CN106589601A - Resin-based crystal whisker composite material and preparation method thereof - Google Patents

Resin-based crystal whisker composite material and preparation method thereof Download PDF

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Publication number
CN106589601A
CN106589601A CN201611160747.9A CN201611160747A CN106589601A CN 106589601 A CN106589601 A CN 106589601A CN 201611160747 A CN201611160747 A CN 201611160747A CN 106589601 A CN106589601 A CN 106589601A
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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
    • 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 resin-based crystal whisker composite material, which is prepared from the following raw materials in parts by weight: 2 to 3 parts of beewax, 4 to 7 parts of aluminum isopropoxide, 1 to 2 parts of zinc diricinoleate, 0.8 to 1 part of sodium alkyl benzene sulfonate, 100 to 130 parts of polypropylene, 24 to 30 parts of 3-(trifluoromethyl) benzophenone, 7 to 9 parts of hydroquinone, 10 to 13 parts of calcium carbonate whisker, 0.4 to 1 part of potassium carbonate, 0.2 to 0.5 part of sodium carbonate, 100 to 120 parts of sulfolane, 0.3 to 1 part of 2-mercapto benzimidazole, 1 to 3 parts of butyl benzyl phthalate, 4 to 6 parts of alkyd resin, 0.8 to 2 parts of polyacrylamide, and 0.1 to 0.2 part of ethylene glycol phenyl ether. A filler can be more favorably dispersed uniformly in a base body, crystal whiskers are prevented from gathering, accumulating and caking, a rheological property of the composite material is improved helpfully, and a mechanical property of a finished product material is improved.

Description

A kind of resin base 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 resin base 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 resin base metal whisker composite and its system Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of resin base metal whisker composite, it is made up of the raw material of following weight parts：
Beeswax 2-3, aluminium isopropoxide 4-7, zinc ricinate 1-2, sodium alkyl benzene sulfonate 0.8-1, polypropylene 100-130,3- (trifluoro Methyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120,2-mercaptobenzimidazole 0.3-1, BBP(Butyl Benzyl Phthalate 1-3, alkyd resin 4-6, polyacrylamide 0.8-2, Ethylene glycol phenyl ether 0.1-0.2.
A kind of preparation method of described resin base metal whisker composite, comprises the following steps：
（1）Above-mentioned beeswax is added in the absolute ethyl alcohol of its weight 7-10 times, in sending into 97-100 DEG C of water-bath, insulated and stirred 20-30 minutes, discharging, with above-mentioned zinc ricinate, is stirred to normal temperature, obtains alcohol dispersion liquid；
（2）Above-mentioned aluminium isopropoxide is added in the deionized water of its weight 15-20 times, is stirred, liter high-temperature is 54-60 DEG C, abovementioned alkyl benzene sulfonic acid sodium salt is added, insulated and stirred 30-50 minute, mix with above-mentioned alcohol dispersion liquid, ultrasonic 4-5 minutes, obtain aluminium Sol dispersion；
（3）By above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, lead to Enter nitrogen, add above-mentioned Alumina gel dispersion liquid, 8-10 hours are reacted at 200-220 DEG C, in being added to deionized water, stand 3- 5 hours, suction filtration washed filter cake absolute ethyl alcohol, deionized water 3-4 time successively, and 2-3 hours are vacuum dried at 30-40 DEG C, Obtain hyperbranched polyarylether ketone；
（4）Above-mentioned hyperbranched polyarylether ketone is added in its weight 10-14 times, 96-98% sulfuric acid solution, nitrogen is passed through, The insulation reaction 6-8 hour 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；
（5）Above-mentioned 2-mercaptobenzimidazole, alkyd resin are mixed, in being added to the absolute ethyl alcohol of compound weight 10-12 times, Stir, it is 70-80 DEG C to rise high-temperature, insulated and stirred 20-30 minute, adds above-mentioned polyacrylamide, is stirred to normal temperature, is obtained Polymer Solution；
（6）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of its weight 27-30 times, is stirred, added above-mentioned Calcium carbonate crystal whisker, Polymer Solution, at 80-85 DEG C 100-120 minutes are incubated, and are passed through nitrogen, and constant temperature stirs 4-5 hours, plus Enter above-mentioned ethylene glycol phenyl ether, stir, suction filtration washs filter cake 3-4 time with dimethylformamide, the vacuum at 120-130 DEG C 20-30 hours are dried, sulfonated polymer modified calcium carbonate is obtained；
（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 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.
Specific embodiment
A kind of resin base metal whisker composite, it is made up of the raw material of following weight parts：
Beeswax 2, aluminium isopropoxide 4, zinc ricinate 1, sodium alkyl benzene sulfonate 0.8, polypropylene 100,3 (trifluoromethyl) benzophenone 24th, hydroquinones 7, calcium carbonate crystal whisker 10, potassium carbonate 0.4, sodium carbonate 0.2, sulfolane 100,2 mercaptobenzimidazoles 0.3, adjacent benzene Dioctyl phthalate butyl benzyl 1, alkyd resin 4, polyacrylamide 0.8, ethylene glycol phenyl ether 0.1.
A kind of preparation method of described resin base metal whisker composite, comprises the following steps：
（1）Above-mentioned beeswax is added in the absolute ethyl alcohol of 7 times of its weight, in sending into 97 DEG C of water-bath, insulated and stirred 20 minutes, Discharging, with above-mentioned zinc ricinate, stirs to normal temperature, obtains alcohol dispersion liquid；
（2）Above-mentioned aluminium isopropoxide is added in the deionized water of 15 times of its weight, is stirred, it is 54 DEG C to rise high-temperature, plus Enter abovementioned alkyl benzene sulfonic acid sodium salt, insulated and stirred 30 minutes mixes with above-mentioned alcohol dispersion liquid, ultrasound 4 minutes obtains Alumina gel dispersion Liquid；
（3）By above-mentioned 3 (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, it is passed through Nitrogen, adds above-mentioned Alumina gel dispersion liquid, reacts 8 hours at 200 DEG C, in being added to deionized water, stands 3 hours, suction filtration, Filter cake absolute ethyl alcohol, deionized water are washed successively 3 times, is vacuum dried 2 hours at 30 DEG C, obtain hyperbranched polyarylether ketone；
（4）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；
（5）Above-mentioned 2 mercaptobenzimidazole, alkyd resin are mixed, in being added to the absolute ethyl alcohol of 10 times of compound weight, stirring Uniformly, it is 70 DEG C to rise high-temperature, and insulated and stirred 20 minutes adds above-mentioned polyacrylamide, stirs to normal temperature, and the son that secures satisfactory grades is molten Liquid；
（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, Polymer Solution, at 80 DEG C 100 minutes are incubated, and are passed through nitrogen, and constant temperature is stirred 4 hours, adds above-mentioned ethylene glycol phenyl Ether, stirs, suction filtration, and filter cake is washed 3 times with dimethylformamide, is vacuum dried 20 hours at 120 DEG C, obtains sulfonated polymer Thing 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 31.8MPa；
Elongation at break 306%.

