Polyphenylene ether / polyamide alloy, and preparation method therefor and use thereof

Abstract

A polyphenylene ether / polyamide alloy, comprising the following components in parts by weight: 20-50 parts of polyphenylene ether; 20-40 parts of polyamide; 10-40 parts of a glass fiber; 3-12 parts of a toughening agent; 0.1-2 parts of a compatibilizer; and 0.2-1.5 parts of a coupling agent, wherein the weight ratio of polyphenylene ether to polyamide is (1.8-1):1. The present invention provides a polyphenylene ether / polyamide alloy having excellent dimensional stability, good hydrolysis resistance, and a weld line strength of greater than or equal to 40 MPa, and being suitable for the water treatment industry.

Description

A polyphenylene ether / polyamide alloy, its preparation method and application Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polyphenylene ether / polyamide alloy, its preparation method, and its application. Background Technology

[0002] Polyphenylene oxide (PPE), an amorphous engineering plastic, possesses advantages such as acid and alkali resistance, high temperature resistance, damp heat resistance, and dimensional stability. However, its high viscosity makes it difficult to process. Introducing polystyrene (PS) into PPE leverages PS's high flowability, damp heat resistance, and dimensional stability, making the resulting PPE / PS alloy highly suitable for use in the water treatment industry. However, PPE / PS suffers from stress cracking, posing a cracking risk to customers during use. To address this issue, the material needs to possess excellent stress cracking resistance while maintaining dimensional stability, hydrolysis resistance, and water pressure resistance.

[0003] To address the issue of stress cracking, some manufacturers have used PPA and PA to replace PS. However, they have found that PA materials cause dimensional changes in the manufactured parts after absorbing water, failing to meet customer requirements. Some customers have also used PP and other materials as substitutes, only to find that the initial dimensions of these materials do not meet their requirements.

[0004] The water treatment industry requires an alloy that meets the requirements of high dimensional stability, hydrolysis resistance, compressive strength, weld line strength, and good stress cracking resistance. PPE / PA alloys can meet the requirements of high compressive strength and good stress cracking resistance, but it is difficult to simultaneously achieve the requirements of hydrolysis resistance, good dimensional stability, and high weld line strength. Summary of the Invention

[0005] The purpose of this invention is to provide a polyphenylene ether / polyamide alloy that is resistant to hydrolysis, has good dimensional stability, and high weld line strength.

[0006] This invention is achieved through the following technical solution:

[0007] A polyphenylene ether / polyamide alloy, comprising the following components by weight:

[0008] 20-50 parts of polyphenylene ether;

[0009] 20-40 parts of polyamide;

[0010] 10-40 parts glass fiber;

[0011] 3-12 parts toughening agent;

[0012] Compatibilizer 0.1-2 parts;

[0013] 0.2-1.5 parts of coupling agent;

[0014] The weight ratio of polyphenylene ether to polyamide is (1.8-1):1;

[0015] The compatibilizer is selected from at least one of maleic ester compatibilizers, acid anhydride compatibilizers, and N-phenylmaleimide.

[0016] Preferably, the weight ratio of polyphenylene ether to polyamide is (1.6-1.2):1.

[0017] Preferably, the compatibilizer is selected from maleate ester compatibilizers.

[0018] The maleic ester compatibilizer is selected from at least one of butyl maleate and butyl fumarate; the anhydride compatibilizer is selected from maleic anhydride.

[0019] The coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, and aluminate coupling agents; preferably, the coupling agent is selected from silane coupling agents.

[0020] The silane coupling agent is selected from at least one of aminosilane coupling agents and methoxysilane coupling agents.

[0021] The toughening agent is selected from any one or more of maleic anhydride-grafted styrene block copolymers and maleic anhydride-grafted ethylene-octene copolymers, wherein the weight content of maleic anhydride is 0.5-3 wt%, preferably 1.0-2 wt%; wherein the styrene block copolymer is selected from at least one of styrene-butadiene-styrene block copolymers, styrene-ethylene / butene-styrene block copolymers, or styrene-ethylene / propylene-styrene block copolymers.

