A high-flow PA / PP composite material and its application

Abstract

This application belongs to the field of polymer compositions, and particularly relates to a high-flowability PA / PP composite material and its application. A high-flowability PA / PP composite material is disclosed, which comprises the following components by weight: 20-60 parts of PA, 1-20 parts of PP, 20-70 parts of functional filler, 0.5-2 parts of flow modifier, and 0-5 parts of other additives. The PA is one or both of PA6 and PA66, the functional filler is one or both of reinforcing filler and heat-conducting filler, and the flow modifier is: R 1 -COOH and R 2 -(OH) m or (NH2) n -R 2 -(OH) m to produce an ester or amide product through an esterification or amidation reaction, wherein R 1 is an alkyl group with 15-19 carbon atoms, R 2 is an alkyl group with 1-6 carbon atoms, m is an integer from 1 to 3, and n is an integer from 0 to 3. Compared with the prior art, the present invention unexpectedly discovers a type of flow modifier that can greatly improve the processing flowability of PA / PP. The solution of this application can significantly improve the pad printing effect of the material at a relatively high PP content, and also has unexpected technical effects.

Description

Technical Field

[0001] The present invention belongs to the field of polymer compositions, and particularly relates to a high-flowability PA / PP composite material and its application. Background Art

[0002] In recent years, with the increasingly wide application of polyamide (PA) engineering plastics, higher requirements have been put forward for its modification, such as low cost, good mechanical properties, good processing fluidity, etc. In the prior art, in order to achieve low cost, on the one hand, resins with lower costs are selected. However, more reinforcing fillers often need to be added to maintain high mechanical properties or a high amount of thermal conductive fillers are added to increase the thermal conductivity of the material. However, the more reinforcing fillers or thermal conductive fillers are added, the worse the processing fluidity of the material becomes. Generally, a flow modifier is selected to improve the processing fluidity of the material. AF-21 is a super flow modifier specially developed for nylon and is widely used to improve the fluidity of polyamide. However, the selection is relatively single, and the modification effect of other lubricants with partial flow modification functions is relatively poor; or an alloy (such as polypropylene, i.e., PP) is selected to improve the problem through the processing fluidity of the alloy material. However, the alloy may bring other problems (such as compatibility) due to the introduction of the alloy resin. The situation is relatively complex, and it is necessary to repeatedly sample and verify whether the performance meets the indicators and eliminate other problems brought by the introduction of the new resin. In addition, in some special requirements (such as when the addition amount of PP is large, it will cause the pad printing performance of the parts to deteriorate), the addition amount of PP is restricted and cannot meet the requirements. Summary of the Invention

[0003] In order to overcome the foregoing problems existing in the prior art, the purpose of the present invention is to provide a new formulation system to further improve the processing fluidity of PA / PP, which is specifically achieved through the following technical solutions:

[0004] A high-flowability PA / PP composite material, by weight, comprises the following components:

[0005] PA 20 - 60 parts

[0006] PP 1 - 20 parts

[0007] Functional filler 20 - 70 parts

[0008] Flow modifier 0.5 - 2 parts

[0009] Other additives 0 - 5 parts

[0010] The PA is one or two of PA6 and PA66, and the functional filler is one or two of a reinforcing filler and a thermal conductive filler.

[0011] The flow modifier is: R 1 -COOH and R 2-(OH)m or (NH2)n-R 2 Esters or amide products produced by the esterification or amidation reaction of -(OH)m, where R 1 is an alkyl group with 15 to 19 carbon atoms, and R 2 is an alkyl group with 1 to 6 carbon atoms, m is an integer from 1 to 3, and n is an integer from 0 to 3.

[0012] Regarding R 1 -COOH can represent long-chain carbon substances with terminal carboxyl groups, such as stearic acid; (NH2)n-R 2 -(OH)m can represent substances containing terminal amino groups and having one or more hydroxyl groups connected by an alkyl chain, and also includes the case where there are hydroxyl groups in the alkyl group of R2. For example, when n is 0, glycerol can react with R1-COOH by esterification to obtain glycerol esters.

