Polyester material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a polyester material as well as a preparation method and application thereof. The polyester material includes: 73 wt% to 83 wt% of polycarbonate; 10 wt% to 15 wt% of a diphenyl sulfone; 3 wt% to 5 wt% of a compatibilizer; and 4 wt% to 7 wt% of other auxiliary agents. The polyester material provided by the invention has excellent mechanical properties, impact resistance, heat resistance and color stability, and can maintain more than 98% of material properties for 1000 hours under the condition of radiation energy of 35 kGy. The method can be applied to the fields of communication, nuclear power stations, medical treatment, food sterilization and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a polyester material and a preparation method and application thereof. Background Art

[0002] Plastics that have a protective effect against neutrons and gamma rays generated by nuclear radiation are called radiation-proof plastics. As the application of plastic materials in food, medical, space and nuclear technology continues to expand, the requirements for the radiation resistance of plastic materials are becoming higher and higher. Radiation includes electromagnetic radiation and ionizing radiation. The wavelength range of electromagnetic radiation is very wide, from 10 -12 m (such as gamma rays) to several hundred meters (such as radio waves). Ionizing radiation refers to radiation that can cause ionization of matter, that is, radiation with a wavelength less than 10 -7 m, electromagnetic waves with energy higher than 10eV, accelerated charged ions, and neutral ions, which can directly or indirectly cause the excitation and ionization of material molecules, causing performance degradation. The radiation protection of plastics requires that the various properties of plastic products do not change significantly in the radiation environment, and do not affect the original function of the product. Summary of the invention

[0003] In view of the shortcomings of the prior art, the present invention aims to provide a polyester material and a preparation method and application thereof. In the present invention, by designing the specific components of the polyester material, and further by the coordination of polycarbonate, a compatibilizer and diphenyl sulfone, a polyester material that not only meets the radiation protection requirements but also has excellent mechanical properties, impact resistance, heat resistance and color stability is prepared. The polyester material can still maintain more than 98% of the material properties under the condition of 35kGy radiation energy for 1000 hours.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides a polyester material, comprising:

[0006] 73 to 83 wt.% polycarbonate;

[0007] 10 to 15 wt% diphenyl sulfone;

[0008] 3 to 5 wt % of a compatibilizer; and

[0009] 4 to 7% by weight of other auxiliaries.

[0010] In the present invention, the added diphenyl sulfone contains two phenyl groups. After being blended with polycarbonate, it reacts with the ester group of polycarbonate under the action of a compatibilizer, thereby increasing the proportion of aromatic rings in the polycarbonate, enhancing the polarity of the molecular chain, and improving the rigidity of the material itself, so that the polyester material provided by the present invention has excellent mechanical properties, impact resistance, heat resistance and color stability, and can maintain more than 98% of the material properties for 1000 hours under the condition of radiation energy of 35 kGy.

[0011] In the polyester material of the present invention, the weight percentage of the polycarbonate in the polyester material is 73%-83%, for example, it can be 73 weight%, 74 weight%, 75 weight%, 76 weight%, 77 weight%, 78 weight%, 79 weight%, 80 weight%, 81 weight%, 82 weight%, 83 weight%, etc., but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable;

[0012] For the purpose of the present invention, the term "polycarbonate (PC)" can be interpreted broadly. In a broad sense, it refers to the general term for polymer compounds containing carbonate in the main chain of the molecule. The linear structure of dihydroxy compound polycarbonate is generally represented by the following general formula:

[0013]

[0014] Wherein, R represents the parent nucleus of the dihydroxy compound HO-R-OH, and depending on the R group, it can be divided into aliphatic polycarbonate, aliphatic-aromatic polycarbonate or aromatic polycarbonate.

[0015] In the polyester material of the present invention, the weight percentage of diphenyl sulfone in the polyester material is 10%-15%, for example, it can be 10 weight%, 11 weight%, 12 weight%, 13 weight%, 14 weight%, 15 weight%, etc., but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; it should be noted that the addition amount of diphenyl sulfone should be 10 weight% or more. If it is too low, the proportion of aromatic rings formed by ester reaction with polycarbonate will be insufficient, and the radiation resistance ability will be difficult to be reflected; if the addition amount is too high, the proportion of aromatic rings formed is sufficient, and the radiation resistance ability cannot be further improved by increasing the addition amount of diphenyl sulfone; in a preferred embodiment, the weight percentage of diphenyl sulfone in the polyester material is 13%-15%. At this proportion, the mechanical properties, impact resistance, heat resistance and color stability of the polyester material are better.

