CN106750932A - A kind of anti-oxidant metal whisker composite and preparation method thereof - Google Patents

A kind of anti-oxidant metal whisker composite and preparation method thereof Download PDF

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CN106750932A
CN106750932A CN201611159598.4A CN201611159598A CN106750932A CN 106750932 A CN106750932 A CN 106750932A CN 201611159598 A CN201611159598 A CN 201611159598A CN 106750932 A CN106750932 A CN 106750932A
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added
mentioned
stirred
hours
oxidant
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L2205/03—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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of anti-oxidant metal whisker composite, it is made up of the raw material of following weight parts：Polypropylene 100 130,3 (trifluoromethyl) benzophenone 24 30, hydroquinones 79, calcium carbonate crystal whisker 10 13, potassium carbonate 0.4 1, sodium carbonate 0.2 0.5, sulfolane 100 120, polyvinylbenzenesulfonic acid 12, diphenyl-imidazole quinoline 0.3 1, palm wax 35, DAA 23, triethanolamine 0.4 1, methyl methacrylate 23, diatomite 10 12, anti-oxidant DLTP 0.3 1.Diphenyl-imidazole quinoline, anti-oxidant DLTP that the present invention is added etc., effectively raises the antioxygenic property of finished composite material, improves the stability of finished product.

Description

A kind of anti-oxidant 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 anti-oxidant metal whisker composite and its preparation side Method.
Background technology
The research of composite is scientific research field very active 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 into polymer and improves the beginning to obtain significant performance It is significant eventually.These composites have very at mechanical performance, the aspect such as electrical property and hot property to polymeric matrix Big enhancing, in the ship automobile higher to mechanical performance and heat resistant requirements, the field such as Aero-Space being capable of extensive use.Have It is that reinforcement only needs to the lifting that little addition is just obtained in that performance on 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；
Preparation and processing for 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 two-phase is had 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 Melt viscosity will certainly be made to be increased, and causes processing temperature further to improve.Although improve processing temperature, composite it is molten Body viscosity is still maintained at a level value higher, and this can not only hinder normal production, reduces efficiency, but also can shorten plus The service life of construction equipment.The processing aid that addition can reduce melt viscosity is one of the approach for solving the problem；
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 rheological property of the material in processing.Dissaving polymer also has concurrently and is produced into This is low, preparation process is simple and the advantages of be easy to industrialization, can be used as the viscosity modifier of polyether-ether-ketone composite material. The sulfonic group that it is carried simultaneously 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 smaller and perfect crystal knot of its diameter dimension Structure, whisker illustrates mechanical property higher, is the effective reinforcement for improving matrix mechanical performance.But this inorganic rigid is filled out The melt viscosity of composite increases when the introducing of material often makes processing, 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 anti-oxidant metal whisker composite and its system Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of anti-oxidant 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, polyvinylbenzenesulfonic acid 1-2, diphenyl-imidazole quinoline 0.3-1, palm wax 3- 5th, DAA 2-3, triethanolamine 0.4-1, methyl methacrylate 2-3, diatomite 10-12, anti-oxidant DLTP 0.3-1.
A kind of preparation method of described anti-oxidant metal whisker composite, comprises the following steps：
（1）Above-mentioned diatomite is calcined 1-2 hours at 700-800 DEG C, is cooled down, wear into fine powder, be added to 10-14 times of its weight Deionized water in, add polyvinylbenzenesulfonic acid, rise high-temperature be 70-80 DEG C, insulated and stirred 30-40 minute, filter, will precipitate Washing 2-3 times, air drying is added in 10-12 times of its weight, 47-50% ethanol solution, is stirred, and is added above-mentioned Triethanolamine, it is ultrasonic 5-7 minutes, obtain hydramine dispersion liquid；
（2）Above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate are mixed, is added in sulfolane, led to Enter nitrogen, reacted 8-10 hours at 200-220 DEG C, be added in deionized water, stand 3-5 hours, suction filtration obtains filter cake；
