CN116102871A - Polyphenyl ether composite material and preparation method and application thereof - Google Patents
Polyphenyl ether composite material and preparation method and application thereof Download PDFInfo
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- CN116102871A CN116102871A CN202211632611.9A CN202211632611A CN116102871A CN 116102871 A CN116102871 A CN 116102871A CN 202211632611 A CN202211632611 A CN 202211632611A CN 116102871 A CN116102871 A CN 116102871A
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- metal hypophosphite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a polyphenyl ether composite material, which comprises 50-80 parts of polyphenyl ether, 0-20 parts of flame retardant, and alkali metal hypophosphite and/or alkaline earth metal hypophosphite in parts by weight; wherein the content of the P element from the alkali metal hypophosphite and/or the alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material. The invention adopts alkali metal hypophosphite and/or alkaline earth metal hypophosphite with specific content to replace a part or all of common phosphite antioxidant, thioester antioxidant and hindered phenol antioxidant and amine antioxidant, and can obviously improve irregular reduction of melt index caused by rearrangement of polyphenyl ether in the high-temperature melting process, thereby improving high-temperature injection molding processing stability, improving processing injection molding appearance defects such as flow marks and the like. Especially when the flame retardant is polyphosphazene flame retardant, the effect is more remarkable.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyphenyl ether composite material, a preparation method and application thereof.
Background
Polyphenylene ether materials (PPE for short) have been widely used in the field of electric appliances because of their excellent insulating properties, flame retardant properties and heat resistance. In the practical use process, the viscosity of the pure PPE material is high, the processing difficulty is high, a certain amount of PS is generally required to be added to adjust the fluidity, but the addition of PS can reduce the flame retardant property of the material. Meanwhile, since PS and PPE are both rigid materials, the glass transition temperature of the PS and PPE is far higher than the room temperature, so that the processing temperature of the PPE material is about 300 ℃, and the appearance problem is easy to cause.
Meanwhile, in order to improve the flame retardant property of the material to V-0, the method adopted at present is mainly a compounding method of adding a halogen-free flame retardant or a halogen-free flame retardant and a flame retardant synergist. However, the addition of these flame retardants further reduces the stability of the polyphenylene ether material while improving the flame retardancy of the material, exacerbating the irregular decrease in flowability caused by rearrangement of the polyphenylene ether resin during high temperature melting.
Patent US6479572 effectively improves the processing stability of the material through an antioxidant IRganox 1076 and a phosphite antioxidant. Patent US4309335 improves the stability of the material during long-term use by introducing phosphites. Patent US4021468 improves the stability of the material during processing by introducing organic sulfides. However, with the progress of processing technology, more and more factories use hot runners to avoid runner losses, etc., which can result in processing temperatures far higher than those of conventional polyphenylene ether materials. However, under the high temperature condition, the traditional phosphite antioxidant, the traditional thioester antioxidant, the traditional hindered phenol antioxidant and the traditional amine antioxidant can not inhibit rearrangement reaction which is easy to occur in the high temperature processing process of the polyphenyl ether, so that the melt index in the flowing process of the melt in the injection processing process is irregularly reduced, and the processing injection appearance defects such as flow marks and the like are caused.
Disclosure of Invention
The invention aims to provide a polyphenyl ether composite material with good injection molding appearance, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the polyphenyl ether composite material comprises 50-80 parts of polyphenyl ether, 0-20 parts of flame retardant, and alkali metal hypophosphite and/or alkaline earth metal hypophosphite in parts by weight; wherein the content of the P element from the alkali metal hypophosphite and/or the alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material.
The alkali metal hypophosphite and/or alkaline earth metal hypophosphite is at least one selected from sodium hypophosphite and calcium hypophosphite.
Preferably, the elemental content of P from the alkali metal hypophosphite and/or alkaline earth metal hypophosphite is 1500-2000 ppm based on the total weight of the polyphenylene ether composite.
Among the polyphenylene ether resins, the commonly used flame retardant may be a phosphate-based flame retardant (e.g., bisphenol A bis (diphenyl phosphate), triphenyl phosphate, etc.), and preferably, the flame retardant is selected from polyphosphazene-based flame retardants. When flame-retardant modification is carried out on polyphenyl ether by adopting polyphosphazene flame retardant, melt fluidity change caused by rearrangement reaction in the high-temperature processing process of the polyphenyl ether is aggravated, but the improvement effect is more remarkable after alkali metal hypophosphite and/or alkaline earth metal hypophosphite are added compared with that of the flame-retardant-free polyphenyl ether.
