CN109096731A - High glow-wire ignition temperature high intensity polyketone composite material and preparation method and application - Google Patents

High glow-wire ignition temperature high intensity polyketone composite material and preparation method and application Download PDF

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Publication number
CN109096731A
CN109096731A CN201810895897.7A CN201810895897A CN109096731A CN 109096731 A CN109096731 A CN 109096731A CN 201810895897 A CN201810895897 A CN 201810895897A CN 109096731 A CN109096731 A CN 109096731A
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ignition temperature
wire ignition
composite material
glow
preparation
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CN109096731B (en
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倪金平
聂帅
陈小鹏
叶耀挺
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Zhejiang Xinli New Material Co Ltd
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Zhejiang Xinli New Material Co Ltd
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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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of high glow-wire ignition temperature high intensity polyketone composite material and preparation method and the application in electronic component is being prepared, which is made of the material of following parts by weight: 40-80 parts of polyketone resin；15-30 parts of polyphenylene oxide (PPO)；15-25 parts of hydroxyapatite；ABS0.5-3 parts；0.1-1 parts of antioxidant；0.1-1 parts of lubricant.The material squeezes out preparation by twin-screw mixing, there is excellent mechanical performance using the material, take into account toughness of material and intensity, meet 750 DEG C of glow wire ignition temperature or more simultaneously, vertical combustion UL-94 V-0 grade, it is particularly suitable to be used to prepare electronic component suitable for electronic apparatus inner structural members.

Description

High glow-wire ignition temperature high intensity polyketone composite material and preparation method and application
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of high glow-wire ignition temperature high intensity polyketone is multiple Condensation material and preparation method thereof and preparing the application in electronic component.
Background technique
Polyketone (Polyketone, abbreviation POK) is by the linear polymer of carbon monoxide, polyolefin polymerization, is a kind of property The excellent engineering plastics of energy, such as high impact, wear-resisting, chemically-resistant solvent etc., can be used for industry, automobile and electronic apparatus Field.POK molecule is mainly made of hydrocarbon, and oxygen index (OI) is not high, and flame retardant property is poor, is limited it in high fire-retardance and is required field It uses.
Application publication number is that the Chinese invention patent application of CN107974076A (application No. is 201711161472.5) is public A kind of enhancing flame-proof PA 6/POK alloy material is opened, including by weight: 50-90 parts of nylon resin, polyketone resin 10-50 Part, 10-20 parts of fire retardant, 4-8 parts of fire retarding synergist, 3-6 parts of compatilizer, 20-35 parts of chopped strand, antioxidant 0.35-0.65, Lubricant 0.4-0.7.Wherein fire retardant uses decabromodiphenylethane, and synergist uses antimony oxide, and vertical combustion performance reaches To V-0 grade.
Application publication number is that CN107903567A (application No. is 201711154792.8) Chinese invention patent application discloses A kind of flame-proof ABS/POK alloy material and preparation method thereof, the material include that the group of mass parts is grouped as: ABS resin 30-65 Part, 10-45 parts of polyketone resin, 13-25 parts of fire retardant, 3-8 parts of fire retarding synergist, 2-5 parts of compatilizer, 0.3-1 parts of antioxidant, add 0.3-1 parts of work auxiliary agent.Fire retardant is decabromodiphenylethane, three (tribromophenoxy) triazines, brominated Polystyrene, brominated epoxy tree Rouge, antimony oxide and haloflex compound are synergist, meet flame retardant property 1.5mm V-0.
Application publication number is that the Chinese invention patent application of CN107227016A (application No. is 201710579384.0) is public A kind of fire-retardant polyketone resin of phosphate flame retardants, major design consisting of ingredient: phosphate flame retardants and polyketone resin are opened. Wherein, phosphate flame retardants: the mass fraction of melamine polyphosphate MPP and hypo-aluminum orthophosphate AHP are 10-20%, fire-retardant full Sufficient UL-94 V-0 rank.