（3）Above-mentioned filter cake is added in hydramine dispersion liquid, insulated and stirred 20-30 minutes at 50-60 DEG C, filtering will be precipitated Washed 3-4 times successively with deionized water, be vacuum dried 2-3 hours at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（4）Above-mentioned DAA is taken, is heated 3-5 minutes at 76-80 DEG C, add above-mentioned diphenyl-imidazole quinoline, insulated and stirred 10- 20 minutes, above-mentioned anti-oxidant DLTP is added, stirred to normal temperature, obtain anti-oxidant alcohol liquid；
（5）Above-mentioned hyperbranched polyarylether ketone is added in 10-14 times of its weight, 96-98% sulfuric acid solution, nitrogen is passed through, Insulation reaction 6-8 hours at 70-75 DEG C, product is added in 2-3 DEG C of water, suction filtration, is washed to neutrality, air drying, Obtain sulfonated poly aryl ether ketone；
（6）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27-30 times of its weight, is stirred, added above-mentioned Calcium carbonate crystal whisker, anti-oxidant alcohol liquid, triethanolamine, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, constant temperature stirring 4- 5 hours, suction filtration washed 3-4 times filter cake with dimethylformamide, was vacuum dried 20-30 hours at 120-130 DEG C, obtained sulfonation Polymer modification calcium carbonate；
（7）Above-mentioned sulfonated polymer modified calcium carbonate is mixed with remaining each raw material, is stirred, send into extruder, melting is squeezed Go out, cool down, obtain final product.
It is an advantage of the invention that：
The present invention makes the sulfonic group being grafted on modifier molecules chain using sulfonation treatment, 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, help to improve The rheological property of composite, improves the mechanical property of finished-product material.Diphenyl-imidazole quinoline, anti-oxidant DLTP that the present invention is added Deng, the antioxygenic property of finished composite material is effectively raised, improve the stability of finished product.
Specific embodiment
A kind of anti-oxidant 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, polyvinylbenzenesulfonic acid 1, diphenyl-imidazole quinoline 0.3, palm wax 3, DAA 2, triethanolamine 0.4, methyl-prop E pioic acid methyl ester 2, diatomite 10, anti-oxidant DLTP 0.3.
A kind of preparation method of described anti-oxidant metal whisker composite, comprises the following steps：
（1）Above-mentioned diatomite is calcined 1 hour at 700 DEG C, is cooled down, wear into fine powder, be added to the deionization of 10 times of its weight In water, polyvinylbenzenesulfonic acid is added, it is 70 DEG C to rise high-temperature, insulated and stirred 30 minutes, filtering, and by precipitation washing 2 times, normal temperature is done It is dry, it is added in 10 times of its weight, 47% ethanol solution, stir, above-mentioned triethanolamine is added, ultrasound 5 minutes is obtained Hydramine dispersion liquid；
（2）Above-mentioned 3 (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate are mixed, is added in sulfolane, be passed through Nitrogen, reacts 8 hours at 200 DEG C, is added in deionized water, stands 3 hours, and suction filtration obtains filter cake；
（3）Above-mentioned filter cake is added in hydramine dispersion liquid, insulated and stirred 20 minutes at 50 DEG C, filter, by precipitation spend from Sub- water is washed 3 times successively, is vacuum dried 2 hours at 30 DEG C, obtains hyperbranched polyarylether ketone；
（4）Above-mentioned DAA is taken, is heated 3 minutes at 76 DEG C, the above-mentioned diphenyl-imidazole quinoline of addition, insulated and stirred 10 minutes, Above-mentioned anti-oxidant DLTP is added, is stirred to normal temperature, obtain anti-oxidant alcohol liquid；
（5）Above-mentioned hyperbranched polyarylether ketone is added in 10 times of its weight, 96% sulfuric acid solution, nitrogen is passed through, at 70 DEG C Lower insulation reaction 6 hours, product is added in 2 DEG C of water, suction filtration, is washed to neutrality, and air drying obtains sulfonated polyether Ketone；
（6）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27 times of its weight, is stirred, add above-mentioned carbonic acid Calcium pyroborate, anti-oxidant alcohol liquid, triethanolamine, 100 minutes are incubated at 80 DEG C, are passed through nitrogen, and constant temperature is stirred 4 hours, suction filtration, will Filter cake is washed 3 times with dimethylformamide, is vacuum dried 20 hours at 120 DEG C, obtains sulfonated polymer modified calcium carbonate；
（7）Above-mentioned sulfonated polymer modified calcium carbonate is mixed with remaining each raw material, is stirred, send into extruder, melting is squeezed Go out, cool down, obtain final product.
Performance test：
Tensile strength 31.9MPa；
Elongation at break 304%.