[0013] Optionally, by weight, it includes the following components:

[0014] PA 30 - 50 parts

[0015] PP 2 - 15 parts

[0016] Thermal conductive filler 10 - 45 parts

[0017] Reinforcing filler 10 - 40 parts

[0018] Compatibilizer 0 - 10 parts

[0019] Other additives 0 - 5 parts

[0020] Flow modifier 0.5 - 2 parts,

[0021] Among them, the sum of the weight parts of the thermal conductive filler and the reinforcing filler is 20 - 65 parts.

[0022] Optionally, for the flow modifier, R1 is an alkyl group with 17 carbon atoms.

[0023] Optionally, the flow modifier includes one or more of N-hydroxymethyl stearamide, stearamide MEA, stearamide DEA, ethylene glycol stearate, diglycol monostearate, and glycerol monostearate.

[0024] N-hydroxymethyl stearamide CAS: 3370 - 35 - 2, and the structural formula is as follows:

[0025]

[0026] Stearamide MEA CAS: 111 - 57 - 9, and the structural formula is as follows:

[0027]

[0028] Stearamide DEA CAS: 93-82-3, with the structural formula as follows:

[0029]

[0030] Ethylene glycol stearate CAS: 111-60-4, with the structural formula as follows:

[0031]

[0032] Glycerol monostearate CAS: 123-94-4, with the structural formula as follows:

[0033]

[0034] Optionally, the heat-conducting filler includes one or more of magnesium hydroxide, calcium carbonate, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silicon carbide, molybdenum disulfide, zinc sulfide, wollastonite, and talcum powder.

[0035] Optionally, the reinforcing filler includes one or more of glass fiber, carbon fiber, and mineral powder.

[0036] Optionally, the other additives include one or more of antioxidant, lubricant, and color powder.

[0037] Optionally, the compatibilizer includes one or more of EPDM-grafted maleic anhydride copolymer, polypropylene-grafted maleic anhydride copolymer, and POE-grafted maleic anhydride copolymer.

[0038] This application also provides an application of the composite material according to the foregoing solution, which is applied to a lamp housing with a wall thickness of less than 1.0 mm for thin-walled products.

[0039] This application also provides an application of a flow modifier for improving the processing flowability of PA / PP composite materials. The flow modifier is an ester or amide product produced by the esterification or amidation reaction of R1-COOH with R2-(OH)m or (NH2)n-R2-(OH)m, where R1 is an alkyl group with 15 to 19 carbon atoms, R2 is an alkyl group with 1 to 6 carbon atoms, m is an integer from 1 to 3, and n is an integer from 0 to 3.

[0040] Optionally, for the flow modifier, R1 is an alkyl group with 17 carbon atoms.

[0041] Optionally, the flow modifier includes one or more of N-hydroxymethyl stearamide, stearamide MEA, stearamide DEA, ethylene glycol stearate, diglycol monostearate, and glycerol monostearate.

[0042] Compared with the prior art, the present invention unexpectedly discovers a class of flow modifiers that can greatly improve the processing flowability of PA / PP. Such substances as stearamide MEA, stearamide DEA, ethylene glycol stearate, diglycol monostearate, glycerol monostearate, etc. contained therein are generally used as antistatic agents, lubricants, etc. in the prior art, and their special flowability improvement characteristics have not been discovered. Or rather, the present application overcomes the technical prejudice in the prior art that they can only be used as antistatic agents and lubricants. In addition, the solution of the present application can greatly improve the pad printing effect of the material at a relatively high PP content, and also has an unexpected technical effect. The applicant believes that the possible principle is: when PP is present, the long-chain carbon at the R 1 end of -COOH of R 1 tends to be in closer contact with PP, and the ester groups or amide groups formed by the reaction and the additional hydroxyl groups tend to be in closer contact with polyamide, destroying and replacing the hydrogen bond binding force between different molecular chains of polyamide. On the one hand, the fluidity of polyamide is improved. On the other hand, through the binding force between R 1 and PP, PP is better embedded between the molecular chains of polyamide, enhancing the flow modification effect of PP on polyamide. Compared with other substances with similar structures such as EBS, PETS, etc., they do not show the same level of flow modification effect as the solution of the present application. The present application provides a flow modifier for PA / PP composites. The effect of the flow modifier used is difficult to predict. Especially for highly filled materials, a high-quality flow modifier is provided, which has significant progress. Description of the Drawings

[0043] Figure 1 It is a shear viscosity curve graph of Examples 1-3 and Comparative Examples 1-3 under the condition of 270°C. Detailed Embodiments

[0044] The following elaborates on the specific embodiments of the present application in detail through examples. However, the specific implementation of the present application does not limit the technical solution of the present application. Any non-substantive changes such as common technical solution replacements in the art using the technical solution described in the embodiments of the present application are within the protection scope of the present application.

