CN109096731B - High glow wire ignition temperature and high strength polyketone composite material and preparation method and application thereof - Google Patents
High glow wire ignition temperature and high strength polyketone composite material and preparation method and application thereof Download PDFInfo
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- CN109096731B CN109096731B CN201810895897.7A CN201810895897A CN109096731B CN 109096731 B CN109096731 B CN 109096731B CN 201810895897 A CN201810895897 A CN 201810895897A CN 109096731 B CN109096731 B CN 109096731B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a high glow wire ignition temperature and high strength polyketone composite material, a preparation method thereof and application thereof in preparing electronic elements, wherein the material comprises the following materials in parts by weight: 40-80 parts of polyketone resin; 15-30 Parts of Polyphenylene Oxide (PPO); 15-25 parts of hydroxyapatite; 0.5-3 parts of ABS; 0.1-1 part of antioxidant; 0.1-1 part of lubricant. The material is prepared by mixing and extruding double screws, has excellent mechanical properties, gives consideration to the toughness and the strength of the material, meets the requirements of the glow wire ignition temperature of more than 750 ℃ and the vertical combustion UL-94V-0 grade, is suitable for internal structural parts of electronic appliances, and is particularly suitable for preparing electronic elements.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high glow wire ignition temperature and high strength polyketone composite material, a preparation method thereof and application thereof in preparing electronic elements.
Background
Polyketone (POK) is a linear polymer polymerized from carbon monoxide and polyolefin, is an engineering plastic with excellent properties, such as high impact strength, wear resistance, chemical solvent resistance and the like, and can be used in the fields of industry, automobiles and electronic and electrical appliances. The POK molecules are mainly composed of carbon and hydrogen, the oxygen index is low, the flame retardant property is poor, and the use of the POK molecules in the field with high flame retardant requirement is limited.
The Chinese invention patent application with the application publication number of CN107974076A (application number of 201711161472.5) discloses a reinforced flame-retardant PA6/POK alloy material, which comprises the following components in parts by weight: 50-90 parts of nylon resin, 10-50 parts of polyketone resin, 10-20 parts of flame retardant, 4-8 parts of flame retardant synergist, 3-6 parts of compatilizer, 20-35 parts of chopped fiber, 0.35-0.65 part of antioxidant and 0.4-0.7 part of lubricant. The fire retardant adopts decabromodiphenylethane, the synergist adopts antimony trioxide, and the vertical combustion performance reaches V-0 level.
The application publication number is CN107903567A (application number is 201711154792.8) Chinese invention patent application discloses a flame-retardant ABS/POK alloy material and a preparation method thereof, and the material comprises the following components in parts by mass: 30-65 parts of ABS resin, 10-45 parts of polyketone resin, 13-25 parts of flame retardant, 3-8 parts of flame retardant synergist, 2-5 parts of compatilizer, 0.3-1 part of antioxidant and 0.3-1 part of processing aid. The flame retardant is decabromodiphenylethane, tri (tribromophenoxy) triazine, brominated polystyrene, brominated epoxy resin, and a compound of antimony trioxide and chlorinated polyethylene as a synergist, and meets the flame retardant property of 1.5mm V-0.
The Chinese invention patent application with the application publication number of CN107227016A (application number of 201710579384.0) discloses a phosphate flame retardant polyketone resin, which mainly comprises the following components: phosphate flame retardants and polyketone resins. Wherein the phosphate flame retardant: the mass portion of the MPP and the AHP is 10-20%, and the flame retardance meets UL-94V-0 level.
According to the technical scheme, the flame retardant can be added to improve the flame retardant property of the POK material, but the POK material cannot meet the high flame retardant requirement, and particularly cannot be used in the environment with the requirement on the ignition temperature of a high glowing filament. Meanwhile, the flame-retardant POK material has low strength and cannot be used for a support member.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a high glow wire ignition temperature and high strength polyketone composite material, a preparation method thereof and application thereof in preparing electronic elements.