[0022] Preferably, the polyphenylene ether resin, tested according to standard ISO 1133-1-2011 at 315°C and 10 kg, has a melt index of 4-90 g / 10 min. The monomer of the polyphenylene ether resin of this invention is 2,6-dimethylphenol.

[0023] The polyamide resin is selected from at least one of aliphatic polyamide resin and semi-aromatic polyamide resin; the aliphatic polyamide resin is selected from at least one of PA66, PA46, PA610, PA612, PA56, PA510, PA512, PA910, PA912, PA913, PA914, PA915, PA616, PA936, PA1010, PA1012, PA1013, PA1014, PA1210, PA1212, PA1213, PA1214, PA614, PA613, PA615, PA616, PA5, PA6, PA11, PA12; the semi-aromatic polyamide is selected from at least one of PA MXD6, PA10T, PA10T1010, PA10T66, PA6T, PA6T66, PA9T.

[0024] Those skilled in the art can choose whether to add 0-2 parts of an additive according to actual needs. The additive is selected from at least one of antioxidants and lubricants.

[0025] Antioxidants can be: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,5-di-tert-butyl-4-hydroxybenzyl dimethylamine; diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; stearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglycerol allyl ether)-1,3,5-triazine; N,N'-hexamethylene di( 3,5-Di-tert-butyl-4-hydroxy-hydrogenated cinnamamide; N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine; octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; triethylene glycol-bis[3-(3,5-dimethyl-4-hydroxyphenyl)propionate]; triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 2,2'-thiodiethyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.

[0026] The lubricant may be at least one of fatty acids and fatty acid derivatives; the fatty acid derivatives are selected from at least one of stearate lubricants and stearate ester lubricants, and the stearate lubricants are selected from at least one of calcium stearate, magnesium stearate, and zinc stearate.

[0027] The preparation method of the polyphenylene ether / polyamide alloy of the present invention includes the following steps: mixing each component evenly according to the formula, extruding and granulating it through a twin-screw extruder, with a screw speed of 250-500 rpm and an extrusion temperature of 230-290℃, to obtain the polyphenylene ether / polyamide alloy.

[0028] The application of the polyphenylene ether / polyamide alloy of the present invention is that the polyphenylene ether / polyamide alloy is used to manufacture water treatment equipment, such as HVAC valve pipes, valve cores, and meter housings.

[0029] The present invention has the following beneficial effects:

[0030] This invention, by adjusting the ratio of PPE / PA materials and adding specific compatibilizers, enables the PPE and PA in the material to possess a bicontinuous phase structure or a transitional state towards an island structure. This results in a material with excellent dimensional stability, hydrolysis resistance, and weld line strength, meeting the industry's requirements for dimensional stability, hydrolysis resistance, and water pressure resistance. Furthermore, coupling agents are used to strengthen the bond between glass fiber and resin, further enhancing the material's strength. The resulting reinforced PPE / PA alloy composition exhibits excellent dimensional stability, hydrolysis resistance, and a weld line strength ≥40 MPa, making it highly suitable for use in the water treatment industry. Detailed Implementation

[0031] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0032] PA66: PA66 U3600 NC001, NVIDIA;

[0033] PA6: PA6 BE3280, Suzhou Hongsheng New Materials;

[0034] PA1010: PA1010, DuPont;

[0035] PA10T: Vicnyl 700-02 NC001, Kingfa Science & Technology;

[0036] PA6T66: NPD-652, NVIDIA;

[0037] Polyphenylene oxide (PPE): at 315℃ and 10kg, the melt index is 20-40g / 10min. PPE LXR040, Bluestar.

[0038] Fiberglass: ECS10-03-568H, Jushi.

[0039] Toughening agent A-1: ​​Maleic anhydride-grafted styrene-butadiene-styrene block copolymer, prepared in-house: prepared by melt mixing SBS and maleic anhydride at a mass ratio of 99.5:0.5 at a mixing temperature of 200℃.

[0040] Toughening agent A-2: Maleic anhydride-grafted styrene-butadiene-styrene block copolymer, prepared in-house: prepared by melt mixing SBS and maleic anhydride at a mass ratio of 99:1.0 at a mixing temperature of 200℃.

