Yellowing-resistant polyphenyl ether composite material as well as product and application thereof

Abstract

The invention belongs to the field of polymer compositions, and particularly relates to an anti-yellowing polyphenyl ether composite material as well as a product and application thereof. The invention provides a yellowing-resistant polyphenyl ether composite material, which is prepared from the following components in parts by weight: 30 to 70 parts of polyphenyl ether resin, 15 to 40 parts of polystyrene, 0 to 15 parts of flame retardant, 0 to 30 parts of reinforcing filler, 0 to 10 parts of compatilizer, 0.1 to 1 part of benzoin, 0.01 to 0.3 part of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and 0 to 5 parts of other auxiliaries. The application accidentally finds that 0.01-0.3 part of DOPO with extremely low parts is introduced into the benzoin processing yellowing resistant system of polyphenyl ether, and through the synergistic effect of benzoin and DOPO components and contents, the processing yellowing resistant performance of polyphenyl ether is further improved in the processing process of polyphenyl ether, and the processing yellowing resistant performance of the polyphenyl ether is further improved. And the yellowing resistance in a hot oxygen environment, a natural environment and a humid and hot environment is also greatly improved.

Description

Technical Field

[0001] The invention belongs to the field of polymer compositions, and in particular relates to a yellowing-resistant polyphenylene ether composite material and a product and application thereof. Background Art

[0002] Polyphenylene oxide resin (PPO) is a high-performance engineering plastic with excellent mechanical properties, heat resistance, electrical insulation and low water absorption. However, PPO also has some disadvantages, such as difficult processing and low impact strength. In order to overcome these disadvantages and improve its comprehensive performance, polystyrene (PS) or high-impact polystyrene (HIPS) is usually used to modify it. Through reasonable proportions, PPO can be comprehensively optimized in terms of mechanical properties, heat resistance, electrical insulation, etc., so that it meets application requirements.

[0003] However, in practical applications, PPO is prone to discoloration during high-temperature processing, and antioxidants and other additives are usually used to improve the discoloration problem of modified polyphenylene ether during processing. Hydroxyketone antioxidant benzoin can effectively inhibit the discoloration of polyphenylene ether resin compositions during thermal processing. However, the applicant found that PPO has a more obvious yellowing tendency in hot oxygen environment, natural storage, and hot and humid environment.

[0004] DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS No. 35948-25-5) contains biphenyl ring and phenanthrene ring structure in its molecular structure, especially the side phosphorus group is introduced in the form of cyclic O=PO bond, which has higher thermal stability and chemical stability than general, non-annulated organic phosphates, and better flame retardant performance. It can be used as a reactive and additive flame retardant. The synthesized flame retardant is halogen-free, smoke-free, non-toxic, non-migrating, and has long-lasting flame retardant performance. It is a highly efficient organic phosphorus flame retardant with good thermal and chemical stability. It can be mixed with resins, plastics and other materials to improve the flame retardant properties of these materials. The Chinese patent with publication number CN101781451 uses 0.05~5 parts of phosphaphenanthrene (DOPO) to improve the color stability of PPE (i.e. PPO). According to the ratio of PPO and DOPO disclosed in the embodiment, and the amount of DOPO added is 1 part or 2 parts, although the information disclosed shows that there is a certain improvement effect, it is easy to produce mold scale on the mold surface and spots on the surface of the product. The technical problems existing in the above patent are also mentioned in the background technology of the publication number CN102432990A. The Chinese patent embodiment with the publication number CN102344663A also adopts a DOPO addition amount of 2% to 8%, specifically 6 parts, and also has the above problems.

[0005] Currently, there is no technical means to solve the yellowing problem of PPO during processing and in hot and oxidative environments, natural environments, and hot and humid environments. Summary of the invention

[0006] In order to overcome the yellowing problem of polyphenylene ether in the prior art, the object of the present invention is to provide a technical solution for improving the yellowing resistance of polyphenylene ether, which is specifically achieved by the following technical solution: A yellowing-resistant polyphenylene ether composite material comprises the following components in parts by weight: Polyphenylene ether resin 30~70 parts Polystyrene 15~40 parts Flame retardant 0~15 parts Reinforced filler 0~30 parts Compatibilizer 0~10 parts Benzoin 0.1~1 part DOPO 0.01~0.3 parts Other additives 0~5 parts.