[0045] It should be noted that:

[0046] Introduction to the raw materials or specific substances used in each embodiment of the present application:

[0047] PA66: Wenzhou Huafeng Group, EP1107;

[0048] PA6: Guangdong Xinhui Meida Acrylic Fiber Co., Ltd., M2000;

[0049] PP: Yongjia Xi 1450T;

[0050] Glass fiber: Jushi Group Co., Ltd., ECS10-4.5-560A;

[0051] Calcium carbonate: Jiangxi Yongfa Chemical Industry Co., Ltd.;

[0052] Antioxidant: Antioxidant 1098;

[0053] EBS (Ethylene bisstearamide): Guangzhou Fenghua Chemical Technology Co., Ltd.;

[0054] Ethylene glycol stearate CAS: 111-60-4;

[0055] Glycerol monostearate CAS: 123-94-4;

[0056] Ethoxylated stearamide CAS: 93-82-3;

[0057] AF-21, Guangzhou Hecheng Industry Co., Ltd.;

[0058] PETS (Pentaerythritol stearate) CAS: 115-83-3, Jiangsu Haian Petrochemical Industry.

[0059] The material preparation methods of the examples and comparative examples are as follows:

[0060] Produced by melt blending and extrusion process. After mixing the raw material components except glass fiber, they are added into the twin-screw extruder through the main feeding port. Glass fiber (if any) is added from the side feeding port. After melt blending, it is extruded, and then obtained the materials of each example and comparative example through cooling, air drying and pelletizing.

[0061] Sample injection molding process: Add the materials of each example and comparative example into the injection molding machine. The injection molding temperature is 250~280 °C, and each test sample is injection molded according to the requirements of each test method.

[0062] The performance test methods are as follows:

[0063] Notched impact strength: Tested according to ISO179-1 standard (23 °C, 1J);

[0064] Unnotched impact strength: Tested according to ISO179-1 standard (23 °C, 4J);

[0065] Pad printing effect: Scratch on the surface of the sample plate with a Dyno pen. By observing the dispersion of the Dyno pen solution on the surface of the sample plate with the naked eye, evaluate the surface tension to reflect the pad printing effect. The grade is divided into 1~5 levels, with 1 level being the lowest (almost no effect) and 5 levels being the highest (clear effect); The Dyno pen can quickly and intuitively detect whether the material is suitable for printing (including pad printing);

[0066] Processing fluidity: 1) Measure the melt index (at 270 °C and 2.16 kg) according to ISO 1133 to evaluate the processing fluidity of the material; 2) Measure the shear viscosity according to GB / T25278-2010 (at 270 °C) to evaluate the processing fluidity of the material. Under the condition of the same shear rate, the lower the shear viscosity, the better the actual processing fluidity.

[0067] The formulations and performance data of the examples and comparative examples are shown in Tables 1 to 3.

[0068] Table 1 shows the formulations (parts by weight) and performance data of Examples 1 to 3 and Comparative Examples 1 to 3.

[0069]

[0070] Table 2 shows the formulations (parts by weight) and performance data of Examples 4 and 5 and Comparative Examples 4 to 9.

[0071]

[0072] Table 3 shows the formulations (parts by weight) and performance data of Examples 6 to 12.

[0073]

[0074] From the data in Tables 1, 2 and 3, it can be seen that:

[0075] By comparing Comparative Example 1 with Example 2, the applicant unexpectedly found that: compared with the blank control group, the ethylene glycol stearate of the present application improved the notched Izod impact strength, unnotched Izod impact strength and melt index performance by 79%, 29% and 48% respectively. The significant improvement in each index is an unexpected technical effect and has remarkable progress.

