CN106589770A - Anti-aging high-flame-retardant automobile instrument socket and preparation method thereof - Google Patents

Anti-aging high-flame-retardant automobile instrument socket and preparation method thereof Download PDF

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Publication number
CN106589770A
CN106589770A CN201611113740.1A CN201611113740A CN106589770A CN 106589770 A CN106589770 A CN 106589770A CN 201611113740 A CN201611113740 A CN 201611113740A CN 106589770 A CN106589770 A CN 106589770A
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parts
composite flame
retardant
retardant agent
flame
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CN201611113740.1A
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金涵声
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Priority to CN201611113740.1A priority Critical patent/CN106589770A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to an anti-aging high-flame-retardant automobile instrument socket and a preparation method thereof. The automobile instrument socket is obtained by carrying out molding and demolding after adding anti-aging high-flame-retardant ABS composite particles into an injection molding machine, the anti-aging high-flame-retardant ABS composite particles are prepared by processing the following raw materials in parts by weight: 80-100 parts of ABS resin, 40-60 parts of PC resin, 5-15 parts of EPDM resin, 6-10 parts of an antioxidant and 8-12 parts of a composite flame retardant, and the composite flame retardant is an ammonium polyphosphate-diatomite/magnetic ordered mesoporous nickel ferrite composite flame retardant prepared by in-situ polymerization. The ammonium polyphosphate-diatomite/magnetic ordered mesoporous nickel ferrite composite flame retardant prepared by in-situ polymerization by taking phosphoric acid and urea as main raw materials and taking diatomite and magnetic ordered mesoporous nickel ferrite as carriers can sufficiently take the synergistic flame-retardant effect of ammonium polyphosphate as well as silicon, ferrum and nickel elements to ensure that an ABS composite has good flame-retardant property; and the ammonium polyphosphate-diatomite/magnetic ordered mesoporous nickel ferrite composite flame retardant can be processed into parts with various shapes by using an injection molding process and is long in service life and good in safety.