Claims (2)

1. a kind of anti-oxidant 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, polyvinylbenzenesulfonic acid 1-2, diphenyl-imidazole quinoline 0.3-1, palm wax 3- 5th, DAA 2-3, triethanolamine 0.4-1, methyl methacrylate 2-3, diatomite 10-12, anti-oxidant DLTP 0.3-1.
2. a kind of preparation method of anti-oxidant metal whisker composite as claimed in claim 1, it is characterised in that including following step Suddenly：
（1）Above-mentioned diatomite is calcined 1-2 hours at 700-800 DEG C, is cooled down, wear into fine powder, be added to 10-14 times of its weight Deionized water in, add polyvinylbenzenesulfonic acid, rise high-temperature be 70-80 DEG C, insulated and stirred 30-40 minute, filter, will precipitate Washing 2-3 times, air drying is added in 10-12 times of its weight, 47-50% ethanol solution, is stirred, and is added above-mentioned Triethanolamine, it is ultrasonic 5-7 minutes, obtain hydramine dispersion liquid；
（2）Above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate are mixed, is added in sulfolane, led to Enter nitrogen, reacted 8-10 hours at 200-220 DEG C, be added in deionized water, stand 3-5 hours, suction filtration obtains filter cake；
（3）Above-mentioned filter cake is added in hydramine dispersion liquid, insulated and stirred 20-30 minutes at 50-60 DEG C, filtering will be precipitated Washed 3-4 times successively with deionized water, be vacuum dried 2-3 hours at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（4）Above-mentioned DAA is taken, is heated 3-5 minutes at 76-80 DEG C, add above-mentioned diphenyl-imidazole quinoline, insulated and stirred 10- 20 minutes, above-mentioned anti-oxidant DLTP is added, stirred to normal temperature, obtain anti-oxidant alcohol liquid；
（5）Above-mentioned hyperbranched polyarylether ketone is added in 10-14 times of its weight, 96-98% sulfuric acid solution, nitrogen is passed through, Insulation reaction 6-8 hours at 70-75 DEG C, product is added in 2-3 DEG C of water, suction filtration, is washed to neutrality, air drying, Obtain sulfonated poly aryl ether ketone；
（6）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27-30 times of its weight, is stirred, added above-mentioned Calcium carbonate crystal whisker, anti-oxidant alcohol liquid, triethanolamine, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, constant temperature stirring 4- 5 hours, suction filtration washed 3-4 times filter cake with dimethylformamide, was vacuum dried 20-30 hours at 120-130 DEG C, obtained sulfonation Polymer modification calcium carbonate；
（7）Above-mentioned sulfonated polymer modified calcium carbonate is mixed with remaining each raw material, is stirred, send into extruder, melting is squeezed Go out, cool down, obtain final product.
CN201611159598.4A 2016-12-15 2016-12-15 A kind of anti-oxidant metal whisker composite and preparation method thereof Pending CN106750932A (en)

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Application Number Priority Date Filing Date Title
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Publication Number Publication Date
CN106750932A true CN106750932A (en) 2017-05-31

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Application publication date: 20170531