CN106589600A - Flame-retardant whisker composite material and preparation method thereof - Google Patents

Flame-retardant whisker composite material and preparation method thereof Download PDF

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Publication number
CN106589600A
CN106589600A CN201611160746.4A CN201611160746A CN106589600A CN 106589600 A CN106589600 A CN 106589600A CN 201611160746 A CN201611160746 A CN 201611160746A CN 106589600 A CN106589600 A CN 106589600A
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mentioned
added
parts
hours
whisker
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胡星光
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Anhui Lifeng Machine Technology Co Ltd
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Anhui Lifeng Machine Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
    • C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame-retardant whisker composite material, consisting of the following raw materials in parts by weight: 100-130 parts of polypropylene, 24-30 parts of 3-(trifluoromethyl) benzophenone, 7-9 parts of p-benzenediol, 10-13 parts of calcium carbonate whiskers, 0.4-1 part of potassium carbonate, 0.2-0.5 part of sodium carbonate, 100-120 parts of sulfolane, 2-3 parts of ammonium polyphosphate, 6-7 parts of zirconium oxychloride, 1-2 parts of sodium myrastate, 0.3-1 part of butyl tin mercaptide, 0.5-1 part of beta-hydroxyl alkyl amide, 8-10 parts of wollastonite powder, 0.5-1 part of dodecyl dimethyl betaine, and 0.2-1 part of tert-butyl p-diphenol. The ammonium polyphosphate and the like are added into the flame-retardant whisker composite material disclosed by the invention, so that the flame retardance of a finished product can be effectively improved, and the safety and fireproofing property of the finished product are can be improved.

