CN106398091A - High efficiency heat resistant flame retardant composition and preparation method thereof - Google Patents

High efficiency heat resistant flame retardant composition and preparation method thereof Download PDF

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Publication number
CN106398091A
CN106398091A CN201610726490.2A CN201610726490A CN106398091A CN 106398091 A CN106398091 A CN 106398091A CN 201610726490 A CN201610726490 A CN 201610726490A CN 106398091 A CN106398091 A CN 106398091A
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fire
parts
flame retardant
preparation
heat
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CN201610726490.2A
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Chinese (zh)
Inventor
钟传新
冯玉国
黄恒
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Guilin Haoxin Science and Technology Service Co Ltd
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Guilin Haoxin Science and Technology Service Co Ltd
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Priority to CN201610726490.2A priority Critical patent/CN106398091A/en
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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76498—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76—Measuring, controlling or regulating
    • B29C2945/76494—Controlled parameter
    • B29C2945/76531—Temperature
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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

Abstract

The invention relates to a high efficiency heat resistant flame retardant composition and a preparation method thereof. The high efficiency heat resistant flame retardant composition includes the following components by weight: 30-45 parts of acrylonitrile-butadiene-styrene graft copolymer ABS, 15-25 parts of a flame retardant, 1-10 parts of a fire retardant synergistic agent, 35-45 parts of a heat-resistant modifier, 0.1-2 parts of barium stearate, 0.1-1 part of a toughener, 1-2 parts of dihydroquinolinone and 3-5 parts of salicylate; the fire retardant synergistic agent is a compound comprising aluminum hydroxide, magnesium carbonate and ultra high molecular weight polysiloxane; the high efficiency heat resistant flame retardant composition prepared by reasonable proportion and combination of all components has high heat resistance, thermal deformation temperature can reach more than 120 DEG C, and is improved by at least 30 DEG C compared with thermal deformation temperature in the prior art, on the premise of satisfying the mechanical properties, flame retardant effect and better stability can be achieved, the mechanical properties are kept in a best level, the preparation method has the advantages of being simple and practicable, and easy to process, cost is reduced, and the preparation method is suitable for popularization and application in the market.