Description

Anti-aging high fire-retardance automobile instrument socket and preparation method thereof
Technical field
The present invention relates to a kind of anti-aging high fire-retardance automobile instrument socket and preparation method thereof.
Background technology
ABS resin(Acrylonitrile-butadiene-styrene copolymer)It is a kind of intensity height, good toughness, easily processed into type Thermoplastics type's Polymer Materials ' Structure.
ABS is the general thermoplastic engineering plastic for growing up 1940's, be a comprehensive mechanical property very Outstanding plastics variety, not only with good rigid, hardness and processing fluidity, and with high tenacity feature, can note Modeling, extrusion or thermoforming.
Most of automobile component is processed with injection molding forming method, the advantage of ABS resin be impact resilience, sound-proofing, Scratch-resistant, heat resistance is more preferably, more attractive than PP, is particularly well-suited to horizontal impact resilience and using the more strict part of temperature. ABS resin is that polyurethane and polyacrylic the third-largest resin are only second to used in automobile.ABS resin can be used for outside in-car and car Shell, the widget such as steering wheel, oil guide pipe and handle and button, car outside includes front radiator grille and lampshade etc., current ABS resin fire resistance and anti ageing property be not good, present invention seek to address that this technical problem, and then it is processed into vapour Car meter socket.
The content of the invention
It is an object of the invention to solve the deficiencies in the prior art, there is provided a kind of anti-aging high fire-retardance automobile instrument socket its Preparation method.
The technical solution adopted for the present invention to solve the technical problems is:
Anti-aging high fire-retardance automobile instrument socket, the automobile instrument socket is added by anti-aging high fire-retardance ABS composite material particle Enter to injection machine back warp shaping, the demoulding obtain, the anti-aging high fire-retardance ABS composite material particle by following weight portion raw material Process:ABS resin 80-100 parts, PC resin 40-60 part, EPDM resin 5-15 parts, antioxidant 6-10 parts, composite flame-proof Agent 8-12 parts, the composite flame-retardant agent is that APP-order mesoporous nickel ferrite based magnetic loaded of diatomite/magnetic prepared by in-situ polymerization is combined Fire retardant, the preparation method of composite flame-retardant agent is specific as follows:85% SPA is poured in reactor, heating stirring, temperature is raised to 60-80 DEG C adds appropriate urea, when temperature is raised to 120-125 DEG C, adds appropriate diatomite and the order mesoporous nickel ferrite based magnetic loaded of magnetic Powder, the min of stirring reaction 10 ~ 20, then solidifies 1-2h by product at 280-320 DEG C, must answer Jing after nano grinder is crushed Close fire retardant.
Preferably, the anti-aging high fire-retardance ABS composite material particle is formed by the Raw material processing of following weight portion:ABS 90 parts of resin, 50 parts of PC resin, 8 parts of EPDM resins, 8 parts of antioxidant, 8 parts of composite flame-retardant agent, the preparation side of composite flame-retardant agent Method is specific as follows:The SPA of 85% concentration is poured in reactor, heating stirring, temperature is raised to 70 DEG C and adds appropriate urea, when When temperature is raised to 122 DEG C, appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, stirring reaction 15min is added then will Product solidifies 1.5h at 300 DEG C, and Jing after nano grinder is crushed composite flame-retardant agent is obtained.
Preferably, phosphoric acid:Urea:Diatomite:The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is:1:(0.6~0.7):(0.2 ~0.3):(0.1-0.2).
Preferably, the antioxidant is pentaerythrite four (3- lauryl thiopropionates) and/or four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, the antioxidant is pentaerythrite four (3- lauryl thiopropionates) and four [β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester in mass ratio 1:The mixture of 2-3.
The preparation method of anti-aging high fire-retardance automobile instrument socket of the present invention is specific as follows:
(1)The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic prepared by in-situ polymerization:By 85% SPA In pouring reactor into, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds Appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20, then by product at 280-320 DEG C Solidification 1-2h, Jing after nano grinder is crushed composite flame-retardant agent is obtained;
(2)ABS resin, PC resin, EPDM resins, antioxidant and composite flame-retardant agent are well mixed, Jing melting mixings, are extruded Granulation is obtained;
(3)Step (2) gained particle is added in injection machine, shaping, the demoulding are obtained final product.
The preparation method of the order mesoporous nickel ferrite based magnetic loaded of magnetic that the present invention is used is as follows:
1)By Ni (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in methyl alcohol, appropriate porous silicon KIT-6 is put into and is filled In the polytetrafluoroethylcontainer container of n-hexane, it is sufficiently stirred for;
2)By solution 1)Raw material be added dropwise over step 2)In, the mixed solution for being formed is sufficiently stirred for, in 70-80 DEG C of heating 5-8h;
3)Step 2) gained solid calcination 1-2 h at 300-320 DEG C;
4)By step 3)Gained solid is cooled to room temperature, polished to be transferred in the round-bottomed flask for filling NaOH solution, in 30- It is refluxed centrifugation after 8-12h under 40 DEG C of water bath conditions to reclaim;
5)By step 4)Gained solid is cleaned to neutrality respectively repeatedly with ethanol and deionized water, vacuum dried.
The invention has the beneficial effects as follows:
(1)Improve the anti-flammability of ABS composite material
With phosphoric acid and urea as primary raw material, with diatomite and the order mesoporous nickel ferrite based magnetic loaded of magnetic as carrier, by in-situ polymerization system The standby order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic, can give full play to APP and element silicon and Cooperative flame retardant effect between iron, nickel element, makes ABS composite material have good fire resistance, it is possible to additionally incorporate appropriate antioxygen Agent, loaded body adsorption storage can continue slowly to discharge active ingredient, extend the service life of ABS composite material.
(2)Reduces cost, reduces the impact to ABS composite material performance
Due to the high fire-retardance smoke-suppressing of the order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic, in resin Addition is appropriate, so affecting little to the physical strength of ABS composite material, is conducive to keeping preferable ABS resin physical strength Performance, while also can reduces cost.