Specifically, the polyphosphazene flame retardant is at least one selected from a cyclotriphosphazene compound, a cyclotetraphosphazene compound, a cyclophosphazene compound, a linear phosphazene compound; the cyclotriphosphazene compound is at least one of hexaphenoxy cyclotriphosphazene, monocyanophenoxy pentaphenoxy cyclotriphosphazene, dicyanophenoxy tetraphenoxy cyclotriphosphazene, tricyanophenoxy cyclotriphosphazene, tetracyanophenoxy diphenoxy cyclotriphosphazene and pentacyanophenoxy monophenoxy cyclotriphosphazene; the cyclotetraphosphazene compound is selected from monocyanophenoxy heptaphenoxy cyclotetraphosphazene, dicyanophenoxy hexaphenoxy cyclotetraphosphazene, tricyanophenoxy pentaphenoxy cyclotetraphosphazene, tetracyanophenoxy tetraphenoxy cyclotetraphosphazene, hexacyanophenoxy diphenoxy cyclotetraphosphazene and heptacyanophenoxy monophenoxy cyclotetraphosphazene; the linear phosphazene compound is selected from polydiphenoxy phosphazenes. The polyphenylene ether has an intrinsic viscosity of 0.3 to 0.6dl as measured by an intrinsic viscosity measuring method using an Ubbelohde viscometer in chloroform at 25 ℃.
The anti-oxidant also comprises 0-0.3 part by weight of an anti-oxidant, wherein the anti-oxidant is at least one selected from pentaerythritol ester anti-oxidant and phosphite ester anti-oxidant. The pentaerythritol ester antioxidant may be pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (Iragnox 1010), and the phosphite antioxidant is selected from phosphite esters (Iragnox 168).
The preparation method of the polyphenyl ether composite material comprises the following components: according to the proportion, the components are uniformly mixed, and extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 260-300 ℃ and the rotating speed range is 250-450 r/min, so as to obtain the polyphenyl ether composite material.
The application of the polyphenyl ether composite material is used for preparing the electronic equipment shell.
The alkali metal or alkaline earth metal hypophosphite is used for inhibiting the melt index change of the polyphenyl ether in the processing process at 280-325 ℃, and comprises 50-80 parts of polyphenyl ether, 0-20 parts of flame retardant and alkali metal or alkaline earth metal hypophosphite in parts by weight; wherein, the content of P element from alkali metal or alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material.
The invention has the following beneficial effects:
the invention adopts the alkali metal or alkaline earth metal hypophosphite with specific content (the content of P element from the alkali metal or alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material) to partially or completely replace the traditional phosphite antioxidant, thioester antioxidant and hindered phenol antioxidant and amine antioxidant, can obviously improve the irregular reduction of melt index caused by rearrangement of polyphenyl ether in the high-temperature melting process, and improves the high-temperature injection molding processing stability (high-temperature retention stability), thereby improving the processing injection molding appearance defects such as flow marks and the like. Especially when the flame retardant is polyphosphazene flame retardant, the effect is more remarkable.
Drawings
Fig. 1: the comparison graph of the flow mark defect on the surface of the injection-molded rear plate is free of flow marks, slight flow marks and obvious flow marks from left to right, and if the flow mark defect on the surface of the square plate is more serious than that of the plate 3, the flow mark defect is serious.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials are as follows:
polyphenylene ether: PPE LXR040 with an intrinsic viscosity of 0.4dl (25 ℃ C.);
flame retardant a: hexaphenoxy cyclotriphosphazene, SPB100, CAS:1184-10-7, otsuka pharmaceutical Co., ltd;
flame retardant B: polydiphenoxy phosphazene, CAS:28212-48-8, benji Kai science and technology Co., ltd;
flame retardant C: RDP, resorcinol bis (diphenyl phosphate): CAS:125997-21-9, wansheng science and technology Co., ltd;
flame retardant D: TPP, triphenyl phosphate: CAS:115-86-6, wansheng science and technology Co., ltd
Flame retardant E: bisphenol a bis (diphenyl phosphate), CAS:5945-33-5, wansheng science and technology Co., ltd;
sodium hypophosphite: CAS:10039-56-2, shanghai Ala Biochemical technologies Co., ltd;
calcium hypophosphite: CAS:7789-79-9, shanghai Ala Biochemical technology Co., ltd;
preparation method of polyphenylene ether composites of examples and comparative examples: according to the proportion, the components are uniformly mixed, and extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 260-300 ℃ and the rotating speed range is 250-450 r/min, so as to obtain the polyphenyl ether composite material.
