is 0 (denoted as Comparative Example 1), respectively, 15ppm (denoted as Comparative Example 2), 21ppm (denoted as Example 5), 50ppm (denoted as Example 4), 0.03% (ie 300ppm, denoted as Example 3), 0.06% (ie 600ppm, denoted as Example 3) 2), 0.08% (ie 800ppm, marked as Example 1), 0.09% (ie 900ppm, marked as Example 6), 0.125% (ie 1250ppm, marked as Example 7), 0.2% (ie 2000ppm, marked as pair Ratio 3), 0.3% (ie 3000 ppm, recorded as Comparative Example 4).

Examples 8-14 and Comparative Examples 5-8

This example and comparative example provide a series of polyethersulfone compositions. Its preparation process is as follows:

(1) Preparation of polyethersulfone polymer

Quantitatively add 36kg sulfolane, 8.79kg 4,4'-dichlorodiphenyl sulfone and 7.51kg 4,4'-dihydroxydiphenyl sulfone in a 100L reaction kettle protected by high-purity nitrogen, stir and heat up and add 33kg sodium carbonate and 3kg Xylene, using solution polycondensation method, kept at 180 ~ 220 ℃ for 5 hours, during the reaction, xylene was continuously discharged reaction water through azeotropy, until after no water was discharged, the salt-forming reaction was over, and the xylene was distilled out. After that, the reaction system was heated to 235°C and kept for 3h. Stop stirring and heating, precipitate the above polymer material into strips in water, and pulverize by a crusher to obtain powdery material, boil with deionized water for 1 hour, and centrifugally filter, repeat 8 to 10 times until the filtrate is detected by silver nitrate. Turbidity means that the by-product salts have been washed away. The purified polymer is dried under vacuum to remove moisture to obtain polyethersulfone polymer.

(2) Preparation of polyethersulfone composition

The polyethersulfone polymer obtained in (1) and 4-tert-butylphenol are mixed uniformly and added to a twin-screw extruder, melted and kneaded at an extrusion temperature of 280-350°C, and extruded and pelletized to obtain a polymer. Ethersulfone composition.

The ratio of the mass of the 4-tert-butylphenol added in the step (2) to the total mass of the polyethersulfone polymer and the 4-tert-butylphenol varies from 0 to 3000 ppm (0 to 0.3%).

Specifically, as shown in Table 2, the ratio of the mass of the 4-tert-butylphenol added in the step (2) to the total mass of the polyethersulfone polymer and the 4-tert-butylphenol is 0 (denoted as Comparative Example 5), respectively, 18ppm (denoted as Comparative Example 6), 22ppm (denoted as Example 11), 55ppm (denoted as Example 11), 0.03% (ie 300ppm, denoted as Example 10), 0.06% (ie 600ppm, as Example 9) ), 0.08% (ie 800 ppm, marked as Example 8), 0.09% (ie 900 ppm, marked as Example 13), 0.123% (ie 1230 ppm, marked as Example 14), 0.2% (ie 2000 ppm, marked as Comparative Example) 7), 0.3% (ie 3000ppm, recorded as Comparative Example 8.)

Example 14

This example provides an aromatic sulfone composition. In the preparation process, except that the selected tert-butyl aromatic phenol compound is 2,4-di-tert-butyl phenol, the rest are the same as those in Example 1.

Example 15

This example provides an aromatic sulfone composition. In the preparation process, except that the selected tert-butyl aromatic phenol compound is 2,4,6-tri-tert-butylphenol, the rest are the same as those in Example 1.

According to the method mentioned above, the content of the tert-butyl aromatic phenolic compound in the obtained aromatic sulfone composition was measured, and the content of the tertiary butyl aromatic phenolic compound in the aromatic sulfone composition provided by each example and the comparative example was obtained, as shown in the table 1 to 3.

Table 1 Proportioning conditions and test results of Examples 1-7 and Comparative Examples 1-4

The proportioning conditions and test results of Table 2 Examples 8-14 and Comparative Examples 5-8

The proportioning conditions and test results of table 3 embodiment 1, 15～16

It can be seen from Table 1 that the addition of t-butyl aromatic phenol compound is beneficial to increase the fluidity of the aromatic sulfone composition and improve the color grade. The greater the addition of t-butyl aromatic phenol compound, the better the fluidity and the higher the color grade. However, as the amount of the tert-butyl aromatic phenol compound added increases, bubbles will be generated and the light transmittance will decrease. Specifically, the polyphenylsulfone compositions in Examples 1 to 7 contain 15 to 1000 ppm of 4-tert-butylphenol, compared with Comparative Example 1, which does not contain 4-tert-butylphenol, the b value is reduced by 2 to 3, and the shear viscosity is reduced by 5 to 10% , the color is obviously lighter, the fluidity is obviously improved, and the change of light transmittance is small. When the content of the comparative example 2 is 10 ppm, its appearance and fluidity are close to those of the comparative example 1, and when the content of the comparative examples 3 and 4 is larger, although the color grade and fluidity are greatly improved, the surface of the color plate appears Obvious bubbles and reduced light transmittance, which are unfavorable for post-processing molding.