[0016] In the polyester material of the present invention, the weight percentage of the compatibilizer in the polyester material is 3%-5%, for example, it can be 3% by weight, 4% by weight, 5% by weight, etc., but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable;

[0017] In the polyester material of the present invention, the weight percentage of the other additives in the polyester material is 4%-7%, for example, it can be 4 weight %, 5 weight %, 6 weight %, 7 weight %, etc., but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] In one embodiment, the melt index of the polycarbonate at 300°C and 1.2kg is 5-30g / 10min, specifically 5, 10, 15, 20, 25, 30g / 10min, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable. Among them, it is worth noting that for the polycarbonate of the present invention, when its melt index is lower than 5g / 10min, the molecular weight of the polycarbonate is too high, which is not conducive to dispersion with diphenyl sulfone and compatibilizer. If the melt index is higher than 30g / 10min, the molecular weight of the polycarbonate will be too low, affecting the performance of the material.

[0019] In one embodiment, the other additives include a toughening agent;

[0020] Preferably, the polyester material includes 3 wt % to 5 wt % of the toughening agent, for example, 3 wt %, 4 wt %, 5 wt %, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] In one embodiment, the polyester material comprises:

[0022] 73 to 83 wt.% polycarbonate;

[0023] 10 to 15 wt% diphenyl sulfone;

[0024] 3 to 5 wt % of a compatibilizer;

[0025] 3 to 5 wt % of a toughening agent; and

[0026] 1 to 2% by weight of other auxiliaries.

[0027] In one embodiment, the toughening agent includes any one of a terpolymer of methyl methacrylate-butadiene-styrene, a silicon-acrylate copolymer, and acrylate, or a combination of at least two thereof.

[0028] In one embodiment, the compatibilizer includes any one of ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, acrylonitrile-styrene-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer, or a combination of at least two thereof.

[0029] In one embodiment, the other additives further include any one or a combination of at least two of an antioxidant, a lubricant, and an anti-ultraviolet agent;

[0030] Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant and / or a compound of an amine antioxidant and a phosphite antioxidant;

[0031] Preferably, the lubricant is silicone masterbatch and / or pentaerythritol stearate;

[0032] Preferably, the anti-ultraviolet agent includes any one of 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, or a combination of at least two thereof.

[0033] In a second aspect, the present invention provides a method for preparing the polyester material as described in the first aspect, the preparation method comprising:

[0034] The polycarbonate with a moisture content of ≤0.1%, diphenyl sulfone, a compatibilizer and other auxiliary agents are mixed, added into an extruder and melt-granulated to obtain the polyester material.

[0035] In one embodiment, the aspect ratio of the extruder is 40-50:1, the temperature range of the extruder is 220-260°C, and the basic screw speed is 300-600rpm / min;

[0036] Preferably, the temperature of each section of the extruder is as follows:

[0037] The temperature of zone 1 is 220-230℃, the temperature of zone 2 is 230-240℃, the temperature of zones 3 to 9 is 240-260℃, and the temperature of the machine head is 240-260℃.

[0038] In a third aspect, the present invention provides a radiation protection product, wherein part or all of the radiation protection product is made of a polyester material, wherein the polyester material is the polyester material described in the first aspect.

[0039] In a fourth aspect, the present invention provides a use of the polyester material as described in the first aspect or the radiation protection product as described in the third aspect in nuclear radiation, ionizing radiation and electromagnetic radiation.

[0040] Based on the above, compared with the prior art, the polyester material provided by the present invention has at least one of the following beneficial technical effects:

[0041] The polyester material provided by the present invention has excellent mechanical properties, impact resistance, heat resistance and color stability, and can maintain more than 98% of the material properties for 1000 hours under the condition of 35kGy radiation energy. It can be applied to the fields of communication, nuclear power plant, medical treatment and food sterilization.