The testing method comprises the following steps:
(1) Thermal retention stability (300 ℃,4min, 10 min) according to standard ISO1133-1:2011, the residence time of the melt in a melt finger instrument at 300 ℃ is 4min and 10min respectively, then a weight of 5kg is applied for extrusion, and the melt index under the corresponding conditions is measured. The difference between the melt indexes of the residence time of 10min and the melt index of 4min is preferably +0.1-2.5 g/10min (the numerical value of 10 min-4 min), and the melt index is preferably +0.5-1.5 g/10min from the aspect of injection molding quality.
(2) Appearance: the polyphenyl ether composite material is molded into a square plate with the thickness of 100 x 2mm, and whether appearance defects such as flow marks and the like exist on the surface or not is observed (shown in figure 1 of the specification).
Table 1: examples 1-6 polyphenylene ether composites each component content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Polyphenylene ether | 60 | 60 | 60 | 60 | 60 | 60 |
| Flame retardant A | 10 | |||||
| Flame retardant B | 10 | |||||
| Flame retardant C | 10 | |||||
| Flame retardant D | 10 | |||||
| Flame retardant E | 10 | |||||
| Sodium hypophosphite | 0.17 | 0.21 | 0.21 | 0.21 | 0.21 | 0.21 |
| P element content from alkali or alkaline earth hypophosphite | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 |
| Retention stability of heat retention, 4min, g/10min | 3.1 | 11.76 | 12.06 | 11.86 | 11.18 | 12.37 |
| Retention stability of heat retention, 10min, g/10min | 3.3 | 12.50 | 12.68 | 12.23 | 11.25 | 12.51 |
| Difference in heat retention stability, g/10min | +0.2 | +0.74 | +0.62 | +0.37 | +0.07 | +0.14 |
| Appearance of | Slight flow marks | No flow lines | No flow lines | Slight flow marks | Slight flow marks | Slight flow marks |
As is clear from examples 2-6 and comparative examples 3/4/5, polyphosphazene flame retardants are significantly affected by sodium hypophosphite than other phosphate flame retardants or no flame retardant is added.
Table 2: examples 7-13 polyphenylene ether composites each component content (parts by weight) and test results
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | |
| Polyphenylene ether | 60 | 60 | 80 | 60 | 60 | 60 | 60 |
| Flame retardant C | 10 | 5 | 10 | 10 | 10 | 10 | 10 |
| Sodium hypophosphite | 0.30 | 0.40 | 0.35 | 0.38 | 0.41 | 0.62 | |
| Calcium hypophosphite | 0.34 | ||||||
| P element content from alkali or alkaline earth hypophosphite | 1500 | 1500 | 1550 | 1750 | 1900 | 2000 | 3000 |
| Retention stability of heat retention, 4min, g/10min | 11.51 | 21.2 | 11.80 | 11.88 | 12.05 | 12.07 | 12.35 |
| Retention stability of heat retention, 10min, g/10min | 12.34 | 21.6 | 12.72 | 12.86 | 13.11 | 13.03 | 12.68 |
| Difference in heat retention stability, g/10min | +0.63 | +0.4 | +0.92 | +0.98 | +1.06 | +0.96 | +0.33 |
| Appearance of | No flow lines | No flow lines | No flow lines | No flow lines | No flow lines | No flow lines | Slight flow marks |
As is clear from examples 4/7/10-13, the content of P element derived from the alkali metal hypophosphite and/or the alkaline earth metal hypophosphite is preferably 1500 to 2000 ppm based on the total weight of the polyphenylene ether composite, and the inhibition of rearrangement of the polyphenylene ether is more remarkable and the appearance is also better.