Technical solution disclosed above can improve the flame retardant property of POK material by adding fire retardant, but be the failure to full Sufficient high fire-retardance requirement especially cannot require to use under environment in high glowing filament ignition temperature.Meanwhile the fire-retardant POK strength of materials is low, It cannot be used for supporter use.
Summary of the invention
The object of the invention is to it is high to provide a kind of high glow-wire ignition temperature in order to solve defect existing for above-mentioned technology Intensity polyketone composite material and preparation method and the application in electronic component is being prepared, which has excellent mechanicalness Can, toughness of material and intensity are taken into account, while meeting 750 DEG C of glow wire ignition temperature or more, vertical combustion UL-94 V-0 grade, Suitable for electronic apparatus inner structural members.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of high glow-wire ignition temperature high intensity polyketone composite material, is made of the material of following parts by weight:
The innovation of the invention consists in that using high strength polyphenylene sulfide material as POK reinforcing agent and fire retarding synergist, benefit It uses porous structure hydroxyapatite as enhancing packing material, while as glowing filament burning intensive, further promoting material Flame retardant property, the ABS of certain content is added, the mechanical property of composite material can be improved, make it have high intensity.The present invention In, polyketone (POK) resin, polyphenylene oxide (PPO), hydroxyapatite, ABS, antioxidant and the lubricant combination of certain content are one It rises, each component can interact, and mutually enhance, so that the composite material that the present invention obtains not only has excellent mechanicalness Can, toughness of material and intensity are taken into account, moreover, meet 750 DEG C of glow wire ignition temperature or more, vertical combustion UL-94 V-0 grade, Suitable for electronic apparatus inner structural members.
Further preferably, the high glow-wire ignition temperature high intensity polyketone composite material, by the material of following parts by weight Material composition:
Most preferably, the high glow-wire ignition temperature high intensity polyketone composite material, by the material group of following parts by weight At:
The high glow-wire ignition temperature high intensity polyketone composite material, glow wire ignition temperature can achieve 750 DEG C, and And mechanical property is very excellent.
Polyketone (POK) resin is the polymer of carbon monoxide and alkene, molecular weight 40000-100000.
The polyphenylene oxide (Polyphenylene Oxide, abbreviation PPO) is unmodified PPO powder.
The hydroxyapatite is porous structure, specific surface area 35-110m2/ g, hydroxyapatite pass through hexadecane Ammonium chloride processing.
The ABS is acrylonitrile-butadiene-styrene terpolymer, wherein acrylonitrile constituent content is in 45%- 65%.
The antioxidant be one or more of antioxidant 1098, antioxidant 1076, irgasfos 168 (including Two kinds).
The lubricant is one of stearate, polyethylene wax or two kinds, and the stearate is tristearin Sour sodium.
A kind of preparation method of high glow-wire ignition temperature high intensity polyketone composite material, comprising the following steps:
By polyketone (POK) resin, polyphenylene oxide (PPO), hydroxyapatite, ABS, antioxidant and mix lubricant, by double Screw mixes squeeze out tie rod, cooling, granulation, obtain high glow-wire ignition temperature high intensity polyketone composite material.
The condition of the twin-screw mixing are as follows: processing temperature is at 245-280 DEG C, and screw speed is in 30-40Hz.
The preparation method of the hydroxyapatite, specifically includes:
Ca(NO3)2Neopelex, polyethylene glycol are added in ethanol solution, 70 DEG C~90 DEG C are added with stirring P2O5Ethanol solution adjusts pH 8~9 with ammonium hydroxide, handles 3h~9h after placing 2~8 days at 700 DEG C~900 DEG C, obtain hydroxyl Apatite.
Ca (the NO3)2In ethanol solution, solvent is ethyl alcohol, Ca (NO3)2Concentration be 0.2mol/L~1mol/L, Further preferably 0.4mol/L~0.6mol/L, most preferably 0.5mol/L.
The P2O5In ethanol solution, solvent is ethyl alcohol, P2O5Concentration be 0.2mol/L~1mol/L, further it is excellent It is selected as 0.4mol/L~0.6mol/L, most preferably 0.5mol/L.