Description

A kind of flame retardant type metal whisker composite and preparation method thereof
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of flame retardant type metal whisker composite and its preparation side Method.
Background technology
The research of composite is the scientific research field for enlivening very much in recent years, and is expected to produce far-reaching shadow to society in future Ring.In the numerous research direction of composite, inorganic filler is incorporated in polymer and is begun with obtaining significant performance and improving It is significant eventually.These composites have very at aspects such as mechanical performance, electrical property and hot propertys to polymeric matrix Big enhancing, can extensively apply in fields such as the ship automobile higher to mechanical performance and heat resistant requirements, Aero-Space.Have It is that reinforcement only needs to the lifting that little addition is just obtained in that performance with regard to this kind of composite more important point, fills out The dispersiveness of material and the interaction between filler and matrix have been largely fixed the quality of material property；
For the preparation and processing of composite are faced with following Railway Project simultaneously：Inorganic filler is with polymeric matrix chemically Composition, structure are all very different to physico-chemical property, it is preferably disperseed in the base, and make two-phase have preferable boundary Face adhesive strength.In addition for material, melt viscosity is a very important index for weighing processing complexity.It is poly- Ether ether ketone generally starts melting at 340 °C, and can possess preferable mobility, the addition of inorganic filler to 370 °C Increase will certainly melt viscosity, and cause processing temperature further to improve.Although improve processing temperature, composite it is molten Body viscosity is still maintained at a higher level value, and this can not only hinder normal production, reduces efficiency, but also can shorten plus The service life of construction equipment.It is one of the approach for solving the problem that addition can reduce the processing aid of melt viscosity；
Sulfonation dissaving polymer possesses highly branched three-dimensional structure, can reduce the entanglement of strand, improves strand Locomitivity, so as to reduce melt viscosity, improves material in the rheological property for adding man-hour.Dissaving polymer also has concurrently and produces into This is low, preparation process is simple and the advantages of be easy to industrialization, can use as the viscosity modifier of polyether-ether-ketone composite material. The sulfonic group that simultaneously it is carried can react to each other with calcium carbonate crystal whisker, so whisker and resin matrix can not only be increased Between interaction, moreover it is possible to be effectively reduced the viscosity of system in compound processing course, improve the dispersiveness of whisker；
Whisker is a kind of bar-like single crystal inorfil with compared with high length-diameter ratio, because of the less and perfect crystal knot of its diameter dimension Structure, whisker illustrates higher mechanical property, is the effective reinforcement for improving matrix mechanical performance.But this inorganic rigid is filled out The introducing of material often makes plus the melt viscosity of man-hour composite increases, and this can not only shorten the service life of process equipment, and And also reduce production efficiency, it would be highly desirable to searching out processing aid can reduce the melt viscosity of composite.Dissaving polymer has There is highly branched tree, the entanglement of polymer molecular chain can be substantially reduced, improve the motion energy of polymer molecular chain Power, reduces the solution melt viscosity of system.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of flame retardant type metal whisker composite and its system Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of flame retardant type metal whisker composite, it is made up of the raw material of following weight parts：
Polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120, APP 2-3, zirconium oxychloride 6-7, myristic acid soda soap 1-2, sulphur Alcohol butyl tin 0.3-1, beta-hydroxy alkylamide 0.5-1, wollastonite in powder 8-10, dodecyldimethylammonium hydroxide inner salt 0.5-1, the tert-butyl group To biphenol 0.2-1.
A kind of preparation method of described flame retardant type metal whisker composite, comprises the following steps：
（1）Above-mentioned zirconium oxychloride is added in its weight 35-40 times, 60-70% salpeter solution, is stirred, in addition Thiol-butyl tin is stated, stirring reaction 10-20 minute, acid solution is obtained；
（2）By above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, lead to Enter nitrogen, 8-10 hours are reacted at 200-220 DEG C, in being added to deionized water, stand 3-5 hours, suction filtration, by filter cake nothing Water-ethanol, deionized water are washed 3-4 time successively, and 2-3 hours are vacuum dried at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（3）Above-mentioned hyperbranched polyarylether ketone is added in its weight 10-14 times, 96-98% sulfuric acid solution, nitrogen is passed through, Above-mentioned acid solution is added, the insulation reaction 6-8 hour at 70-75 DEG C is added to product in 2-3 DEG C of water, suction filtration, washed To neutrality, air drying obtains sulfonated poly aryl ether ketone；
（4）Above-mentioned wollastonite in powder is sent in the sulfuric acid solution of 10-13mol/l, 1-2 nitric acid is soaked, is filtered, by precipitation washing 3-4 time, mix with above-mentioned dodecyldimethylammonium hydroxide inner salt, calcium carbonate crystal whisker, be added to the deionization of compound weight 4-6 times In water, stir, obtain whisker dispersion liquid；
（5）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of its weight 27-30 times, is stirred, added above-mentioned Whisker dispersion liquid, at 80-85 DEG C 100-120 minutes are incubated, and are passed through nitrogen, and constant temperature stirring 4-5 hours, suction filtration uses filter cake Dimethylformamide is washed 3-4 time, and 20-30 hours are vacuum dried at 120-130 DEG C, obtains sulfonated polymer modified calcium carbonate；
（6）The above-mentioned tert-butyl group is added in the absolute ethyl alcohol of its weight 5-7 times to biphenol, it is 63-80 DEG C to rise high-temperature, plus Enter above-mentioned myristic acid soda soap, sulfonated polymer modified calcium carbonate, insulated and stirred 20-30 minute, filter, by precipitation washing 2-3 It is secondary, 1-2 hours are vacuum dried at 50-60 DEG C, obtain composite modified filler；
（7）Above-mentioned composite modified filler is mixed with remaining each raw material, is stirred, send into extruder, melting extrusion is cooled down, Obtain final product.
It is an advantage of the invention that：
The present invention processes the sulfonic group for making to be grafted on modifier molecules chain using sulfonation, can produce phase interaction with calcium carbonate crystal whisker With so that filler is combined more tight with matrix, when effect is stressed, interface can well transmit stress to carbon Sour calcium pyroborate, makes whisker consume most active force, thus is effectively improved the mechanical property of material, and hyperbranched poly The dissaving structure of aryl ether ketone improves the processing characteristics of composite, and polymeric matrix strand is twined there is provided effective solution Knot, reduces the melt viscosity of composite, is conducive to the motion of polymer molecular chain, enhances two alternate interface phase interactions With additionally being able to be more beneficial for filler dispersed in the base, it is to avoid whisker aggregation, pile up and lump, contribute to improving The rheological property of composite, improves the mechanical property of finished-product material.Present invention adds APP etc., can effectively carry The fire resistance of high finished product, improves the fire safety of finished product.
Specific embodiment
A kind of flame retardant type metal whisker composite, it is made up of the raw material of following weight parts：
Polypropylene 100,3 (trifluoromethyl) benzophenone 24, hydroquinones 7, calcium carbonate crystal whisker 10, potassium carbonate 0.4, sodium carbonate 0.2, Sulfolane 100, APP 2, zirconium oxychloride 6, myristic acid soda soap 1, thiol-butyl tin 0.3, beta-hydroxy alkylamide 0.5, silicon Limestone flour 8, the dodecyldimethylammonium hydroxide inner salt 0.5, tert-butyl group are to biphenol 0.2.
A kind of preparation method of described flame retardant type metal whisker composite, comprises the following steps：
（1）Above-mentioned zirconium oxychloride is added in 35 times of its weight, 60% salpeter solution, is stirred, add above-mentioned mercaptan Butyl tin, stirring reaction 10 minutes, obtains acid solution；
（2）By above-mentioned 3 (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, it is passed through Nitrogen, at 200 DEG C react 8 hours, in being added to deionized water, stand 3 hours, suction filtration, by filter cake absolute ethyl alcohol, go from Sub- water is washed successively 3 times, is vacuum dried 2 hours at 30 DEG C, obtains hyperbranched polyarylether ketone；
（3）Above-mentioned hyperbranched polyarylether ketone is added in 10 times of its weight, 96% sulfuric acid solution, nitrogen is passed through, in addition Acid solution is stated, insulation reaction 6 hours at 70 DEG C are added to product in 2 DEG C of water, suction filtration, be washed to neutrality, normal temperature is done It is dry, obtain sulfonated poly aryl ether ketone；
（4）Above-mentioned wollastonite in powder is sent in the sulfuric acid solution of 10mol/l, 1 nitric acid is soaked, is filtered, by precipitation washing 3 times, Mix with above-mentioned dodecyldimethylammonium hydroxide inner salt, calcium carbonate crystal whisker, in being added to the deionized water of 4 times of compound weight, stir Mix uniform, obtain whisker dispersion liquid；
（5）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27 times of its weight, is stirred, add above-mentioned whisker Dispersion liquid, at 80 DEG C 100 minutes are incubated, and are passed through nitrogen, and constant temperature is stirred 4 hours, and suction filtration washs filter cake with dimethylformamide 3 times, it is vacuum dried 20 hours at 120 DEG C, obtains sulfonated polymer modified calcium carbonate；
（6）The above-mentioned tert-butyl group is added in the absolute ethyl alcohol of 5 times of its weight to biphenol, it is 63 DEG C to rise high-temperature, in addition Myristic acid soda soap, sulfonated polymer modified calcium carbonate are stated, insulated and stirred 20 minutes is filtered, by precipitation washing 2 times, at 50 DEG C Lower vacuum drying 1 hour, obtains composite modified filler；
（7）Above-mentioned composite modified filler is mixed with remaining each raw material, is stirred, send into extruder, melting extrusion is cooled down, Obtain final product.
Performance test：
Tensile strength 31.5MPa；
Elongation at break 302%.