Claims (2)

1. a kind of resin base metal whisker composite, it is characterised in that it is made up of the raw material of following weight parts：
Beeswax 2-3, aluminium isopropoxide 4-7, zinc ricinate 1-2, sodium alkyl benzene sulfonate 0.8-1, polypropylene 100-130,3- (trifluoro Methyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120,2-mercaptobenzimidazole 0.3-1, BBP(Butyl Benzyl Phthalate 1-3, alkyd resin 4-6, polyacrylamide 0.8-2, Ethylene glycol phenyl ether 0.1-0.2.
2. a kind of preparation method of resin base metal whisker composite as claimed in claim 1, it is characterised in that including following step Suddenly：
（1）Above-mentioned beeswax is added in the absolute ethyl alcohol of its weight 7-10 times, in sending into 97-100 DEG C of water-bath, insulated and stirred 20-30 minutes, discharging, with above-mentioned zinc ricinate, is stirred to normal temperature, obtains alcohol dispersion liquid；
（2）Above-mentioned aluminium isopropoxide is added in the deionized water of its weight 15-20 times, is stirred, liter high-temperature is 54-60 DEG C, abovementioned alkyl benzene sulfonic acid sodium salt is added, insulated and stirred 30-50 minute, mix with above-mentioned alcohol dispersion liquid, ultrasonic 4-5 minutes, obtain aluminium Sol dispersion；
（3）By above-mentioned 3- (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate mixing, in being added to sulfolane, lead to Enter nitrogen, add above-mentioned Alumina gel dispersion liquid, 8-10 hours are reacted at 200-220 DEG C, in being added to deionized water, stand 3- 5 hours, suction filtration washed filter cake absolute ethyl alcohol, deionized water 3-4 time successively, and 2-3 hours are vacuum dried at 30-40 DEG C, Obtain hyperbranched polyarylether ketone；
（4）Above-mentioned hyperbranched polyarylether ketone is added in its weight 10-14 times, 96-98% sulfuric acid solution, nitrogen is passed through, The insulation reaction 6-8 hour 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；
（5）Above-mentioned 2-mercaptobenzimidazole, alkyd resin are mixed, in being added to the absolute ethyl alcohol of compound weight 10-12 times, Stir, it is 70-80 DEG C to rise high-temperature, insulated and stirred 20-30 minute, adds above-mentioned polyacrylamide, is stirred to normal temperature, is obtained Polymer Solution；
（6）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of its weight 27-30 times, is stirred, added above-mentioned Calcium carbonate crystal whisker, Polymer Solution, at 80-85 DEG C 100-120 minutes are incubated, and are passed through nitrogen, and constant temperature stirs 4-5 hours, plus Enter above-mentioned ethylene glycol phenyl ether, stir, suction filtration washs filter cake 3-4 time with dimethylformamide, the vacuum at 120-130 DEG C 20-30 hours are dried, sulfonated polymer modified calcium carbonate is obtained；
（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.
CN201611160747.9A 2016-12-15 2016-12-15 Resin-based crystal whisker composite material and preparation method thereof Pending CN106589601A (en)

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Application Number Priority Date Filing Date Title
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Publications (1)

Publication Number Publication Date
CN106589601A true CN106589601A (en) 2017-04-26

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Application publication date: 20170426