[0007] Optionally, the polystyrene comprises high impact polystyrene.

[0008] Optionally, the flame retardant includes one or more of phosphate ester and nitrogen-phosphorus flame retardants.

[0009] Optionally, the reinforcing filler includes one or two of glass fiber, carbon fiber, and mineral powder.

[0010] Optionally, the compatibilizer includes one or more of SEBS, PPO-g-MAH, and SEBS-g-MAH.

[0011] Optionally, the other additives include one or more of lubricants, flow modifiers, light stabilizers, and color powders.

[0012] The present application also provides a yellowing-resistant polyphenylene ether composite material product, which is made of the composite material described in any of the above technical solutions.

[0013] The present application also provides an application of benzoin and DOPO in improving the yellowing resistance of polyphenylene ether, which comprises the following components in parts by weight: Polyphenylene ether resin 30~70 parts Polystyrene 15~40 parts Flame retardant 0~15 parts Reinforced filler 0~30 parts Compatibilizer 0~10 parts Benzoin 0.1~1 part DOPO 0.01~0.3 parts Other additives 0~5 parts.

[0014] Compared with the prior art, the present application unexpectedly discovered that by introducing an extremely low amount of 0.01 to 0.3 parts of DOPO into the polyphenylene ether benzoin processing yellowing resistance system, through the synergistic effect of benzoin and DOPO components and contents, the polyphenylene ether not only further improves the processing yellowing resistance of the polyphenylene ether during the processing process, but also greatly increases the yellowing resistance in hot oxygen environment, natural environment, and hot and humid environment.

[0015] Compared with the prior art, the addition of a higher proportion of DOPO solves the problem of yellowing during processing, so that the initial color of the processed parts is better. However, in the presence of a higher proportion of DOPO, the polyphenylene ether composite parts may also decompose / oxidize and degrade to yellow in a hot and oxidative environment, a natural environment, and a hot and humid environment (light, humidity, temperature, etc. are different from the factors affecting the injection molding process), which affects the actual use of the parts. In addition, DOPO itself will also degrade and turn yellow, and the more the proportion, the more obvious it is. It also avoids the problem of mold scale on the mold surface and spots on the surface of the parts, and overcomes the technical prejudice of the prior art that the addition amount is 0.05~5 parts or 2%~8%, that is, it is not within the range shown that the addition amount has a good effect, and this trend is not revealed in the embodiments. Generally speaking, within a certain range, the more the addition amount, the better the effect. The technical effect of selecting the content range in the present application is unexpected.

[0016] The present application scheme has a low DOPO dosage, high material mechanical property retention, and low formulation cost. It can reduce the yellowing problem of polyphenylene ether during processing and in hot and oxidative environments, natural environments, and hot and humid environments, and has outstanding substantive characteristics and significant progress. DETAILED DESCRIPTION

[0017] The specific implementation methods of the present application are described in detail below through examples, but the specific implementation of the present application does not serve as a limitation on the technical solution of the present application. Any non-substantial changes such as replacing common technical solutions in the field with the technical solutions described in the examples of the present application are within the scope of protection of the present application.

[0018] It should be noted that the raw materials of this application are specifically: PPO (polyphenylene ether): LXR045 Nantong Xingchen Synthetic Materials Co., Ltd. PS (polystyrene): GPPS-123 Shanghai Secco Petrochemical Co., Ltd. HIPS (high impact polystyrene): POLYSTYROL S 495F NATURAL BASF, Germany Glass fiber: 560A China Jushi Co., Ltd. Flame retardant: WSFR-BDP Zhejiang Wansheng Co., Ltd. Lubricant: Calcium stearate Hangzhou Oil Chemical Co., Ltd. Compatibilizer: SEBS Kraton G1651 HU Kraton Corporation, USA Toner: Phthalocyanine Blue K6907, BASF, Germany Benzoin: BENZOIN Korea Miwon Special Chemical Co., Ltd. DOPO: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, CAS No. 35948-25-5 Shouguang Weidong Chemical Co., Ltd.