The purpose of the invention can be realized by the following technical scheme:
a high glow wire ignition temperature and high strength polyketone composite material comprises the following materials in parts by weight:
the invention has the innovation points that the high-strength polyphenylene sulfide material is used as a POK reinforcing agent and a flame-retardant synergist, the hydroxyapatite with a porous structure is used as a reinforcing filling material and is also used as a glow wire combustion reinforcing agent, the flame-retardant property of the material is further improved, and the mechanical property of the composite material can be improved by adding the ABS with a specific content, so that the composite material has high strength. In the invention, the Polyketone (POK) resin, the polyphenylene oxide (PPO), the hydroxyapatite, the ABS, the antioxidant and the lubricant with specific contents are combined together, and the components can interact and mutually reinforce, so that the composite material obtained by the invention not only has excellent mechanical properties, but also has material toughness and strength, and meets the requirements of the glow wire ignition temperature of more than 750 ℃ and the vertical combustion UL-94V-0 grade, and is suitable for internal structural components of electronic and electrical appliances.
Further preferably, the high glow wire ignition temperature and high strength polyketone composite material is composed of the following materials in parts by weight:
most preferably, the high glow wire ignition temperature and high strength polyketone composite material is composed of the following materials in parts by weight:
the high glow wire ignition temperature and high strength polyketone composite material has the glow wire ignition temperature of 750 ℃ and excellent mechanical properties.
The Polyketone (POK) resin is a polymer of carbon monoxide and olefin, and has a molecular weight of 40000-100000.
The Polyphenylene Oxide (PPO) is unmodified PPO powder.
The hydroxyapatite is of a porous structure, and the specific surface area is 35-110m2And/g, treating hydroxyapatite with hexadecyl ammonium chloride.
The ABS is acrylonitrile-butadiene-styrene terpolymer, wherein the content of an acrylonitrile component is 45-65%.
The antioxidant is one or more than two (including two) of antioxidant 1098, antioxidant 1076 and antioxidant 168.
The lubricant is one or two of stearate and polyethylene wax, and the stearate is sodium stearate.
A preparation method of a high glow wire ignition temperature and high strength polyketone composite material comprises the following steps:
mixing Polyketone (POK) resin, polyphenylene oxide (PPO), hydroxyapatite, ABS, an antioxidant and a lubricant, extruding and bracing by double screws, cooling and granulating to obtain the high glow wire ignition temperature and high strength polyketone composite material.
The conditions of the twin-screw mixing are as follows: the processing temperature is 245 ℃ and 280 ℃, and the screw rotating speed is 30-40 Hz.
The preparation method of the hydroxyapatite specifically comprises the following steps:
Ca(NO3)2adding sodium dodecyl benzene sulfonate and polyethylene glycol into the ethanol solution, adding P under stirring at 70-90 DEG C2O5Adjusting the pH of the ethanol solution to 8-9 by using ammonia water, standing for 2-8 days, and treating at 700-900 ℃ for 3-9 h to obtain hydroxyapatite.
The above-mentionedCa (NO) of3)2In the ethanol solution, the solvent is ethanol and Ca (NO)3)2The concentration of (B) is 0.2 to 1mol/L, more preferably 0.4 to 0.6mol/L, and most preferably 0.5 mol/L.
Said P2O5In the ethanol solution, the solvent is ethanol, P2O5The concentration of (B) is 0.2 to 1mol/L, more preferably 0.4 to 0.6mol/L, and most preferably 0.5 mol/L.
The Ca (NO) is3)2Ethanol solution, sodium dodecyl benzene sulfonate, polyethylene glycol and P2O5The dosage ratio of the ethanol solution is 80-120 mL: 8-12 g: 8-12 g: 45-55 mL, most preferably 100 mL: 10 g: 10 g: 50 mL.
More preferably, P is added with stirring at 75 to 85 DEG C2O5Ethanol solution, most preferably, P is added with stirring at 80 deg.C2O5Ethanol solution.
More preferably, the treatment is carried out for 4 to 6 days at 750 to 850 ℃ for 5 to 7 hours, and most preferably, the treatment is carried out for 5 days at 800 ℃ for 6 hours.
The high glow wire ignition temperature and high strength polyketone composite material has a high glow wire ignition temperature, achieves the V-0 grade of vertical combustion, maintains high impact of the material, has high strength, is suitable for products with high strength and high flame retardant requirements, and is particularly suitable for the fields of electronic elements and the like.