[0042] Other features and beneficial effects of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other beneficial effects of the present invention can be achieved and obtained by the structures specifically pointed out in the description and claims. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments; the technical features designed in different implementation modes of the present invention described below can be combined with each other as long as they do not conflict with each other; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0044] In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meanings as those generally understood by ordinary technicians in the field to which the present invention belongs, and cannot be understood as limiting the present invention; it should be further understood that the terms used in the present invention should be understood to have the same meanings as these terms in the context of this specification and in the relevant fields, and should not be understood in an idealized or overly formal sense, unless explicitly defined in the present invention.

[0045] The following examples are used to illustrate the present invention in more detail but are not intended to limit the present invention in any way.

[0046] The sources of the raw materials used in the examples and comparative examples of the present invention are as follows, but are not limited to the following raw materials:

[0047] Polycarbonate: Covestro's 2805;

[0048] Diphenyl sulfone: diphenyl sulfone from Hubei Xinyuhong Biopharmaceutical Technology Co., Ltd.

[0049] The compatibilizer adopts PTW from DowDuPont;

[0050] Other additives used:

[0051] The toughening agent is S-2501 from Mitsubishi Rayon of Japan;

[0052] Antioxidant: Tianjin Lianlong 1076 and 168 are compounded in a weight ratio of 1:1;

[0053] Lubricant: Dow Corning's silicone masterbatch MB50-002;

[0054] Anti-ultraviolet agent: UV-234 from Tianjin Lianlong;

[0055] The weight ratio of the antioxidant, lubricant and anti-ultraviolet agent added is 3:4:3.

[0056] Table 1 List of components in the examples

[0057] Component / weight% Example 1 Example 2 Example 3 Example 4 Example 5 Polycarbonate 82 78 76 73 77 Diphenyl sulfone 10 12 14 15 13 Toughening agent 3 3 4 5 5 Compatibilizer 3 5 4 5 3 Other additives 2 2 2 2 2

[0058] Table 2 List of components of comparative examples

[0059] Component / weight% Comparative Example 1 Comparative Example 2 Comparative Example 3 Polycarbonate 92 83 76 Diphenyl sulfone 0 9 16 Toughening agent 3 3 3 Compatibilizer 3 3 3 Other additives 2 2 2

[0060] The formulation compositions of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1 and Table 2:

[0061] The preparation method of the polyester material in the embodiments and comparative examples of the present invention comprises the following steps:

[0062] (1) drying the polycarbonate in a forced air dryer at 100-120° C. for 3 hours, controlling the moisture content of the material to ≤ 0.1%;

[0063] (2) adding diphenyl sulfone, toughening agent, compatibilizer, other additives and polycarbonate with a moisture content of ≤0.1% into a high-speed mixer according to a weight ratio and mixing for 3 minutes to obtain a mixture;

[0064] (3) adding the mixed material obtained in step (2) into a twin-screw extruder, undergoing melt plasticization, shearing and kneading, and finally extruding through a die head, drawing, cooling, pelletizing, and drying to obtain a polyester material resistant to ionizing radiation.

[0065] The aspect ratio of the twin-screw extruder in step (3) is 40-50:1, the temperature range of the extruder is 220-260°C, and the screw speed is 300-600rpm / min; specifically, the temperature of each section of the twin-screw extruder is 220-230°C in zone 1, 230-240°C in zone 2, 240-260°C in zones 3 to 9, and the die head temperature is 240-260°C.

[0066] It should be noted that the specific parameters or some commonly used reagents in the above embodiments are specific embodiments or preferred embodiments of the present invention, rather than limiting the present invention; those skilled in the art can make adaptive adjustments within the scope of the present invention.

[0067] The raw material formula and preparation method of Comparative Example 1 are basically the same as those of Example 1, except that diphenyl sulfone is not added;

[0068] The raw material formula and preparation method of Comparative Example 2 are basically the same as those of Example 1, except that the addition ratio of diphenyl sulfone is reduced;

[0069] The raw material formula and preparation method of Comparative Example 3 are basically the same as those of Example 1, except that the addition ratio of diphenyl sulfone is increased.