[0019] In each embodiment and comparative example, each raw material component is weighed according to the weight ratio. If there is glass fiber, the components except the glass fiber are premixed in a high-speed mixer to obtain a premix. The premix is ​​then fed into a twin-screw extruder from a main feeding port, and the glass fiber is fed from a side feeding port. After melt blending, extrusion, cooling, air drying, and granulation, a modified polyphenylene ether composite material is obtained.

[0020] Preparation of test pieces: The modified polyphenylene ether composite materials prepared in the above embodiments and comparative examples were placed in an oven and dried at 110°C for 3 hours. The test color plates were prepared by injection molding according to the requirements of GB / T 17592-2008: Chinese National Standard "Plastic Color Determination Part 2: Multi-angle Colorimeter Method", with the injection molding temperature of 270-300°C and the mold temperature of 80-120°C.

[0021] The performance test method is as follows: Yellowing resistance: 1) Initial color: The Lab value of the color plate after the injection molding is measured by the CM-36dG colorimeter produced by Konica Minolta represents the initial color, which reflects the yellowing resistance of the formula. It should be noted that since the color powder used in the embodiment of the present application is blue, the b value is initially negative. The smaller the b value (the more negative), the bluer the color, that is, the better the yellowing resistance. On the contrary, the larger the b value, the worse the yellowing resistance. Although the L value can represent the brightness to a certain extent, in this application, the darker the blue color, the lower the L value may be. The L value cannot be used to reflect the yellowing resistance trend of the material.

[0022] 2) Thermal Oxygen Yellowing: Indicates the yellowing resistance of the material under thermal oxygen conditions. Place the color plate in an oven at 120°C, measure the color value (Lab value) after 4h and 8h respectively, and calculate the change DE compared to the initial color (i.e. DealtE: the total color difference between two color samples calculated based on the CIELAB color space). The smaller the DE, the less color change, that is, the better the yellowing resistance.

[0023] 3) Natural placement: Indicates the yellowing resistance of the material in a natural placement environment. Place the color plate on an unobstructed color plate rack outdoors for 7 days and measure the DE of the color plate compared to the initial color. The smaller the DE, the less color change, that is, the better the yellowing resistance.

[0024] 4) Double 85 test: indicates the yellowing resistance of materials in a hot and humid environment. Place the color plate in an environment with a temperature of about 85°C and a humidity of about 85% (i.e. 85RH) for 10 days, and measure the change DE between the color plate and the initial color. The smaller the DE, the less the color change, that is, the better the yellowing resistance.

[0025] The components and properties of the embodiments and comparative examples are shown in Table 1 and Table 2. In the table, the toner in each embodiment and comparative example is 1 part, the lubricant is 0.3 parts, and the flame retardant is 12 parts, which are not repeated in the table. In addition, the components in the table are all parts by weight.

[0026] Table 1 shows the components and performance test data in Examples 1 to 7

[0027] Table 2 shows the components and performance test data in Comparative Examples 1 to 7

[0028] The data of the embodiments and comparative examples in the above table show that by introducing a very low amount of 0.01 to 0.3 parts of DOPO into the polyphenylene ether benzoin processing yellowing resistance system, the synergistic effect of the components and contents of benzoin and DOPO can not only further improve the processing yellowing resistance of the polyphenylene ether during the processing, but also greatly increase the yellowing resistance in a hot and oxidative environment, a natural environment, and a hot and humid environment.

[0029] Specifically, Comparative Example 5 uses 0.6 parts of benzoin antioxidant, and Comparative Example 7 uses 0.6 parts of DOPO. Compared with the blank control of Comparative Example 1, the initial color b value after processing is lower, which can improve the processing yellowing resistance. Especially Comparative Example 5, the effect is better. However, the applicant found that benzoin has poor yellowing resistance in hot oxygen environment, natural storage, and hot and humid environment, and even the effect of natural storage for 7 days is worse than that of Comparative Example 1 without adding antioxidant. Comparative Example 7 adds 0.1 parts of DOPO alone, and the improvement of processing yellowing performance is poor, but the effect of hot oxygen yellowing, natural storage for 7 days, and 10 days of double 85 experiments is better than that of Comparative Example 1 and Comparative Example 5.