Compared with the prior art, the invention has the following advantages:
the novel point of the invention is that the high-strength polyphenylene sulfide material is used as POK reinforcing agent and flame-retardant synergist, the porous hydroxyapatite is used as reinforcing filling material, and simultaneously, the porous hydroxyapatite is used as glowing filament combustion enhancer, so that the flame-retardant property of the material is further improved.
According to the invention, the strength and the flame retardant property of the POK material are improved by utilizing the high strength and the self-flame retardant property of the polyphenyl ether material; the porous hydroxyapatite reinforced POK material has the functions of heat insulation, oxygen isolation and smoking, and has the effect of improving the burning of the glow wire.
Detailed Description
The invention will now be further illustrated by reference to the following examples:
examples 1 to 3 and comparative examples 1 to 2
POK (M330A, Xiaoxing, Korea), PPO (646, Saber base), ABS (727, Qimei company, Taiwan), hydroxyapatite, antioxidant (1098, basf) and lubricant (sodium stearate, hair base chemical) are mixed, and subjected to double-screw physical extrusion drawing, cooling and granulation to obtain the product, wherein the double-screw mixing extrusion processing temperature is 245-.
The preparation method of the hydroxyapatite comprises the following steps: 100mL of 0.5mol/LCa (NO)3)2Ethanol solution [ Ca (NO)3)2In the ethanol solution, the solvent is ethanol and Ca (NO)3)2Has a concentration of 0.5mol/L]Adding 10g sodium dodecyl benzene sulfonate and 10g polyethylene glycol (PEG-400, molecular weight 380-2O5Ethanol solution (P)2O5In the ethanol solution, the solvent is ethanol, P2O5The concentration of (2) is 0.5mol/L), ammonia water is used for adjusting the pH value to 8.5, the mixture is placed for 5 days and then treated for 6 hours at 800 ℃, and hydroxyapatite is obtained.
The material proportions of examples 1 to 3 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
| Raw materials | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| POK | 65 | 55 | 55 | 70 | 75 |
| PPO | 15 | 25 | 30 | 0 | 30 |
| ABS | 1 | 1 | 2 | 0 | 2 |
| Hydroxyapatite | 15 | 20 | 25 | 25 | 0 |
| Sodium stearate | 0.3 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant 1098 | 0.2 | 0.2 | 0.5 | 0.5 | 0.5 |
The pellets were injection molded into corresponding test specimens according to ISO test standards, and then tested after being left for 24 hours in an environment of 23. + -. 2 ℃ and 50. + -. 5% relative humidity, with the results shown in Table 2.
TABLE 2
| Item | Unit of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Tensile strength | MPa | 69 | 74 | 78 | 58 | 65 |
| Bending strength | MPa | 88 | 93 | 103 | 82 | 75 |
| Flexural modulus | MPa | 3000 | 3800 | 4500 | 2800 | 2500 |
| Charpy unnotched impact | kJ/m2 | 120 | 115 | 105 | 145 | 150 |
| Glow wire ignition temperature | ℃ | 650 | 700 | 750 | 500 | 500 |
| Vertical combustion | Class | V-0 | V-0 | V-0 | V-1 | V-1 |
The POK materials obtained in the embodiments 1-3 have high glowing filament ignition temperature, vertical combustion reaches V-0 grade, high impact of the materials is kept, and meanwhile, the POK materials have high strength, are suitable for products with high strength and high flame retardant requirements, and are particularly suitable for the fields of electronic elements and the like.
Comparative example 1
The PPO and the ABS are not adopted in the comparative example 1, the POK is enhanced by adopting the hydroxyapatite in the comparative example 1, the flame retardant grade reaches V-1 grade, and the hydroxyapatite, the ABS and the PPO are introduced in the examples 1-3 for compounding, so that the glowing filament ignition temperature of the material is increased while the material is enhanced, and the vertical combustion reaches V-0 grade.
Comparative example 2
Comparative example 2 does not adopt hydroxyapatite, comparative example 2 adopts PPO and ABS to strengthen POK, PPO flame-retardant grade is adopted to reach V-1 to improve the rigidity of the material, the PPO material is given play to the self-flame-retardant property of the material, the vertical combustion reaches V-1 grade, in examples 1-3, PPO is adopted, porous hydroxyapatite is introduced, the glow wire ignition temperature of the material is further improved through the effects of blocking, carbon formation and the like, and the vertical combustion reaches V-0 grade.