Ca (the NO3)2Ethanol solution, neopelex, polyethylene glycol, P2O5The dosage of ethanol solution it Than for 80~120mL:8~12g:8~12g:45~55mL, most preferably 100mL:10g:10g:50mL.
Further preferably, 75 DEG C~85 DEG C are added with stirring P2O5Ethanol solution is most preferably added with stirring at 80 DEG C P2O5Ethanol solution.
Further preferably, 5h~7h is handled after placing 4~6 days at 750 DEG C~850 DEG C, most preferably, 800 after placing 5 days 6h is handled at DEG C.
High glow-wire ignition temperature high intensity polyketone composite material of the present invention has high glowing filament ignition temperature, vertical combustion Reach V-0 grade, keeps that there is high intensity while material HI high impact, be suitable for high-intensitive, high fire-retardance and require product, it is especially suitable For fields such as electronic components.
Compared with prior art, the present invention has the advantage that
The innovation of the invention consists in that using high strength polyphenylene sulfide material as POK reinforcing agent and fire retarding synergist, benefit It uses porous structure hydroxyapatite as enhancing packing material, while as glowing filament burning intensive, further promoting material Flame retardant property.
The present invention promotes the intensity and flame retardant property of POK material using the high intensity of polyphenyl ether material and from anti-flammability；It adopts Enhance POK material with porous structure hydroxyapatite, while porous structure has heat-insulated, oxygen barrier, smoking effect, it is scorching hot to material Silk burning has improvement and promotes effect.
Specific embodiment
Below with reference to embodiment, the invention will be further described:
Examples 1 to 3 and comparative example 1~2
By POK (M330A, South Korea's Hyosung), PPO (646, husky uncle basis), ABS (727, Taiwan Qi Mei company), hydroxyl Twin-screw physics is passed through in base apatite, antioxidant (1098, BASF) and lubricant (odium stearate sends out base chemicals) mixing Extrusion tie rod, cooling, granulation obtain product, and twin-screw mixing squeezes out processing temperature at 245-280 DEG C, and screw speed is in 30- 40Hz。
The preparation method of hydroxyapatite: 100mL 0.5mol/LCa (NO3)2Ethanol solution [Ca (NO3)2Ethanol solution In, solvent is ethyl alcohol, Ca (NO3)2Concentration be 0.5mol/L] in be added 10g neopelex, 10g polyethylene glycol (PEG-400, molecular weight 380-420) is slowly added to 50mL P under 80 DEG C of stirrings2O5Ethanol solution (P2O5In ethanol solution, Solvent is ethyl alcohol, P2O5Concentration be 0.5mol/L), adjust pH 8.5 with ammonium hydroxide, handle 6h at 800 DEG C after placing 5 days, obtain Hydroxyapatite.
Embodiment 1-3 and comparative example 1-2 material mixture ratio are specifically shown in Table 1.
Table 1
Raw material Embodiment 1 Embodiment 2 Embodiment 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
Odium stearate 0.3 0.5 0.5 0.5 0.5
Antioxidant 1098 0.2 0.2 0.5 0.5 0.5
Gained pellet is molded into corresponding batten according to ISO testing standard, then in 23 ± 2 DEG C, 50 ± 5% relative humidity It places under environment and is tested afterwards for 24 hours, test that the results are shown in Table 2.
Table 2
Project Unit Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2
Tensile strength MPa 69 74 78 58 65
Bending strength MPa 88 93 103 82 75
Bending modulus MPa 3000 3800 4500 2800 2500
The impact of Charpy non-notch 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
POK material obtained by embodiment 1-3 has high glowing filament ignition temperature, and vertical combustion reaches V-0 grade, keeps material Expect that there is high intensity while HI high impact, be suitable for high-intensitive, high fire-retardance and require product, is particularly suitable for the neck such as electronic component Domain.
Comparative example 1
Comparative example 1 does not use PPO and ABS, and comparative example 1 enhances POK using hydroxyapatite, and flame retardant rating reaches V-1 Rank, Examples 1 to 3 introduces hydroxyapatite, ABS is compounded with PPO material, while playing enhancing to material, promotes material Glowing filament ignition temperature, vertical combustion reach V-0 grades.
