Polyphenylene ether resin composition and polyphenylene ether composite, and preparation methods therefor and use thereof

Abstract

Disclosed in the present invention are a polyphenylene ether resin composition and a polyphenylene ether composite, and preparation methods therefor and the use thereof. The polyphenylene ether resin composition of the present invention is obtained by reacting polyphenylene ether with a naphthoic acid compound in a melt. The polyphenylene ether has a repeat unit of the structure below: (I), wherein R1, R2, R3 and R4 are each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbyloxy, or halohydrocarbyloxy. The naphthoic acid compound is at least one of naphthoic acid or hydroxynaphthoic acid. Compared with a polyphenylene ether resin, in a melt, the polyphenylene ether resin composition can not only improve the gas barrier property of the polyphenylene ether composite, but also improve the processing stability of the polyphenylene ether composite during high-temperature injection molding.

Description

Polyphenyl ether resin composition, polyphenyl ether composite material and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer compound composition, more particularly, to a polyphenyl ether composition, a polyphenyl ether composite material and a preparation method and application thereof. BACKGROUND

[0002] Polyphenyl ether resin (PPE) is widely used in the field of electrical and film materials due to its high heat resistance, excellent mechanical properties and electrical properties. However, the melt viscosity of most polyphenyl ether resins is very high, which leads to difficult processing. Generally, it is necessary to cooperate with polystyrene resin (PS) with good compatibility to improve the fluidity, so as to realize good forming processing performance. However, the polyphenyl ether resin and the polystyrene resin both contain a large number of rigid groups, so that the injection molding processing temperature is high. The thermal oxygen stability of the polyphenyl ether resin is poor, and the higher processing temperature is easy to cause rearrangement of the polyphenyl ether resin in the injection molding process, so as to cause irregular decrease of the melt fluidity and reduce the processing stability.

[0003] At present, the thermal oxygen stability of the polyphenyl ether resin is improved mainly by adding phosphite or thioester antioxidant, or using salicylic acid or salicylate to end-cap. However, with the progress of processing technology, more and more factories use hot runner to avoid flow loss. The processing temperature of this process is much higher than that of the traditional polyphenyl ether material, which leads to limited improvement effect of phosphite antioxidant, thioester antioxidant and other antioxidants on the thermal oxygen stability of the polyphenyl ether resin. Although the use of salicylic acid or salicylate end-capping can inhibit the rearrangement reaction to some extent to improve the processing stability, the gas barrier property of the end-capped polyphenyl ether resin composite material is low. SUMMARY

[0004] The purpose of the present application is to overcome the defects and deficiencies of the existing end-capped polyphenyl ether composite material with poor gas barrier property, and to provide a polyphenyl ether resin composition.

[0005] Another purpose of the present application is to provide a preparation method of the polyphenyl ether resin composition.

[0006] Still another purpose of the present application is to provide an application of the polyphenyl ether resin composition in preparing a polyphenyl ether composite material.

[0007] Another purpose of the present application is to provide a polyphenyl ether composite material.

[0008] The above purposes of the present application are achieved by the following technical solutions.

[0009] The present application protects a polyphenyl ether resin composition obtained by reacting polyphenyl ether and naphthoic acid compound in a melt;

[0010] The polyphenylene ether has a repeating unit with the following structure:

[0011] R1, R2, R3, R4 are independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, halogenated alkyl, hydroxyl or halogenated hydroxyl;

[0012] The naphthoic acid compound is at least one of naphthoic acid or hydroxynaphthoic acid.

[0013] The inventors have found that after the naphthoic acid compound and the polyphenylene ether are reacted in a melt state, the polyphenylene ether resin composition obtained can not only significantly improve the gas barrier property of the polyphenylene ether composite material, but also effectively reduce the oxidation activity of the side methyl groups in the polyphenylene ether resin, thereby avoiding the generation of back-biting effects during the melt processing process, reducing the tendency of rearrangement crosslinking reaction of the polyphenylene ether resin during the melt processing process, and further improving the high-temperature injection molding processing stability of the polyphenylene ether composite material. The inventors speculate that the reason may be that the naphthoic acid compound and the polyphenylene ether both form a quinone structure in a melt state, and then undergo DA diene addition, thereby achieving the end-capping of the naphthoic acid compound on the polyphenylene ether.