[0070] The polyester materials in the above examples and comparative examples were subjected to performance tests, and the test items were as follows:

[0071] (1) Tensile strength: tested in accordance with ISO 527 standard;

[0072] (2) Flexural strength: tested in accordance with ISO 178 standard;

[0073] (3) Impact strength: tested in accordance with ISO 180 standard;

[0074] (4) Heat deformation temperature: tested in accordance with ISO 75 standard;

[0075] (5) Color appearance: Tested visually and with a colorimeter (color difference value within 0.3 is not obvious visually; 0.5-1.0 is slight visual discoloration; and above 1.0 is obvious visual discoloration).

[0076] The test steps are as follows:

[0077] 1. First, three sets of test specimens were made from the polyester materials prepared in the embodiments and comparative examples;

[0078] 2. After placing the first set of test specimens prepared in each embodiment and comparative example in a constant temperature and humidity chamber at a temperature of 23° C. and a humidity of 50% for 48 hours, a conventional performance test was performed, and the test data obtained was used as the original value for comparison with the experimental data of the second and third sets. The test results are shown in Table 3;

[0079] 3. The second set of test specimens prepared in each embodiment and comparative example were placed in an irradiation device, irradiated for 100 hours under the condition of a radiation energy of 35 kGy, and then placed in a constant temperature and humidity chamber at a temperature of 23° C. and a humidity of 50% for 48 hours to test the performance. The test results are shown in Table 4;

[0080] 4. The third set of test specimens prepared in each embodiment and comparative example were placed in an irradiation device and irradiated for 1000 hours under the condition of a radiation energy of 35 kGy. The performance was then tested after being placed in a constant temperature and humidity chamber at a temperature of 23°C and a humidity of 50% for 48 hours. The test results are shown in Table 4.

[0081] Table 3 Performance test table of test specimens under normal laboratory conditions

[0082]

[0083] Table 4 Performance test table of the test specimens under the condition of irradiation with radiation energy of 35kGy for 100 hours

[0084]

[0085]

[0086] Table 5 Performance retention rate after irradiation with radiation energy of 35 kGy for 100 hours

[0087]

[0088]

[0089] Table 6 Performance test table of test specimens under the condition of irradiation with radiation energy of 35kGy for 1000 hours

[0090]

[0091]

[0092] Table 7 Performance retention rate after irradiation with radiation energy of 35 kGy for 1000 hours

[0093] Test items Tensile Strength Bending Strength Impact strength Heat Deflection Temperature Color Appearance Retention rate ％ ％ ％ ％ - Example 1 98.20 98.27 98.19 98.20 - Example 2 98.50 98.57 98.52 98.41 - Example 3 98.85 98.8 98.81 98.80 - Example 4 99.21 99.09 99.03 99.04 - Example 5 98.65 98.60 98.61 98.62 - Comparative Example 1 84.08 84.92 84.64 84.66 - Comparative Example 2 95.06 95.03 95.00 94.98 - Comparative Example 3 99.15 99.03 99.02 99.03 -

[0094] By comparing Example 1 and Comparative Example 1, it can be seen that without adding diphenyl sulfone, the data are basically consistent when tested under conventional laboratory conditions; however, under the irradiation condition of radiation energy of 35 kGy, after irradiation for 100 hours, the percentage value of the reduction of various performance data is about 4%, and the color difference value is 0.60; and under the irradiation condition of radiation energy of 35 kGy, after irradiation for 1000 hours, the percentage value of the reduction of various performance data reaches an astonishing 16%, and the color difference value is 1.33.