Similarly, it can be found from Table 2 that the polyethersulfone compositions in Examples 8 to 14 contain 15 to 1000 ppm of 4-tert-butylphenol, compared with Comparative Example 5, which does not contain 4-tert-butylphenol, the b value decreases by 2 to 3, and the shear viscosity When it is reduced by 6 to 12%, the color is obviously lighter, the fluidity is obviously improved, and the change of light transmittance is small. At the same time, when the content of Comparative Example 6 is 10 ppm, its appearance and fluidity are close to those of Comparative Example 5, while when the content of Comparative Examples 7 and 8 is larger, although the color grade and fluidity are greatly improved, the color plate There are obvious bubbles on the surface and the light transmittance is reduced, which is unfavorable for post-processing and molding.

It can be seen from the above that it is advantageous to keep the content of the t-butyl aromatic phenol compound in the aromatic sulfone polymer within a certain range. Among them, when its content is 35-820ppm, the comprehensive properties such as fluidity, color grade, light transmittance and appearance quality are better; when its content is 200-710ppm, the fluidity, color grade, light transmittance and appearance quality are better. The overall performance is better.

In addition, it can be seen from Table 3 that 800 ppm of 2,4-di-tert-butylphenol or 2,4,6-tri-tert-butylphenol was added during blending, and the composition obtained after extrusion and granulation (tert-butylphenol in the composition) was obtained. The content of butyl aromatic phenol compound is about 710ppm) can achieve the same effect as adding 4-tert-butylphenol in Example 1, that is, the color becomes lighter, the fluidity is improved, the light transmittance is maintained, and the color plate surface has no bubbles.

Those of ordinary skill in the art will appreciate that the embodiments herein are intended to help readers understand the principles of the present invention, and it should be understood that the scope of protection of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations without departing from the essence of the present invention according to the technical teaching disclosed in the present invention, and these modifications and combinations still fall within the protection scope of the present invention.

Claims (10)

1. An aromatic sulfone composition characterized by comprising an aromatic sulfone polymer and a tert-butyl aromatic phenol compound; the aromatic sulfone composition contains a tert-butyl aromatic phenol compound in an amount of 15 to 1000 ppm.

2. The aromatic sulfone composition of claim 1, wherein the content of the tert-butyl aromatic phenol compound in the aromatic sulfone composition is from 35 to 820 ppm.

3. The aromatic sulfone composition of claim 2, wherein the content of the tert-butyl aromatic phenol compound in the aromatic sulfone composition is 200 to 710 ppm.

4. The aromatic sulfone composition of claim 1, wherein the tertiary-butyl aromatic phenol compound has a molecular weight of 100 to 500 g/mol.

5. The aromatic sulfone composition of claim 4, wherein the tert-butyl aromatic phenol compound is one or more of 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, p-tert-butylcatechol, or 4, 6-di-tert-butylresorcinol.

6. The aromatic sulfone composition of claim 1, wherein the aromatic sulfone polymer is one or more of polyphenylsulfone, polyethersulfone, polysulfone, polyethersulfone, polyethersulfoneketon, or polyphenylsulfone.

7. The aromatic sulfone composition of claim 1, wherein the aromatic sulfone polymer is obtained by polymerization of an aromatic sulfone monomer.

8. The aromatic sulfone composition of claim 7, wherein the aromatic sulfone monomer is one or more of 4,4 '-dichlorodiphenyl sulfone, 4' -biphenol, 2 '-bis (4-hydroxyphenyl) propane, or 4, 4' -dihydroxydiphenyl sulfone.

9. A method for preparing an aromatic sulfone composition described in any one of claims 1 to 8, characterized by comprising the steps of: and uniformly mixing the aromatic sulfone polymer and the tert-butyl aromatic phenol compound, melting and mixing, extruding and granulating to obtain the aromatic sulfone composition.

10. Use of an aromatic sulfone composition according to any one of claims 1 to 8 for the preparation of a transparent article.