[0014] The primary lower alkyl group can be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, isopentyl, 2-methylbutyl, n-hexyl, 2,3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylheptyl, 3-methylheptyl or 4-methylheptyl; and the secondary lower alkyl group can be isopropyl, sec-butyl or 3-pentyl.

[0015] Optionally, the mass percentage of the naphthoic acid compound relative to the polyphenylene ether is 0.05% to 3.5%, preferably 0.5% to 2%; and specifically can be 0.1%, 0.15%, 0.2%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 2.75%, 3% or 3.3%.

[0016] Optionally, the intrinsic viscosity of the polyphenylene ether is 0.09 to 0.51 dL / g, preferably 0.37 to 0.41 dL / g; and specifically can be 0.1 dL / g, 0.15 dL / g, 0.2 dL / g, 0.25 dL / g, 0.3 dL / g, 0.35 dL / g, 0.4 dL / g, 0.45 dL / g or 0.5 dL / g.

[0017] The intrinsic viscosity of the polyphenylene ether can be measured by dissolving the polyphenylene ether in a chloroform solution at 25°C, and then using an Ubbelohde viscometer to measure the intrinsic viscosity of the polyphenylene ether.

[0018] Typically, the molecular structure of the polyphenylene ether comprises at least one end group as follows:

[0019] Optionally, the naphthoic acid is at least one of 1-naphthoic acid and / or 2-naphthoic acid; the hydroxynaphthoic acid is at least one of 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 6-hydroxy-2-naphthoic acid or 3,7-dihydroxy-2-naphthoic acid.

[0020] Preferably, R1 and R2 are C 1-4 alkyl (preferably methyl), and R3 and R4 are hydrogen.

[0021] The present application also protects a preparation method of the above-mentioned polyphenylene ether resin composition, comprising the following steps: mixing the polyphenylene ether resin with the naphthoic acid compound and then melt-extruding at 80-300°C to obtain the polyphenylene ether resin composition.

[0022] Preferably, the temperature of a zone of the melt-extruding extruder is 80-100°C, and the temperature of the second zone to the tenth zone is 250-300°C; the screw rotation speed of the melt-extruding extruder is 300-400 rpm, and the screw length-diameter ratio is 36-46:1.

[0023] The application of the above-mentioned polyphenylene ether resin composition in preparing a polyphenylene ether composite material is also within the protection scope of the present application.

[0024] The present application also protects a polyphenylene ether composite material, comprising the following components in parts by weight:

[0025] The above-mentioned polyphenylene ether resin composition is 50-93 parts, the antioxidant is 0-3 parts, and the PS resin is 2-32 parts.

[0026] Optionally, the antioxidant can be at least one of a phenolic antioxidant, a phosphorus antioxidant or a sulfur antioxidant; specifically, it can be Irganoc 1010, Irganox 1076, Irganox 3114, Irganox 245, STAB AO-80, STAB AO-30, Naugard 412S, Naugard 445, Revonox 510, Revonox 608, Irganox 168 or STAB PEP-36.

[0027] Optionally, the PS resin can be at least one of GPPS, MIPS or HIPS, and the melt mass flow rate thereof measured according to the ISO 1183-1:2019 standard (200°C, 5kg) is 0.5-30 g / 10min, preferably 1-12 g / min.

[0028] Optionally, the polyphenyl ether composite further comprises 1-12 parts by weight of a toughening agent and 7-18 parts by weight of a flame retardant.

[0029] Specifically, the toughening agent is one or more of ethylene-propylene rubber, nitrile rubber, butadiene rubber, ethylene-vinyl acetate copolymer, polyolefin elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, and styrene-ethylene / propylene-styrene block copolymer.

[0030] Specifically, the flame retardant is at least one of phosphate ester compound, phosphate salt, and phosphazene.

[0031] Optionally, the phosphate ester compound is at least one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triamyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, trimethylphenyl phosphate, triditolyl phosphate, methylphenyl diphenyl phosphate, dimethylphenyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, tetraphenyl (bisphenol-A) diphosphate, and tetraphenyl resorcinol diphosphate.

[0032] The phosphate salt is at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, melamine, melamine pyrophosphate, melamine orthophosphate, phosphoric acid amide, polyphosphoric acid melamine, polyphosphoric acid ammonium, and polyphosphoric acid amide.

[0033] The phosphazene compound is a straight-chain polyphosphazene, which is obtained by ring-opening polymerization of hexachlorocyclotriphosphazene to generate dichlorophosphazene, and then substituted by phenoxy and / or alkoxy groups.