Description

A kind of efficient heat-resisting fire-retardant combination and preparation method thereof
Technical field
The invention belongs to new forms of energy and environmental protection and energy saving technical field, more particularly, to a kind of efficient heat-resisting fire-retardant combination and its Preparation method.
Background technology
The ternary that acrylonitrile-butadiene-phenylethene grafted copolymer ABS is made up of styrene, butadiene, acrylonitrile is altogether Polymers, has concentrated the chemicals-resistant characteristic of cinnamic high fluidity, the rubber toughness of butadiene and acrylonitrile, has had excellent Processing characteristics, resistance to low temperature, electrical insulation capability, resistance to chemical corrosion and high glaze and excellent plating performance, have simultaneously There are the excellent characteristics such as creep resistant is good, dimensional stability is high, molding shrinkage is little, should in fields such as military project, automobile, electronic apparatus With widely.But the oxygen index (OI) of one side acrylonitrile-butadiene-phenylethene grafted copolymer ABS only has 18, belongs to easy fuel wood Material, and heat resistance is not high, and general heat distortion temperature is 82-84 DEG C.Therefore when for electronic and electrical equipment, mostly need into Row flame-proof heat-resistant is modified, to reach fire safety use requirement.
Accordingly, it would be desirable to develop a kind of low cost, high-performance, the superelevation heat-proof combustion-resistant ABS composition of handling ease.
Content of the invention
In view of the problems of prior art, the present invention provide a kind of primary and foremost purpose of the present invention be to provide a kind of super High-temp resistant fire-retarding ABS composition, said composition has high heat-resisting, inexpensive, high fire-retardance effect and its stability, its every mechanics Performance all keeps optimum balance.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
The invention provides a kind of efficient heat-resisting fire-retardant combination, including the component of following weight portion：Acrylic nitrile-butadiene two Alkene-phenylethene grafted copolymer ABS30-45 part, fire retardant 15-25 part, fire retarding synergist 1-10 part, heat-proof modifier 35-45 Part, barium stearate 0.1-2 part, toughener, 0.1-1 part, EEDQ 1-2 part, salicylate 3-5 part；Wherein, described fire-retardant association The compound that effect agent is made up of aluminium hydroxide, magnesium carbonate and super high molecular weight polysiloxanes.
The invention has the beneficial effects as follows：Inventor's early stage has carried out the screening experiment of substantial amounts of component and consumption, unexpected Discovery, technical scheme has high-fire resistance, heat distortion temperature by the combination of rational proportioning and each component Can reach more than 120 degree, at least improve 30 degree compared with prior art, simultaneously under the premise of meeting mechanical property, reach flame retardant effect And stability is more excellent, its every mechanical property all keeps optimum balance, and preparation method is simple, handling ease, simultaneously Reduce cost, be suitable for commercially popularization and application.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described acrylonitrile-butadiene-phenylethene grafted copolymer ABS30 part, described fire retardant 15, described 1 part of fire retarding synergist, 35 parts of described heat-proof modifier, 0.1 part of described barium stearate, 0.1 part of described toughener, described dihydro quinoline 1 part of quinoline, 3 parts of described salicylate.
Further, described super high molecular weight polysiloxanes is phenyl polysiloxane.
Further, the molecular weight of described phenyl polysiloxane >=30,000, when temperature is 25 DEG C, its viscosity >= 500mPa·s.
Further, described heat-proof modifier is N- isopropylmaleimide, N- CYCLOHEXANE maleimide, poly- (N- N- octadecyl maleimide), one or more of N-phenylmaleimide and poly- (N-n- butyl maleimide) Mixture.
The present invention also provides a kind of preparation method of above-mentioned efficient heat-resisting fire-retardant combination, comprises the steps：A, general are each Component raw material is sufficiently mixed 10-60 minute by proportioning in high-speed mixer；B, by said mixture through delicate metering feeding Device is transported in double screw extruder, and each section of extruder temperature of extruder controls between 180～240 DEG C, twin-screw extrusion The draw ratio of machine is 25～40, and screw speed is 200-800 rev/min, and under shearing, mixing and the conveying of screw rod, material obtains With abundant fusing, compound, then through extruding pelletization, be dried to obtain flame-proof ABS particle；C, flame-proof ABS particle is added to injection It is processed into required batten in machine, cooling, pelletizing, be packaged into finished product；Described injecting condition is：190-230 DEG C of barrel temperature, mould 60～70 DEG C of temperature, injection pressure 6-10MPa.
Specific embodiment
Hereinafter the principle and feature of the present invention is described, example is served only for explaining the present invention, is not intended to limit Determine the scope of the present invention.
The invention provides a kind of efficient heat-resisting fire-retardant combination, including the component of following weight portion：Acrylic nitrile-butadiene two Alkene-phenylethene grafted copolymer ABS 30-45 part, fire retardant 15-25 part, fire retarding synergist 1-10 part, heat-proof modifier 35-45 Part, barium stearate 0.1-2 part, toughener, 0.1-1 part, EEDQ 1-2 part, salicylate 3-5 part；Wherein, described fire-retardant association The compound that effect agent is made up of aluminium hydroxide, magnesium carbonate and super high molecular weight polysiloxanes.
Inventor's early stage has carried out the screening experiment of substantial amounts of component and consumption, is found surprisingly that, the technology of the present invention Scheme has high-fire resistance by the combination of rational proportioning and each component, and heat distortion temperature can reach more than 120 degree, more existing There is technology at least to improve 30 degree, simultaneously under the premise of meeting mechanical property, reach flame retardant effect and stability is more excellent, its every power Learn performance and all keep optimum balance, and preparation method is simple, handling ease, reduces cost, is suitable in market simultaneously Upper popularization and application.
To be introduced below by specific embodiment.
Embodiment 1
A kind of efficient heat-resisting fire-retardant combination of high-efficiency environment friendly, described acrylonitrile-butadiene-phenylethene grafted copolymer ABS30 part, described fire retardant 15,1 part of described fire retarding synergist, 35 parts of described heat-proof modifier, 0.1 part of described barium stearate, 0.1 part of described toughener, 1 part of described EEDQ, 3 parts of described salicylate；Wherein, described fire retarding synergist is by hydroxide The compound of aluminium, magnesium carbonate and super high molecular weight polysiloxanes composition.Described super high molecular weight polysiloxanes is the poly- silica of phenyl Alkane, molecular weight >=30,000 of described phenyl polysiloxane, when temperature is 25 DEG C, its viscosity >=500mPa s.Described heat-resisting change Property agent be N- isopropylmaleimide, N- CYCLOHEXANE maleimide, poly- (N-n- octadecyl maleimide), N- phenyl The mixture of one or more of maleimide and poly- (N-n- butyl maleimide)；Described barium stearate is vinyl Bis-stearamides.
Embodiment 2
A kind of efficient heat-resisting fire-retardant combination of high-efficiency environment friendly, described acrylonitrile-butadiene-phenylethene grafted copolymer ABS340 part, described fire retardant 20,5 parts of described fire retarding synergist, 40 parts of described heat-proof modifier, 1 part of described barium stearate, institute State 0.5 part of toughener, 1.5 parts of described EEDQ, 4 parts of described salicylate.Disclosed in remaining component proportion and embodiment one Content identical.
Embodiment 3
A kind of efficient heat-resisting fire-retardant combination of high-efficiency environment friendly, described acrylonitrile-butadiene-phenylethene grafted copolymer ABS345 part, described fire retardant 25,6 parts of described fire retarding synergist, 45 parts of described heat-proof modifier, 2 parts of described barium stearate, institute State 1 part of toughener, 2 parts of described EEDQ, 5 parts of described salicylate.
Comparative example 1
In this comparative example, fire retarding synergist is by answering that antimony oxide, titanium dioxide and super high molecular weight polysiloxanes form Join thing, remaining component is all same as Example 1.
Comparative example 2
In this comparative example, fire retarding synergist is by answering that antimony oxide, titanium dioxide and super high molecular weight polysiloxanes form Join thing, and EEDQ is replaced by phosphite ester equivalent, remaining component is all same as Example 1.
Comparative example 3
In this comparative example, fire retarding synergist is by antimony oxide, talcum powder and superelevation HMW band methyl polysiloxane Compound, and EEDQ replaced by styrene equivalent, and remaining component is all same as Example 1.
The present invention also provides a kind of preparation method of efficient heat-resisting fire-retardant combination described in above-described embodiment, including as follows Step：A, each component raw material is sufficiently mixed 10-60 minute by proportioning in high-speed mixer；B, will said mixture through accurate The pay-off of metering is transported in double screw extruder, and each section of extruder temperature of extruder controls between 180～240 DEG C, The draw ratio of double screw extruder is 25～40, and screw speed is 200-800 rev/min, in shearing, mixing and the conveying of screw rod Under, material fully melted, compound, then through extruding pelletization, be dried to obtain flame-proof ABS particle；C, flame-proof ABS particle is added Enter and be processed into required batten in injection machine, cooling, pelletizing, be packaged into finished product；Described injecting condition is：Barrel temperature 190- 230 DEG C, 60～70 DEG C of mold temperature, injection pressure 6-10MPa.
The preparation method of the efficient heat-resisting fire-retardant combination that the present invention provides is simple, and handling ease reduces simultaneously Cost, is suitable for commercially popularization and application
Measure of merit
Respectively measure above-described embodiment and comparative example preparation high-efficiency environment friendly efficient heat-resisting fire-retardant combination be added to foster Grow to the clean-up effect with water quality in pond in pond, and respectively COD clearance and heavy metal copper ion concentration are measured.
Test result is as shown in table 1.
Table 1
Technical scheme be can be seen that according to the data in table 1 there is higher heat resistance, heat distortion temperature can Reach more than 120 degree, improve 30 degree about compared with prior art, its mechanical property is also improved, and is meeting mechanical property simultaneously simultaneously Under the premise of energy, reach flame retardant effect and stability is more excellent, its every mechanical property all keeps optimum balance, and preparation method letter Single easy, handling ease, reduces cost simultaneously, is suitable for commercially popularization and application.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and Within principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.

