CN106750935A - A kind of environmentally friendly metal whisker composite and preparation method thereof - Google Patents
A kind of environmentally friendly metal whisker composite and preparation method thereof Download PDFInfo
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- CN106750935A CN106750935A CN201611160757.2A CN201611160757A CN106750935A CN 106750935 A CN106750935 A CN 106750935A CN 201611160757 A CN201611160757 A CN 201611160757A CN 106750935 A CN106750935 A CN 106750935A
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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)
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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
- C08G65/48—Polymers modified by chemical after-treatment
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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
- 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
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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
- 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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Abstract
The invention discloses a kind of environmentally friendly metal whisker composite, it is made up of the raw material of following weight parts:Polyvinyl butyral resin 0.6 1, calcium propionate 23, 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, the phosphoamide 0.7 1 of saturation 18, short and long-chain acyl triglyceride molecules 0.6 1, microcrystalline wax 34, sorbierite 24, casein 0.5 1, diatomite 7 10.Composite of the invention is free of poisonous and hazardous volatile materials, and Safety and Environmental Protection is good, and combination property is superior.
Description
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of environmentally friendly metal whisker composite and preparation method thereof.
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 environmentally friendly metal whisker composite and its preparation
Method.
The present invention is achieved by the following technical solutions:
A kind of environmentally friendly metal whisker composite, it is made up of the raw material of following weight parts:
Polyvinyl butyral resin 0.6-1, calcium propionate 2-3, polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, to benzene
Diphenol 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120, the phosphinylidyne of saturation 18
Amine 0.7-1, short and long-chain acyl triglyceride molecules 0.6-1, microcrystalline wax 3-4, sorbierite 2-4, casein 0.5-1, diatomite 7-10.
A kind of preparation method of described environmentally friendly metal whisker composite, comprises the following steps:
(1)Above-mentioned calcium propionate, the phosphoamide of saturation 18 are mixed, is added in the deionized water of 27-30 times of compound weight, stirred
Mix uniform, obtain acid amides 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 adds filter cake
Ultrasonic 3-4 minutes in above-mentioned acid amides dispersion liquid, precipitation absolute ethyl alcohol, deionized water are washed 3-4 times in filtering successively, then
It is vacuum dried 2-3 hours at 30-40 DEG C, obtains hyperbranched polyarylether ketone;
(3)Above-mentioned diatomite is calcined 1-2 hours at 600-700 DEG C, cooled down, worn into fine powder, be added to 10-12mol/l's
In NaOH, insulated and stirred 40-50 minutes at 57-60 DEG C, filtering, by precipitation washing 3-4 times, air drying obtains modified
Diatomite in powder;
(4)Above-mentioned hyperbranched polyarylether ketone, modification infusorial earth powder are mixed, 10-14 times of compound weight, 96-98% is added to
Sulfuric acid solution in, be passed through nitrogen, insulation reaction 6-8 hours at 70-75 DEG C, product is added in 2-3 DEG C of water, take out
Filter, is washed to neutrality, and air drying obtains sulfonated poly aryl ether ketone;
(5)Above-mentioned microcrystalline wax is taken, is added in the absolute ethyl alcohol of 10-13 times of its weight, add above-mentioned short and long-chain acyl triglyceride molecules, feeding
To in 100-110 DEG C of oil bath, insulated and stirred 4-10 minutes, discharging was mixed with above-mentioned polyvinyl butyral resin, calcium carbonate crystal whisker
Close, it is ultrasonic 3-4 minutes, obtain whisker alcohol dispersion liquid;
(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
Whisker alcohol dispersion liquid, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, suction filtration, by filter cake
Washed 3-4 times with dimethylformamide, be vacuum dried 20-30 hours at 120-130 DEG C, obtain 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.
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.Composite of the invention is free of poisonous and hazardous volatilization
Property material, Safety and Environmental Protection is good, and combination property is superior.
Specific embodiment
A kind of environmentally friendly metal whisker composite, it is made up of the raw material of following weight parts:
Polyvinyl butyral resin 0.6, calcium propionate 2, polypropylene 100,3 (trifluoromethyl) benzophenone 24, hydroquinones 7, calcium carbonate
Whisker 10, potassium carbonate 0.4, sodium carbonate 0.2, sulfolane 100, the phosphoamide 0.7 of saturation 18, short and long-chain acyl triglyceride molecules 0.6, microcrystalline wax
3rd, sorbierite 2, casein 0.5, diatomite 7.