[0030] Compared with Example 3, Comparative Example 5 and Comparative Example 7, the addition of 0.1 parts of DOPO and 0.5 parts of benzoin significantly reduced the initial color b value compared with the addition of 0.6 parts of DOPO or benzoin alone. At the same time, the yellowing resistance effect of the thermal oxygen yellowing (4h, 8h), natural placement for 7 days, and 10 days was significantly improved. This shows that the two have a synergistic effect.

[0031] Comparative Example 6 also uses 0.5 parts of benzoin and 1 part of DOPO to compound. However, when 1 part of DOPO is used, a small amount of spots are observed on the surface of the workpiece with the naked eye, which is not conducive to practical application. The defects mentioned in the background technology exist. The improvement of the yellowing resistance during processing is not obvious. Compared with Comparative Example 5, the addition of 1 part of DOPO reduces the yellowing resistance of benzoin to the material during processing. The applicant believes that it may be because a large amount of DOPO has squeezed out the interaction between benzoin and the "yellowing functional groups" in PPO, resulting in the inability to show its own advantage of yellowing resistance during processing. In the double 85 tests of thermal oxidative yellowing (4h, 8h), natural placement for 7 days, and 10 days in Comparative Example 6, although the yellowing resistance effect is better than that of Comparative Example 5, it has not yet reached the effect of adding DOPO alone as a whole.

[0032] Compared with Example 6, in Example 3, the addition amount of DOPO was reduced to 0.1 parts, which was reduced by 10 times. The overall initial color, thermal oxygen yellowing (4h, 8h), natural placement for 7 days, and 10 days of double 85 tests, the yellowing resistance effect was much better than that of Comparative Example 6, which was an unexpected technical effect. It is inferred that it may be because both are dispersed in the "yellowing functional groups" in PPO and can interact with each other, making up for the shortcomings of each other.

[0033] Compared with Example 3, the anti-yellowing effects of Examples 1 and 2 with 0.3 and 0.01 parts of DOPO added are inferior to that of 0.1 parts, which also shows that the more DOPO is added, the better the anti-yellowing effect is.

[0034] It should be noted that the materials used in the above embodiments can be selected or replaced by those skilled in the art according to their needs, and this does not exceed the protection scope of this application.

Claims

1. A yellowing-resistant polyphenylene ether composite material, characterized in that: In parts by weight, it includes the following components: Polyphenylene ether resin 30~70 parts Polystyrene 15~40 parts Flame retardant 0~15 parts Reinforced filler 0~30 parts Compatibilizer 0~10 parts Benzoin 0.1~1 part DOPO 0.01~0.3 parts Other additives 0~5 parts.

2. The composite material according to claim 1, characterized in that The polystyrene includes high impact polystyrene.

3. The composite material according to claim 1, characterized in that The flame retardant includes one or more of phosphate ester and nitrogen-phosphorus flame retardants.

4. The composite material according to claim 1, characterized in that The reinforcing filler includes one or two of glass fiber, carbon fiber and mineral powder.

5. The composite material according to claim 1, characterized in that The compatibilizer includes one or more of SEBS, PPO-g-MAH, and SEBS-g-MAH.

6. The composite material according to claim 1, characterized in that The other auxiliary agents include one or more of lubricants, flow modifiers, light stabilizers, and toners.

7. A yellowing-resistant polyphenylene ether composite material product, characterized in that: Made from the composite material according to any one of claims 1 to 6.

8. Application of benzoin and DOPO in improving the yellowing resistance of polyphenylene ether, characterized in that: In parts by weight, it includes the following components: Polyphenylene ether resin 30~70 parts Polystyrene 15~40 parts Flame retardant 0~15 parts Reinforced filler 0~30 parts Compatibilizer 0~10 parts Benzoin 0.1~1 part DOPO 0.01~0.3 parts Other additives 0~5 parts.

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