Claims (6)

1. a kind of efficient heat-resisting fire-retardant combination is it is characterised in that include the component of following weight portion：Acrylonitrile-butadiene-benzene Grafted ethylene copolymer ABS 30-45 part, fire retardant 15-25 part, fire retarding synergist 1-10 part, heat-proof modifier 35-45 part, firmly Resin acid barium 0.1-2 part, toughener, 0.1-1 part, EEDQ 1-2 part, salicylate 3-5 part；Wherein, described fire retarding synergist The compound being made up of aluminium hydroxide, magnesium carbonate and super high molecular weight polysiloxanes.
2. efficient heat-resisting fire-retardant combination according to claim 1 is it is characterised in that described acrylonitrile-butadiene-benzene second Alkene graft copolymer ABS30 part, described fire retardant 15,1 part of described fire retarding synergist, 35 parts of described heat-proof modifier is described hard 0.1 part of resin acid barium, 0.1 part of described toughener, 1 part of described EEDQ, 3 parts of described salicylate.
3. a kind of efficient heat-resisting fire-retardant combination according to claim 1 it is characterised in that：The poly- silicon of described super high molecular weight Oxygen alkane is phenyl polysiloxane.
4. a kind of efficient heat-resisting fire-retardant combination according to claim 3 it is characterised in that：Described phenyl polysiloxane Molecular weight >=30,000, when temperature is 25 DEG C, its viscosity >=500mPa s.
5. a kind of efficient heat-resisting fire-retardant combination according to claim 1 it is characterised in that：Described heat-proof modifier is N- Isopropylmaleimide, N- CYCLOHEXANE maleimide, poly- (N-n- octadecyl maleimide), N- benzyl maleimide The mixture of one or more of amine and poly- (N-n- butyl maleimide).
6. the efficient heat-resisting fire-retardant combination as described in a kind of any one as Claims 1 to 5 preparation method it is characterised in that： Comprise the steps：
A, each component raw material is sufficiently mixed 10-60 minute by proportioning in high-speed mixer；
B, said mixture is transported in double screw extruder through the pay-off of delicate metering, each section of screw rod of extruder Between 180～240 DEG C, the draw ratio of double screw extruder is 25～40 to temperature control, and screw speed is 200-800 rev/min Clock, under the shearing of screw rod, mixing and conveying, material fully melted, compound, then through extruding pelletization, be dried to obtain resistance Combustion ABS particle；
C, flame-proof ABS particle is added in injection machine and is processed into required batten, cooling, pelletizing, be packaged into finished product；Described injection Condition is：190-230 DEG C of barrel temperature, 60～70 DEG C of mold temperature, injection pressure 6-10MPa.
CN201610726490.2A 2016-08-25 2016-08-25 High efficiency heat resistant flame retardant composition and preparation method thereof Pending CN106398091A (en)

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