Claims (2)

1. a kind of flame retardant type metal whisker composite, it is characterised in that it is made up of the raw material of following weight parts：
Polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120, APP 2-3, zirconium oxychloride 6-7, myristic acid soda soap 1-2, sulphur Alcohol butyl tin 0.3-1, beta-hydroxy alkylamide 0.5-1, wollastonite in powder 8-10, dodecyldimethylammonium hydroxide inner salt 0.5-1, the tert-butyl group To biphenol 0.2-1.
2. a kind of preparation method of flame retardant type metal whisker composite as claimed in claim 1, it is characterised in that including following step Suddenly：
（1）Above-mentioned zirconium oxychloride is added in its weight 35-40 times, 60-70% salpeter solution, is stirred, in addition Thiol-butyl tin is stated, stirring reaction 10-20 minute, acid solution is obtained；
（2）By above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, lead to Enter nitrogen, 8-10 hours are reacted at 200-220 DEG C, in being added to deionized water, stand 3-5 hours, suction filtration, by filter cake nothing Water-ethanol, deionized water are washed 3-4 time successively, and 2-3 hours are vacuum dried at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（3）Above-mentioned hyperbranched polyarylether ketone is added in its weight 10-14 times, 96-98% sulfuric acid solution, nitrogen is passed through, Above-mentioned acid solution is added, the insulation reaction 6-8 hour at 70-75 DEG C is added to product in 2-3 DEG C of water, suction filtration, washed To neutrality, air drying obtains sulfonated poly aryl ether ketone；
（4）Above-mentioned wollastonite in powder is sent in the sulfuric acid solution of 10-13mol/l, 1-2 nitric acid is soaked, is filtered, by precipitation washing 3-4 time, mix with above-mentioned dodecyldimethylammonium hydroxide inner salt, calcium carbonate crystal whisker, be added to the deionization of compound weight 4-6 times In water, stir, obtain whisker dispersion liquid；
（5）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of its weight 27-30 times, is stirred, added above-mentioned Whisker dispersion liquid, at 80-85 DEG C 100-120 minutes are incubated, and are passed through nitrogen, and constant temperature stirring 4-5 hours, suction filtration uses filter cake Dimethylformamide is washed 3-4 time, and 20-30 hours are vacuum dried at 120-130 DEG C, obtains sulfonated polymer modified calcium carbonate；
（6）The above-mentioned tert-butyl group is added in the absolute ethyl alcohol of its weight 5-7 times to biphenol, it is 63-80 DEG C to rise high-temperature, plus Enter above-mentioned myristic acid soda soap, sulfonated polymer modified calcium carbonate, insulated and stirred 20-30 minute, filter, by precipitation washing 2-3 It is secondary, 1-2 hours are vacuum dried at 50-60 DEG C, obtain composite modified filler；
（7）Above-mentioned composite modified filler is mixed with remaining each raw material, is stirred, send into extruder, melting extrusion is cooled down, Obtain final product.
CN201611160746.4A 2016-12-15 2016-12-15 Flame-retardant whisker composite material and preparation method thereof Pending CN106589600A (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
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Application publication date: 20170426