The anti-aging high fire-retardance ABS plastic of the present invention has preferable anti-flammability, can be processed into Shooting Technique various The part of shape, can be used to make in automobile and the widget such as car outer enclosure, steering wheel and handle and button, using the longevity Life length, security is good.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.
Raw materials used in the embodiment of the present invention is commercial convenient source.
Embodiment 1:
Anti-aging high fire-retardance automobile instrument socket, the automobile instrument socket is added by anti-aging high fire-retardance ABS composite material particle Enter to injection machine back warp shaping, the demoulding obtain, the anti-aging high fire-retardance ABS composite material particle by following weight portion raw material Process:80 parts of ABS resin, 40 parts of PC resin, 5 parts of EPDM resins, 6 parts of antioxidant, 8 parts of composite flame-retardant agent is described multiple Close the order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic that fire retardant is prepared by in-situ polymerization, composite flame-proof The preparation method of agent is specific as follows:85% SPA is poured in reactor, heating stirring, temperature is raised to 60 DEG C and adds appropriate urine Element, when temperature is raised to 125 DEG C, adds appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10, Then product is solidified into 2h at 280 DEG C, Jing after nano grinder is crushed composite flame-retardant agent, phosphoric acid is obtained:Urea:Diatomite:Magnetic The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of property is:1:0.6:0.2:0.1, the antioxidant is (the 3- lauryl sulphur of pentaerythrite four For propionic ester);
The preparation method of anti-aging high fire-retardance automobile instrument socket of the present invention is specific as follows:By ABS resin, PC resin, EPDM resins, antioxidant and composite flame-retardant agent are well mixed, Jing melting mixings, and gained particle is added to note by extruding pelletization In molding machine, shaping, the demoulding are obtained final product.
Embodiment 2:
Anti-aging high fire-retardance automobile instrument socket, the automobile instrument socket is added by anti-aging high fire-retardance ABS composite material particle Enter to injection machine back warp shaping, the demoulding obtain, the anti-aging high fire-retardance ABS composite material particle by following weight portion raw material Process:100 parts of ABS resin, 60 parts of PC resin, 15 parts of EPDM resins, 10 parts of antioxidant, 12 parts of composite flame-retardant agent, institute The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic that composite flame-retardant agent is prepared by in-situ polymerization is stated, is combined The preparation method of fire retardant is specific as follows:85% SPA is poured in reactor, heating stirring, it is suitable that temperature is raised to 80 DEG C of additions Amount urea, when temperature is raised to 120 DEG C, adds appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, stirring reaction 20 Min, then solidifies 1h by product at 320 DEG C, and Jing after nano grinder is crushed composite flame-retardant agent, phosphoric acid are obtained:Urea:Diatom Soil:The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is:1:0.7:0.3:0.2, the antioxidant is four [β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester;
The preparation method of anti-aging high fire-retardance automobile instrument socket of the present invention is specific as follows:By ABS resin, PC resin, EPDM resins, antioxidant and composite flame-retardant agent are well mixed, Jing melting mixings, and gained particle is added to note by extruding pelletization In molding machine, shaping, the demoulding are obtained final product.
Embodiment 3:
Anti-aging high fire-retardance automobile instrument socket, the automobile instrument socket is added by anti-aging high fire-retardance ABS composite material particle Enter to injection machine back warp shaping, the demoulding obtain, the anti-aging high fire-retardance ABS composite material particle by following weight portion raw material Process:90 parts of ABS resin, 50 parts of PC resin, 8 parts of EPDM resins, 8 parts of antioxidant, 8 parts of composite flame-retardant agent is described multiple Close the order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic that fire retardant is prepared by in-situ polymerization, composite flame-proof The preparation method of agent is specific as follows:85% SPA is poured in reactor, heating stirring, temperature is raised to 70 DEG C and adds appropriate urine Element, when temperature is raised to 122 DEG C, adds appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 15, Then product is solidified into 1.5h at 300 DEG C, Jing after nano grinder is crushed composite flame-retardant agent, phosphoric acid is obtained:Urea:Diatomite: The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is:1:0.65:0.25:0.15, the antioxidant is four [β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters Mass ratio 1:2 mixture;
The preparation method of anti-aging high fire-retardance automobile instrument socket of the present invention is specific as follows:By ABS resin, PC resin, EPDM resins, antioxidant and composite flame-retardant agent are well mixed, Jing melting mixings, and gained particle is added to note by extruding pelletization In molding machine, shaping, the demoulding are obtained final product.
Comparative example
90 parts of ABS resin, 50 parts of PC resin, 8 parts of EPDM resins, ABS resin, PC resin, EPDM mixed with resin is uniform, and Jing melts Melt mixing, extruding pelletization is added to gained particle in injection machine, shaping, the demoulding are obtained final product.
Test case
The thick prints of 1.6mm are cut to the automobile instrument socket of embodiment 1-3, anti-flammability test is carried out, fire resistance is specifically counted According to being shown in Table 1.
In sum, the present invention can significantly improve the anti-flammability of ABS composite material:With phosphoric acid and urea as main former Material, with diatomite and the order mesoporous nickel ferrite based magnetic loaded of magnetic as carrier, the APP-diatomite/magnetic prepared by in-situ polymerization Order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent, can give full play to the cooperative flame retardant between APP and element silicon and iron, nickel element Effect, makes ABS composite material have good fire resistance.
Embodiment described above is one kind preferably scheme of the present invention, not makees any pro forma to the present invention Limit, also have other variants and remodeling on the premise of without departing from the technical scheme described in claim.