[0041] Toughening agent A-3: Maleic anhydride-grafted styrene-butadiene-styrene block copolymer, prepared in-house: SBS and maleic anhydride are melt-blended at a mass ratio of 98:2 at a mixing temperature of 200℃.

[0042] Toughening agent A-4: Maleic anhydride-grafted styrene-butadiene-styrene block copolymer, prepared in-house: prepared by melt mixing SBS and maleic anhydride at a mass ratio of 97:3.0 at a mixing temperature of 200℃.

[0043] Toughening agent B: Maleic anhydride-grafted styrene-ethylene / butene-styrene block copolymer, with a maleic anhydride content of approximately 0.8%, BCD-1, Nanhai Baichen.

[0044] Toughening agent C: Maleic anhydride-grafted styrene-ethylene / propylene-styrene block copolymer, prepared in-house: SEEPS and maleic anhydride were melt-blended at a mass ratio of 99:1.

[0045] Toughening agent D: Maleic anhydride-grafted ethylene-octene copolymer, GMG5805, maleic anhydride content of 0.5-1%, Jia Yirong;

[0046] Compatibilizer A: Butyl maleate, Jiangsu Runfeng Synthetic Technology;

[0047] Compatibilizer B: Butyl fumarate, Hubei Zhonglong Kangcheng Fine Chemical Co., Ltd.;

[0048] Compatibilizer C: Maleic anhydride, Guangzhou Mohai Trading Co., Ltd.

[0049] Compatibilizer D: N-phenylmaleimide, Guangzhou Yuanda New Materials Co., Ltd.;

[0050] Compatibilizer E: Butyric anhydride, Jiangsu Bost Chemical Technology;

[0051] Coupling agent A: Aminosilane coupling agent, JH-A110, Hubei Jianghan New Materials;

[0052] Coupling agent B: Methoxysilane coupling agent, trimethoxysilane, Wuhan Xingzhongcheng Technology Co., Ltd.;

[0053] Coupling agent C: Titanate coupling agent, KR-TTS, Kenrich Petrochemicals, USA;

[0054] Coupling agent D: Aluminate coupling agent, LD-B-1, Lida Chemical;

[0055] Antioxidant: Antioxidant 1010 and Antioxidant 168 are compounded in a weight ratio of 1:2.

[0056] Preparation method of polyphenylene ether / polyamide alloy in the examples and comparative examples: The components are mixed evenly according to the formula, and then extruded and granulated by a twin-screw extruder at a screw speed of 350-400 rpm and an extrusion temperature of 230-290℃ to obtain polyphenylene ether / polyamide alloy.

[0057] Test methods:

[0058] (1) Shrinkage rate: A rectangular plate of 200*80*2mm was injection molded, and the length dimension of the material was tested after 2 days. The result was x mm. The shrinkage rate of the material was calculated according to (200-x) / 200*100%. The dimensional stability of the material was compared by comparing the size of the shrinkage rate.

[0059] (2) Weld line tensile strength: In accordance with ISO 527-1:2019, type 1A weld line tensile specimens were prepared, and the test rate was 10 mm / min. The water pressure resistance of the material was evaluated by the weld line strength.

[0060] (3) Hydrolysis resistance: The ISO standard Type 1A tensile specimen was placed in a double 85 aging chamber for 1000 hours and the tensile performance retention rate before and after aging was tested for evaluation. The tensile rate was 10 mm / min.

[0061] Table 1: Weight contents and test results of each component in the polyphenylene ether / polyamide alloys of Examples 1-7

[0062]

[0063] As can be seen from Examples 1 / 6 / 7 / 8, the preferred weight ratio of polyphenylene ether to polyamide results in lower shrinkage, better weld line strength, and better hydrolysis resistance.

[0064] Table 2: Weight contents and test results of each component in the polyphenylene ether / polyamide alloys of Examples 8-14

[0065]

[0066] As can be seen from Examples 1 / 9-11, the technical effect is better when the preferred maleic anhydride grafting rate is achieved.

[0067] Further, as can be seen from Examples 1 / 9-14, when the maleic anhydride grafting rate of toughening agents with different main chains is within the preferred range, the shrinkage rate and hydrolysis resistance are better.