A kind of preparation method of described environmentally friendly metal whisker composite, comprises the following steps:
(1)Above-mentioned calcium propionate, the phosphoamide of saturation 18 are mixed, is added in the deionized water of 27 times of compound weight, stirred
Uniformly, acid amides dispersion liquid is obtained;
(2)Above-mentioned 3 (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate are mixed, is added in sulfolane, be passed through
Nitrogen, is reacted 8 hours at 200 DEG C, is added in deionized water, stands 3 hours, and filter cake is added to above-mentioned acid amides by suction filtration
In dispersion liquid, precipitation absolute ethyl alcohol, deionized water are washed in ultrasound 3 minutes, filtering 3 times successively, then vacuum is done at 30 DEG C
Dry 2 hours, obtain hyperbranched polyarylether ketone;
(3)Above-mentioned diatomite is calcined 1 hour at 600 DEG C, cooled down, worn into fine powder, be added to the NaOH of 10mol/l
In, insulated and stirred 40 minutes at 57 DEG C, filtering, by precipitation washing 3 times, air drying obtains modification infusorial earth powder;
(4)Above-mentioned hyperbranched polyarylether ketone, modification infusorial earth powder are mixed, 10 times of compound weight, 96% sulfuric acid is added to
In solution, nitrogen is passed through, be added to product in 2 DEG C of water by insulation reaction 6 hours at 70 DEG C, and suction filtration is washed to neutrality,
Air drying, obtains sulfonated poly aryl ether ketone;
(5)Above-mentioned microcrystalline wax is taken, is added in the absolute ethyl alcohol of 10 times of its weight, add above-mentioned short and long-chain acyl triglyceride molecules, be sent to
In 100 DEG C of oil bath, insulated and stirred 4 minutes, discharging mixes with above-mentioned polyvinyl butyral resin, calcium carbonate crystal whisker, 3 points of ultrasound
Clock, obtains whisker alcohol dispersion 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 whisker
Alcohol dispersion liquid, 100 minutes are incubated at 80 DEG C, are passed through nitrogen, and constant temperature is stirred 4 hours, and suction filtration washes filter cake with dimethylformamide
Wash 3 times, be vacuum dried 20 hours at 120 DEG C, obtain 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 31.8MPa;
Elongation at break 309%.
Claims (2)
1. a kind of environmentally friendly metal whisker composite, it is characterised in that it is made up of the raw material of following weight parts:
Polyvinyl butyral resin 0.6-1, calcium propionate 2-3, polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, to benzene
Diphenol 7-9, calcium carbonate crystal whisker 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120, the phosphinylidyne of saturation 18
Amine 0.7-1, short and long-chain acyl triglyceride molecules 0.6-1, microcrystalline wax 3-4, sorbierite 2-4, casein 0.5-1, diatomite 7-10.
2. a kind of preparation method of environmentally friendly metal whisker composite as claimed in claim 1, it is characterised in that including following step
Suddenly:
(1)Above-mentioned calcium propionate, the phosphoamide of saturation 18 are mixed, is added in the deionized water of 27-30 times of compound weight, stirred
Mix uniform, obtain acid amides 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 adds filter cake
Ultrasonic 3-4 minutes in above-mentioned acid amides dispersion liquid, precipitation absolute ethyl alcohol, deionized water are washed 3-4 times in filtering successively, then
It is vacuum dried 2-3 hours at 30-40 DEG C, obtains hyperbranched polyarylether ketone;
(3)Above-mentioned diatomite is calcined 1-2 hours at 600-700 DEG C, cooled down, worn into fine powder, be added to 10-12mol/l's
In NaOH, insulated and stirred 40-50 minutes at 57-60 DEG C, filtering, by precipitation washing 3-4 times, air drying obtains modified
Diatomite in powder;
(4)Above-mentioned hyperbranched polyarylether ketone, modification infusorial earth powder are mixed, 10-14 times of compound weight, 96-98% is added to
Sulfuric acid solution in, be passed through nitrogen, insulation reaction 6-8 hours at 70-75 DEG C, product is added in 2-3 DEG C of water, take out
Filter, is washed to neutrality, and air drying obtains sulfonated poly aryl ether ketone;
(5)Above-mentioned microcrystalline wax is taken, is added in the absolute ethyl alcohol of 10-13 times of its weight, add above-mentioned short and long-chain acyl triglyceride molecules, feeding
To in 100-110 DEG C of oil bath, insulated and stirred 4-10 minutes, discharging was mixed with above-mentioned polyvinyl butyral resin, calcium carbonate crystal whisker
Close, it is ultrasonic 3-4 minutes, obtain whisker alcohol dispersion liquid;
(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
Whisker alcohol dispersion liquid, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, suction filtration, by filter cake
Washed 3-4 times with dimethylformamide, be vacuum dried 20-30 hours at 120-130 DEG C, obtain 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.
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