[0076] By comparing Comparative Examples 2 and 3 with Examples 1 and 2: on the one hand, AF-21, which is often used as a flow modifier in polyamide (AF-21 is a super flow modifier specially developed for nylon, and its main component is adipic acid), has a much worse effect on improving the flow of the material than adding the ethylene glycol stearate described in the present application. On the other hand, the notched Izod impact strength and unnotched Izod impact strength of the material are also greatly improved. Specifically, when adding 0.5 parts, the notched Izod impact strength, unnotched Izod impact strength and melt index performance are improved by 51%, 38% and 4% respectively. When adding 1 part, the notched Izod impact strength, unnotched Izod impact strength and melt index performance are improved by 74%, 24% and 36% respectively. Unexpected effects have been achieved and remarkable progress has also been made.

[0077] Example 2 compared with Comparative Examples 6 and 7: 1 part of ethylene glycol stearate was added. Compared with 1 part of PETS, the melt index increased by 35%. Compared with 1 part of EBS, the notched Izod impact strength, unnotched Izod impact strength, and melt index performance increased by 59%, 13%, and 60% respectively. It has unexpected technical effects. Especially the significant increase in the melt index shows remarkable progress.

[0078] Example 6 compared with Comparative Examples 8 and 9: The resin was PA66, and 1 part of ethylene glycol stearate was added. Compared with the blank control, the notched Izod impact strength, unnotched Izod impact strength, and melt index performance increased by 51%, 17%, and 26% respectively. Compared with 1 part of AF-21, the notched Izod impact strength, unnotched Izod impact strength, and melt index performance increased by 43%, 21%, and 39% respectively. It has unexpected technical effects. Especially compared with the commonly used flow modifier AF-21, it shows remarkable progress.

[0079] Examples 7 and 8 compared with Comparative Examples 1 and 3: It shows that ethoxylated fatty acid amide and glycerol monostearate can also achieve technical effects equivalent to those of ethylene glycol stearate. Compared with the blank control and the addition of the flow modifier AF-21, the notched Izod impact strength, unnotched Izod impact strength, and melt index performance have increased significantly, showing remarkable progress.

[0080] From the data in Tables 1 to 3, it can be seen that by adding ethylene glycol stearate, ethoxylated fatty acid amide, and glycerol monostearate in this application, the pad printing performance of the PA / PP alloy material can be greatly improved.

[0081] Table 4 Shear viscosity performance test data of Examples 1, 2, 3 and Comparative Examples 1, 2, 3

[0082] The shear viscosity performance test data of Examples 1, 2, 3 and Comparative Examples 1, 2, 3 described in Table 4. Figure 1 It is a curve graph made according to the data in Table 4. As shown in Table 4 and Figure 1 shown, compared with Comparative Examples 1, 2, 3, the shear viscosity curves of Examples 1, 2, 3 are all lower than those of the comparative examples. Especially for Examples 2 and 3, they are significantly lower than those of Comparative Examples 1, 2, 3, indicating that the processing fluidity of the formulation with the addition of ethylene glycol stearate is better than that of the blank and AF-21, having unexpected technical effects.

[0083] It should be noted that the above content described in this specification is only an example illustration of the technical solution of the present invention. Any simple changes or equivalent changes made based on the features and principles described in the inventive concept of this patent are included in the protection scope of this patent.

Claims

1. A high-flow PA / PP composite material, characterized in that, By weight parts, it comprises the following components: PA 50 - 60 parts PP 5 - 8 parts Functional filler 20 - 65 parts Flow modifier 0.5 - 2 parts Other additives 0 - 5 parts The PA is one or two of PA6 and PA66, the functional filler is one or two of reinforcing filler and heat-conducting filler, and the flow modifier includes one or several of stearamide DEA, ethylene glycol stearate, and glycerol monostearate.

2. The composite material according to claim 1 or as described above, characterized in that, The heat-conducting filler includes one or several of magnesium hydroxide, calcium carbonate, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silicon carbide, molybdenum disulfide, zinc sulfide, wollastonite, and talcum powder.

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

4. The composite material according to claim 1, wherein The other additives include one or several of antioxidant, lubricant, and color powder.

5. Use of the composite material according to any one of claims 1 to 4, characterized in that It is applied to the lamp housing with a wall thickness of less than 1.0 mm for thin-walled products.

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