Table 3: comparative example polyphenylene ether composite Each component content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Polyphenylene ether | 60 | 60 | 60 | 60 | 60 |
| Flame retardant A | 10 | 10 | 10 | - | - |
| Flame retardant D | 10 | ||||
| Sodium hypophosphite | 0.10 | 0.72 | - | - | - |
| P element content from alkali or alkaline earth hypophosphite | 500 | 3500 | - | - | - |
| Retention stability of heat retention, 4min, g/10min | 11.1 | 12.9 | 16.7 | 3.5 | 15.2 |
| Retention stability of heat retention, 10min, g/10min | 9.5 | 11.6 | 13.9 | 1.2 | 13.5 |
| Difference in heat retention stability, g/10min | -1.60 | -1.30 | -2.80 | -2.3 | -1.7 |
| Appearance of | Slight flow marks | Severe flow marks | Severe flow marks | Severe flow marks | Severe flow marks |
As is clear from comparative example 1, if the addition amount of sodium hypophosphite is too low, the inhibition effect on the rearrangement reaction of polyphenylene ether during the high temperature melting is not remarkable.
As is clear from comparative example 2, too high an amount of sodium hypophosphite is added, which is also liable to cause the occurrence of flow marks.
Claims (10)
1. The polyphenyl ether composite material is characterized by comprising 50-80 parts of polyphenyl ether, 0-20 parts of flame retardant, and alkali metal hypophosphite and/or alkaline earth metal hypophosphite in parts by weight; wherein the content of the P element from the alkali metal hypophosphite and/or the alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material.
2. The polyphenylene ether composite according to claim 1, wherein the alkali metal hypophosphite and/or alkaline earth metal hypophosphite is at least one selected from sodium hypophosphite and calcium hypophosphite.
3. The polyphenylene ether composite according to claim 1, wherein the elemental content of P from the alkali metal hypophosphite and/or alkaline earth metal hypophosphite is 1500 to 2000 ppm based on the total weight of the polyphenylene ether composite.
4. The polyphenylene ether composite according to claim 1, wherein the flame retardant is selected from polyphosphazene flame retardants.
5. The polyphenyl ether composite material according to claim 4, wherein the polyphosphazene flame retardant is at least one selected from the group consisting of a cyclotriphosphazene compound, a cyclotetraphosphazene compound, a cyclophosphazene compound and a linear phosphazene compound; the cyclotriphosphazene compound is at least one of hexaphenoxy cyclotriphosphazene, monocyanophenoxy pentaphenoxy cyclotriphosphazene, dicyanophenoxy tetraphenoxy cyclotriphosphazene, tricyanophenoxy cyclotriphosphazene, tetracyanophenoxy diphenoxy cyclotriphosphazene and pentacyanophenoxy monophenoxy cyclotriphosphazene; the cyclotetraphosphazene compound is at least one of monocyanophenoxy heptaphenoxy cyclotetraphosphazene, dicyanophenoxy hexaphenoxy cyclotetraphosphazene, tricyanophenoxy pentaphenoxy cyclotetraphosphazene, tetracyanophenoxy tetraphenoxy cyclotetraphosphazene, hexacyanophenoxy diphenoxy cyclotetraphosphazene and heptacyanophenoxy monophenoxy cyclotetraphosphazene; the linear phosphazene compound is selected from polydiphenoxy phosphazenes.
6. The polyphenylene ether composite according to claim 1, wherein the polyphenylene ether has an intrinsic viscosity of 0.3 to 0.6dl as measured by an intrinsic viscosity of a brookfield viscometer in chloroform at 25 ℃.
7. The polyphenyl ether composite material according to claim 1, further comprising 0-0.3 parts by weight of an antioxidant, wherein the antioxidant is at least one selected from pentaerythritol ester antioxidants and phosphite ester antioxidants.
8. The method for preparing the polyphenyl ether composite material as set forth in any one of claims 1 to 7, which is characterized by comprising the following components: according to the proportion, the components are uniformly mixed, and extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 260-300 ℃ and the rotating speed range is 250-450 r/min, so as to obtain the polyphenyl ether composite material.
9. Use of the polyphenylene ether composite according to any one of claims 1 to 7 for the preparation of an electronic device housing.
10. The alkali metal or alkaline earth metal hypophosphite is used for inhibiting the melt index change of the polyphenyl ether in the processing process at 280-325 ℃, and is characterized by comprising 50-80 parts of polyphenyl ether, 0-20 parts of flame retardant, alkali metal hypophosphite and/or alkaline earth metal hypophosphite in parts by weight; wherein the content of the P element from the alkali metal hypophosphite and/or the alkaline earth metal hypophosphite is 1000-3000ppm based on the total weight of the polyphenyl ether composite material.
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