Claims (6)

1. anti-aging high fire-retardance automobile instrument socket, it is characterised in that:The automobile instrument socket is answered by anti-aging high fire-retardance ABS Condensation material particle is added to the shaping of injection machine back warp, the demoulding and obtains, and the anti-aging high fire-retardance ABS composite material particle is by following The Raw material processing of weight portion is formed:ABS resin 80-100 parts, PC resin 40-60 part, EPDM resin 5-15 parts, antioxidant 6- 10 parts, composite flame-retardant agent 8-12 parts, the composite flame-retardant agent is that APP-diatomite/magnetic prepared by in-situ polymerization is orderly Mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent, the preparation method of composite flame-retardant agent is specific as follows:85% SPA is poured in reactor, plus Thermal agitation, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds appropriate diatomite and magnetic Then product is solidified 1-2h, Jing nanometers by the order mesoporous ferrous acid nickel by powder of property, the min of stirring reaction 10 ~ 20 at 280-320 DEG C Pulverizer obtains composite flame-retardant agent after crushing.
2. anti-aging high fire-retardance automobile instrument socket according to claim 1, it is characterised in that:The anti-aging high fire-retardance ABS composite material particle is formed by the Raw material processing of following weight portion:90 parts of ABS resin, 50 parts of PC resin, 8 parts of EPDM resins, 8 parts of antioxidant, 8 parts of composite flame-retardant agent, the preparation method of composite flame-retardant agent is specific as follows:The SPA of 85% concentration is poured into In reactor, heating stirring, temperature is raised to 70 DEG C and adds appropriate urea, when temperature is raised to 122 DEG C, adds appropriate diatomite With the order mesoporous ferrous acid nickel by powder of magnetic, stirring reaction 15min, then product is solidified into 1.5h, Jing nanometer pulverizations at 300 DEG C Machine obtains composite flame-retardant agent after crushing.
3. anti-aging high fire-retardance automobile instrument socket according to claim 1 and 2, it is characterised in that:Phosphoric acid:Urea:Silicon Diatomaceous earth:The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is:1:(0.6~0.7):(0.2~0.3):(0.1-0.2).
4. anti-aging high fire-retardance automobile instrument socket according to claim 1 and 2, it is characterised in that:The antioxidant For pentaerythrite four (3- lauryl thiopropionates) and/or four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta Four alcohol esters.
5. anti-aging high fire-retardance automobile instrument socket according to claim 4, it is characterised in that:The antioxidant is season Penta tetrol four (3- lauryl thiopropionates) and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters are pressed Mass ratio 1:The mixture of 2-3.
6. the preparation method of the anti-aging high fire-retardance automobile instrument socket described in a kind of claim 1-5 any one, its feature It is:The preparation method is specific as follows:
(1)The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic prepared by in-situ polymerization:By 85% SPA In pouring reactor into, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds Appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20, then by product at 280-320 DEG C Solidification 1-2h, Jing after nano grinder is crushed composite flame-retardant agent is obtained;
(2)ABS resin, PC resin, EPDM resins, antioxidant and composite flame-retardant agent are well mixed, Jing melting mixings, are extruded Granulation;
(3)Step (2) gained particle is added in injection machine, shaping, the demoulding are obtained final product.
CN201611113740.1A 2016-12-07 2016-12-07 Anti-aging high-flame-retardant automobile instrument socket and preparation method thereof Pending CN106589770A (en)

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Application Number Priority Date Filing Date Title
CN201611113740.1A CN106589770A (en) 2016-12-07 2016-12-07 Anti-aging high-flame-retardant automobile instrument socket and preparation method thereof

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102389837A (en) * 2011-09-23 2012-03-28 常州大学 Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof
US20130079443A1 (en) * 2011-09-28 2013-03-28 Bayer Intellectual Property Gmbh Flame-retardant pc/abs compositions having good impact strength, flowability and chemical resistance
CN103073862A (en) * 2013-01-10 2013-05-01 苏州安鸿泰新材料有限公司 Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof
CN103937144A (en) * 2014-04-30 2014-07-23 山东瀚氏汽车零部件有限公司 ABS (acrylonitrile-butadiene-styrene) plastic for automobile inner ornaments and preparation method thereof
CN105754436A (en) * 2016-04-24 2016-07-13 龙泉市嘉文木业有限公司 Water and mildew resistant paint for wooden wireless loudspeaker tea set box and preparing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102389837A (en) * 2011-09-23 2012-03-28 常州大学 Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof
US20130079443A1 (en) * 2011-09-28 2013-03-28 Bayer Intellectual Property Gmbh Flame-retardant pc/abs compositions having good impact strength, flowability and chemical resistance
CN103073862A (en) * 2013-01-10 2013-05-01 苏州安鸿泰新材料有限公司 Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof
CN103937144A (en) * 2014-04-30 2014-07-23 山东瀚氏汽车零部件有限公司 ABS (acrylonitrile-butadiene-styrene) plastic for automobile inner ornaments and preparation method thereof
CN105754436A (en) * 2016-04-24 2016-07-13 龙泉市嘉文木业有限公司 Water and mildew resistant paint for wooden wireless loudspeaker tea set box and preparing method thereof

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