[0095] It can be seen from the data in Tables 2 to 7 that when the added diphenyl sulfone of the polyester material of the present invention reaches 10% by weight or more, the mechanical properties, impact strength and heat resistance of the material can maintain more than 98% of the initial properties after irradiation for 1000 hours under the irradiation condition of 35kGy of radiation energy, and the color difference value is within 0.3. This is because diphenyl sulfone contains two phenyl groups. After being blended with polycarbonate, it reacts with the ester group of polycarbonate under the action of a compatibilizer, thereby increasing the proportion of aromatic rings of polycarbonate, enhancing the polarity of the molecular chain, and improving the rigidity of the material itself, thereby greatly improving the radiation resistance of the polyester material provided by the present invention; and it can be seen from the experimental results of Example 1 and Comparative Example 2 that only 9% by weight of diphenyl sulfone is added to the polyester material prepared in Comparative Example 2. Under conventional laboratory conditions and irradiation conditions of 35KGy of radiation energy for 100 hours, the performance data can still be compared with that of Example 1. The results are basically the same, but after 1000 hours of irradiation, the mechanical properties, impact strength and heat resistance of the polyester material obtained in Comparative Example 2 only maintain 95% of the initial properties, that is, when the addition amount of diphenyl sulfone in the polyester material is less than 10% by weight, the obtained polyester material is irradiated under the condition of 35 kGy of radiation energy, and after 1000 hours of irradiation, the performance values ​​will be significantly reduced. This is because only after the ester group reaction with polycarbonate forms a sufficient aromatic ring ratio, its radiation resistance can be fully exerted; further, it can be seen from the experimental structure of Example 4 and Comparative Example 3 that when the addition amount of diphenyl sulfone in Example 4 is 15%, after irradiation under the condition of 35 kGy of radiation energy, after 1000 hours of irradiation, its performance retention percentage and the △E value of color appearance change are both optimal. Further increasing the addition amount will not continue to improve the radiation resistance, and it is easy to cause a comprehensive reduction in other aspects of performance.

[0096] In addition, those skilled in the art should understand that, although there are many problems in the prior art, each embodiment or technical solution of the present invention can be improved in only one or several aspects, without having to solve all the technical problems listed in the prior art or background technology at the same time. Those skilled in the art should understand that the content not mentioned in a claim should not be used as a limitation on the claim.

[0097] Although the terms such as polycarbonate, compatibilizer, other additives, toughening agent, antioxidant, lubricant, anti-ultraviolet agent, etc. are used more frequently in this article, the possibility of using other terms is not excluded. These terms are used only to more conveniently describe and explain the essence of the present invention; interpreting them as any additional restrictions is contrary to the spirit of the present invention; the terms "first", "second", etc. (if any) in the description and claims of the embodiments of the present invention are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence.

[0098] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyester material, characterized in that: The polyester material comprises: 73 to 83 wt.% polycarbonate; 10 to 15 wt% diphenyl sulfone; 3 to 5 wt % of a compatibilizer; and 4 to 7% by weight of other auxiliaries.

2. The polyester material according to claim 1, characterized in that: The polycarbonate has a melt index of 5-30 g / 10 min at 300° C. and 1.2 kg.

3. The polyester material according to claim 1, characterized in that: The other additives include toughening agents; Preferably, the polyester material comprises 3 to 5 wt% of toughening agent.

4. The polyester material according to claim 3, characterized in that: The toughening agent includes any one of a terpolymer of methyl methacrylate-butadiene-styrene, a silicon-acrylate copolymer, and acrylate, or a combination of at least two of them.

5. The polyester material according to claim 1, characterized in that: The compatibilizer includes any one of ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, acrylonitrile-styrene-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer, or a combination of at least two thereof.

6. The polyester material according to claim 1 or 3, characterized in that: The other additives also include any one or a combination of at least two of antioxidants, lubricants, and anti-ultraviolet agents; Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant and / or a compound of an amine antioxidant and a phosphite antioxidant; Preferably, the lubricant is silicone masterbatch and / or pentaerythritol stearate; Preferably, the anti-ultraviolet agent includes any one of 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, or a combination of at least two thereof.

7. A method for preparing a polyester material according to any one of claims 1 to 6, characterized in that: The preparation method comprises: The polycarbonate with a moisture content of ≤0.1%, diphenyl sulfone, a compatibilizer and other auxiliary agents are mixed, added into an extruder and melt-granulated to obtain the polyester material.

8. The polyester material according to claim 7, characterized in that The aspect ratio of the extruder is 40-50:1, the temperature range of the extruder is 220-260°C, and the basic screw speed is 300-600rpm / min; Preferably, the temperature of each section of the extruder is as follows: The temperature of zone 1 is 220-230℃, the temperature of zone 2 is 230-240℃, the temperature of zones 3 to 9 is 240-260℃, and the temperature of the machine head is 240-260℃.

9. A radiation protection product, characterized in that: The radiation protection product is partially or entirely made of polyester material, wherein the polyester material is the polyester material according to any one of claims 1-6.

10. Use of the polyester material according to any one of claims 1 to 6 or the radiation protection product according to claim 9 in nuclear radiation, ionizing radiation and electromagnetic radiation.

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