[0034] Optionally, the polyphosphazene can be one of monocyanophenoxy pentaphenoxy cyclotriphosphazene, dicyanophenoxy tetraphenoxy cyclotriphosphazene, tricyanophenoxy triphenoxy cyclotriphosphazene, tetracyanophenoxy diphenyl cyclotriphosphazene, pentacyanophenoxy monophenoxy cyclotriphosphazene, monocyanophenoxy heptaphenoxy cyclotetraphosphazene, dicyanophenoxy hexaphenoxy cyclotetraphosphazene, tricyanophenoxy pentaphenoxy cyclotetraphosphazene, tetracyanophenoxy tetraphenoxy cyclotetraphosphazene, pentacyanophenoxy triphenoxy cyclotetraphosphazene, hexacyanophenoxy diphenyl cyclotetraphosphazene, and heptacyanophenoxy monophenoxy cyclotetraphosphazene.

[0035] Among the above phosphazene compounds, preferred are polyphenoxy phosphazene having phenoxy as a substituent and obtainable from a mixture of cyclic and straight-chain chlorophosphazene, phenoxy phosphazene having a 4,4 sulfone diphenyl group cross-linking structure, phenoxy phosphazene having a 2,2-(4, diphenyl) isopropylidene cross-linking structure, and polyphosphazene having both cyanophenoxy and phenoxy as substituents.

[0036] In addition, the polyphenylene ether composite material described above can further contain other additives such as plasticizers, release agents, dyes, pigments and other resins imparting other properties, as long as the effects of the present application are not impaired, and a person skilled in the art can make a routine selection according to actual needs.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] The polyphenylene ether resin composition of the present application not only can significantly improve the gas barrier property of the polyphenylene ether composite material, but also can effectively reduce the oxidative activity of the side methyl groups in the polyphenylene ether resin, avoid the generation of effects such as backbiting in the melt processing process, thereby reducing the tendency of rearrangement crosslinking reaction of the polyphenylene ether resin in the melt processing process, and further improving the high-temperature injection molding processing stability of the polyphenylene ether composite material. DETAILED DESCRIPTION

[0039] The present application will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present application in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present application are commercially available raw materials and reagents.

[0040] 1. Raw materials and reagents

[0041] (1) Polyphenylene ether

[0042] PPE-1, brand PPE LXR040, manufacturer Bluestar, intrinsic viscosity 0.39-0.41 dL / g;

[0043] PPE-2, brand PPE LXR045, manufacturer Bluestar, intrinsic viscosity 0.44-0.46 dL / g;

[0044] PPE-3, brand PPE LXR050, manufacturer Bluestar, intrinsic viscosity 0.50-0.51 dL / g;

[0045] PPE-4, brand SA9000, manufacturer Sabic, intrinsic viscosity 0.09-0.12 dL / g.

[0046] (2) Styrene-based resin (PS resin), brand PS 350s, commercially available;

[0047] (3) Toughening agent, brand SEBS 6151, commercially available;

[0048] (4) Flame retardant, polyphosphazene, brand SPB100, commercially available;

[0049] (5) 2-hydroxy-3-naphthoic acid, 2-naphthoic acid and salicylic acid are all commercially available;

[0050] (6) The antioxidant is compounded by antioxidant 1010 and antioxidant 168 at a mass ratio of 1:2, and both the antioxidant 1010 and the antioxidant 168 are commercially available.

[0051] 2. The polyphenylene ether resin composition can be prepared by the following preparation method:

[0052] The polyphenylene ether is mixed with the naphthoic acid compound, and then melt-extruded by a twin-screw extruder (the temperature of the twin-screw extruder from zone 1 to zone 10 is 80℃, 250℃, 250℃, 250℃, 250℃, 260℃, 270℃, 260℃, 290℃ and 270℃, respectively, the screw rotation speed is 400 rpm, and the screw length-diameter ratio is 40-1), to obtain the polyphenylene ether resin composition, as shown in Table 1.

[0053] Table 1 Polyphenylene ether resin compositions 1-9

[0054] 3. The polyphenylene ether composite material of each embodiment and the comparative example of the present application is prepared by the following preparation method:

[0055] The polyphenylene ether resin composition, the PS resin, the toughening agent, the flame retardant and the antioxidant are mixed, and then melt-extruded by a twin-screw extruder at 270-290℃, to obtain the polyphenylene ether composite material.