[0068] Table 3: Weight contents and test results of each component in the polyphenylene ether / polyamide alloys of Examples 15-20

[0069]

[0070] As can be seen from Examples 1 / 15 / 16 / 17, maleic ester compatibilizers are preferred.

[0071] As can be seen from Examples 1 / 18 / 19 / 20, silane coupling agents are preferred.

[0072] Table 4: Weight contents and test results of each component in the comparative polyphenylene ether / polyamide alloy

[0073]

[0074] As shown in Comparative Example 1, butyric anhydride cannot be used as a compatibilizer.

[0075] As can be seen from Comparative Example 2, if the content of PA66 is too high, the shrinkage rate is too high and the hydrolysis resistance is poor.

[0076] As can be seen from Comparative Example 3, if the content of polyphenylene ether is too high, the weld line strength is poor.

[0077] As can be seen from Comparative Example 4, the lack of compatibilizer results in low weld line strength and poor hydrolysis resistance due to compatibility defects.

[0078] As shown in Comparative Example 5, if the compatibilizer content is too high, the weld line strength will be severely reduced, and the hydrolysis resistance will also decrease.

[0079] As can be seen from Comparative Example 6, when no coupling agent is present, the weld line strength is poor and the hydrolysis resistance is not high.

Claims

1. A polyphenylene ether / polyamide alloy, characterized in that, By weight, it includes the following components: 20-50 parts of polyphenylene ether; 20-40 parts of polyamide; 10-40 parts glass fiber; 3-12 parts toughening agent; Compatibilizer 0.1-2 parts; 0.2-1.5 parts of coupling agent; The weight ratio of polyphenylene ether to polyamide is (1.8-1):1; The compatibilizer is selected from at least one of maleic ester compatibilizers, acid anhydride compatibilizers, and N-phenylmaleimide.

2. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The weight ratio of polyphenylene ether to polyamide is (1.6-1.2):

1.

3. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The compatibilizer is selected from maleic ester compatibilizers; the maleic ester compatibilizer is selected from at least one of butyl maleate and butyl fumarate; the acid anhydride compatibilizer is selected from maleic anhydride.

4. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, and aluminate coupling agents; preferably, the coupling agent is selected from silane coupling agents; the silane coupling agent is selected from at least one of aminosilane coupling agents and methoxysilane coupling agents.

5. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The toughening agent is selected from any one or more of maleic anhydride-grafted styrene block copolymers and maleic anhydride-grafted ethylene-octene copolymers, wherein the weight content of maleic anhydride is 0.5-3.0 wt%, preferably 1.0-2 wt%; wherein the styrene block copolymer is selected from at least one of styrene-butadiene-styrene block copolymers, styrene-ethylene / butene-styrene block copolymers, or styrene-ethylene / propylene-styrene block copolymers.

6. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The polyphenylene ether resin described herein, when tested according to standard ISO 1133-1-2011 at 315℃ and 10kg, has a melt index of 4-90g / 10min.

7. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The polyamide resin is selected from at least one of aliphatic polyamide resin and semi-aromatic polyamide resin; the aliphatic polyamide resin is selected from at least one of PA66, PA46, PA610, PA612, PA56, PA510, PA512, PA910, PA912, PA913, PA914, PA915, PA616, PA936, PA1010, PA1012, PA1013, PA1014, PA1210, PA1212, PA1213, PA1214, PA614, PA613, PA615, PA616, PA5, PA6, PA11, PA12; the semi-aromatic polyamide is selected from at least one of PA MXD6, PA10T, PA10T1010, PA10T66, PA6T, PA6T66, PA9T.

8. The polyphenylene ether / polyamide alloy according to claim 1, characterized in that, The product also includes 0-2 parts by weight of additives, wherein the additives are selected from at least one of antioxidants and lubricants.

9. A method for preparing the polyphenylene ether / polyamide alloy according to any one of claims 1-8, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, granulating them by extrusion through a twin-screw extruder at a screw speed of 250-500 rpm and an extrusion temperature of 230-290℃ to obtain a polyphenylene ether / polyamide alloy.

10. The application of the polyphenylene ether / polyamide alloy according to any one of claims 1-8, characterized in that, The polyphenylene ether / polyamide alloy is used to manufacture water treatment equipment.

Images