It can be seen that in the embodiments 1-3, Polyketone (POK) resin, polyphenylene oxide (PPO), hydroxyapatite, ABS, an antioxidant and a lubricant with specific contents are combined together, and the components can interact and mutually reinforce, so that the composite material obtained by the invention not only has excellent mechanical properties, but also has material toughness and strength, and meets the requirements of the glow wire ignition temperature of more than 750 ℃ and the vertical combustion UL-94V-0 grade, and is suitable for internal structural components of electronic and electrical appliances.
The above description is only an embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any insubstantial modifications made by using the design concept should fall within the scope of infringing the present invention.
Claims (4)
1. The preparation method of the high glow wire ignition temperature and high strength polyketone composite material is characterized in that the high glow wire ignition temperature and high strength polyketone composite material is prepared from the following materials in parts by weight:
55-65 parts of polyketone resin;
15-30 parts of polyphenyl ether;
15-25 parts of hydroxyapatite;
1-2 parts of ABS;
0.2-0.5 part of antioxidant;
0.3-0.8 part of lubricant;
the polyketone POK resin is a polymer of carbon monoxide and olefin, and has a molecular weight of 40000-100000;
the method comprises the following steps:
mixing polyketone resin, polyphenyl ether, hydroxyapatite, ABS, an antioxidant and a lubricant, extruding and bracing by double screws, cooling and granulating to obtain the high glow wire ignition temperature and high strength polyketone composite material;
the preparation method of the hydroxyapatite specifically comprises the following steps:
Ca(NO3)2adding sodium dodecyl benzene sulfonate and polyethylene glycol into an ethanol solution, and adding P under stirring at 70-90 DEG C2O5Adjusting the pH of the ethanol solution to 8-9 by using ammonia water, standing for 2-8 days, and treating at 700-900 ℃ for 3-9 h to obtain hydroxyapatite;
the Ca (NO) is3)2In the ethanol solution, the solvent is ethanol and Ca (NO)3)2The concentration of (a) is 0.2-1 mol/L;
said P2O5In the ethanol solution, the solvent is ethanol, P2O5The concentration of (a) is 0.2-1 mol/L;
the Ca (NO) is3)2Ethanol solution, sodium dodecyl benzene sulfonate, polyethylene glycol and P2O5The dosage ratio of the ethanol solution is 80-120 mL: 8-12 g: 8-12 g: 45-55 mL.
2. The method for preparing the high glow wire ignition temperature and high strength polyketone composite material according to claim 1, wherein the conditions of the twin-screw mixing are as follows: the processing temperature is 245-280 ℃.
3. The method for preparing a high glow-wire ignition temperature and high strength polyketone composite material according to claim 1, wherein the high glow-wire ignition temperature and high strength polyketone composite material is prepared from the following materials in parts by weight:
55 parts of polyketone resin;
30 parts of polyphenyl ether;
25 parts of hydroxyapatite;
2 parts of ABS;
0.5 part of antioxidant;
0.5 part of lubricant.
4. Use of a high glow-wire ignition temperature and high strength polyketone composite prepared by the preparation method according to any one of claims 1 to 3 in the preparation of electronic components.
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| CN114276669B (en) * | 2021-12-30 | 2023-06-06 | 黄河三角洲京博化工研究院有限公司 | Polyketone resin composite material and preparation method thereof |
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| CN103160108A (en) * | 2011-12-09 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same |
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| DE2457148C3 (en) * | 1973-12-04 | 1979-01-11 | Mitsubishi Rayon Co. Ltd., Tokio | Flameproof resin masses |
| CN1093730C (en) * | 1998-06-23 | 2002-10-30 | 北京化工大学 | Heat-resistant fire-retardant plane-shaped exothermic body and producing method therefor |
| JP2017521533A (en) * | 2014-07-18 | 2017-08-03 | ヒョスン コーポレーション | Polyketone resin composition with excellent oil resistance |
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| CN103160108A (en) * | 2011-12-09 | 2013-06-19 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant polyphenylene oxide/polyamide 6 blend alloy as well as preparation and application for same |
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| 溶胶-凝胶法制备羟基磷灰石粉体化学机理分析;魏佳等;《哈尔滨理工大学材料科学与工程学院学报》;20080228;第13卷(第1期);66-69页 * |
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