[0056] 4. Performance test

[0057] (1) The heat residence stability (300℃, 4min, 10min) is tested according to the standard ISO1133-1:2011, the melt is kept at 300℃ in the melt indexer for 4min and 10min respectively, then a 5kg weight is applied to extrude, and the melt index under the corresponding condition is measured. The heat residence stability is defined as the ratio of the melt index of the residence time of 10min to that of 4min (10min value / 4min value) x 100%, and the closer the heat residence stability is to 100%, the better the high-temperature injection molding processing stability of the polyphenylene ether composite material is.

[0058] (2) The oxygen permeability is tested according to ISO 15105-1:2007, the pressure is 101kPa, the temperature is 23℃, the sample thickness is 1mm, and the unit of the oxygen permeability is cm 3 / cm 2 .s.cmHg.

[0059] Examples 1-11 and Comparative Examples 1-2

[0060] The weight parts of each component in the polyphenylene ether composite material in Examples 1-11 and Comparative Examples 1-2 are shown in Table 2.

[0061] Table 2: Weight fraction of each component in polyphenylene ether composite material in Examples 1-11 and Comparative Examples 1-2

[0062] According to the data in Table 2, the thermal retention stability ratio of the polyphenylene ether composite material in Examples 1-11 is 96%-103.5%, indicating that the melt flow rate of the polyphenylene ether composite material changes little at 300℃ for 4min and 10min in the melt indexer; and the oxygen permeability of the polyphenylene ether composite material is less than or equal to 14.2cm 3 / cm 2 .s.cmHg, indicating that the polyphenylene ether composite material of the present application not only has good high-temperature injection molding processing stability, but also has excellent gas barrier properties.

[0063] The above examples of the present application are merely examples for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A polyphenylene ether resin composition, characterized by, obtained by reacting polyphenylene ether and naphthoic acid compound in melt; the polyphenylene ether has repeating units with the following structure: R1, R2, R3, R4 are independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, halogenated alkyl, hydroxyl or halogenated hydroxyl; the naphthoic acid compound is at least one of naphthoic acid or hydroxyl naphthoic acid.

2. The polyphenylene ether resin composition according to claim 1, wherein The mass percentage of the naphthoic acid compound relative to the polyphenylene ether is 0.05% to 3.5%.

3. The polyphenylene ether resin composition according to claim 2, wherein The mass percentage of the naphthoic acid compound relative to the polyphenylene ether is 0.5% to 2%.

4. The polyphenylene ether resin composition according to Claim 1, wherein The intrinsic viscosity of the polyphenylene ether is 0.09 to 0.51 dL / g.

5. The polyphenylene ether resin composition according to Claim 4, wherein The intrinsic viscosity of the polyphenylene ether is 0.37 to 0.41 dL / g.

6. The polyphenylene ether resin composition according to Claim 1, wherein The naphthoic acid is 1-naphthoic acid and / or 2-naphthoic acid; The hydroxyl naphthoic acid is at least one of 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, 6-hydroxy-2-naphthoic acid or 3,7-dihydroxy-2-naphthoic acid.

7. The polyphenylene ether resin composition according to Claim 1, wherein R1and R2are C 1-4 alkyl, and R3and R4are hydrogen.

8. A method for producing the polyphenylene ether resin composition according to any one of claims 1 to 7, characterized by, comprising the following steps: The polyphenylene ether is mixed with the naphthoic acid compound and then melt-extruded at 250 to 330°C to obtain the polyphenylene ether resin composition.

9. Use of the polyphenylene ether resin composition according to any one of claims 1 to 7 in the preparation of polyphenylene ether composite material.

10. A polyphenylene ether composite material characterized by comprising: by weight, comprising the following components: The polyphenylene ether resin composition according to any one of claims 1 to 7 is 50 to 93 parts, antioxidant is 0 to 3 parts, and PS resin is 2 to 32 parts.

11. The polyphenylene ether composite of claim 10, wherein by weight, further comprising the following components: toughening agent 1 to 12 parts, and flame retardant 7 to 18 parts 12. The polyphenylene ether composite of claim 11, wherein The toughening agent is one or more of ethylene-propylene rubber, nitrile rubber, cis-butadiene rubber, ethylene-vinyl acetate copolymer, polyolefin elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer or styrene-ethylene / propylene-styrene block copolymer.

13. The polyphenylene ether composite of claim 11, wherein The flame retardant is at least one of phosphate ester compound, phosphate or phosphine oxide.

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