Comparative example 2
Comparative example 2 does not use hydroxyapatite, and comparative example 2 enhances POK using PPO and ABS, using PPO flame retardant rating Reach V-1 and promote material stiffness, play PPO material from fire-retardant improvement Flame Retardancy energy, vertical combustion reaches V-1 rank, real While example 1~3 is applied using PPO, introduce porous hydroxyapatite, by barrier, at carbon the effects of, further promote material and burn Heated filament initiation temperature, vertical combustion reach V-0 grades.
As it can be seen that Examples 1 to 3 using polyketone (POK) resin of certain content, polyphenylene oxide (PPO), hydroxyapatite, Together with lubricant combination, each component can interact for ABS, antioxidant, mutually enhance so that the present invention obtain it is compound Material not only has excellent mechanical performance, takes into account toughness of material and intensity, moreover, meet 750 DEG C of glow wire ignition temperature with On, vertical combustion UL-94V-0 grade is suitable for electronic apparatus inner structural members.
It above are only specific embodiments of the present invention, but the design concept of the present invention is not limited to this, it is all to utilize this structure Think of makes a non-material change to the present invention, and should all belong to behavior that violates the scope of protection of the present invention.

Claims (10)

1. a kind of high glow-wire ignition temperature high intensity polyketone composite material, which is characterized in that by the material group of following parts by weight At:
2. high glow-wire ignition temperature high intensity polyketone composite material according to claim 1, which is characterized in that by following The material of parts by weight forms:
3. high glow-wire ignition temperature high intensity polyketone composite material according to claim 1, which is characterized in that by following The material of parts by weight forms:
4. the preparation side of described in any item high glow-wire ignition temperature high intensity polyketone composite materials according to claim 1~3 Method, which comprises the following steps:
By polyketone resin, polyphenylene oxide, hydroxyapatite, ABS, antioxidant and mix lubricant, mixes to squeeze out by twin-screw and draw Item, cooling, granulation obtain high glow-wire ignition temperature high intensity polyketone composite material.
5. the preparation method of high glow-wire ignition temperature high intensity polyketone composite material according to claim 4, feature It is, the condition of the twin-screw mixing are as follows: processing temperature is at 245-280 DEG C.
6. the preparation method of high glow-wire ignition temperature high intensity polyketone composite material according to claim 4, feature It is, the preparation method of the hydroxyapatite specifically includes:
Ca(NO3)2Neopelex, polyethylene glycol are added in ethanol solution, 70 DEG C~90 DEG C are added with stirring P2O5Second Alcoholic solution adjusts pH 8~9 with ammonium hydroxide, handles 3h~9h after placing 2~8 days at 700 DEG C~900 DEG C, obtain hydroxy-apatite Stone.
7. the preparation method of high glow-wire ignition temperature high intensity polyketone composite material according to claim 6, feature It is, the Ca (NO3)2In ethanol solution, solvent is ethyl alcohol, Ca (NO3)2Concentration be 0.2mol/L~1mol/L.
8. the preparation method of high glow-wire ignition temperature high intensity polyketone composite material according to claim 6, feature It is, the P2O5In ethanol solution, solvent is ethyl alcohol, P2O5Concentration be 0.2mol/L~1mol/L.
9. the preparation method of high glow-wire ignition temperature high intensity polyketone composite material according to claim 6, feature It is, the Ca (NO3)2Ethanol solution, neopelex, polyethylene glycol, P2O5The ratio between dosage of ethanol solution is 80~120mL:8~12g:8~12g:45~55mL.
10. described in any item high glow-wire ignition temperature high intensity polyketone composite materials are in preparation electricity according to claim 1~3 Application in subcomponent.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109825027A (en) * 2019-02-28 2019-05-31 威海联桥新材料科技股份有限公司 A kind of ABS/POK alloy exempts from sprayed on material and preparation method thereof
CN114276669A (en) * 2021-12-30 2022-04-05 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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CN114276669A (en) * 2021-12-30 2022-04-05 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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