CN106750934A - A kind of hydrophobic type metal whisker composite and preparation method thereof - Google Patents
A kind of hydrophobic type metal whisker composite and preparation method thereof Download PDFInfo
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- CN106750934A CN106750934A CN201611160756.8A CN201611160756A CN106750934A CN 106750934 A CN106750934 A CN 106750934A CN 201611160756 A CN201611160756 A CN 201611160756A CN 106750934 A CN106750934 A CN 106750934A
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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
Abstract
The invention discloses a kind of hydrophobic type metal whisker composite, it is made up of the raw material of following weight parts：Calcium ricinoleate 0.7 2, 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 100 120,1H, 1H, 2H, 2H perfluoro decyls triethoxysilane 0.5 1, hydroxy stearic acid 23, propylene glycol alginate 0.5 1, butyl titanate 68, the methylimidazole 0.6 1 of alum 0.8 1,1,2, n salicylanilides 0.1 0.3.Composite of the invention has good hydrophobic performance, and combination property is superior.
Description
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of hydrophobic type 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 hydrophobic type metal whisker composite and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of hydrophobic type metal whisker composite, it is made up of the raw material of following weight parts：
Calcium ricinoleate 0.7-2, polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate are brilliant
Must 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120,1H, 1H, 2H, 2H- perfluoro decyl triethoxy
Silane 0.5-1, hydroxy stearic acid 2-3, propylene glycol alginate 0.5-1, butyl titanate 6-8, alum 0.8-1,1,2-
Methylimidazole 0.6-1, n- salicylanilide 0.1-0.3.
A kind of preparation method of described hydrophobic type metal whisker composite, comprises the following steps：
（1）Above-mentioned butyl titanate is added in the deionized water of 24-30 times of its weight, is stirred, liter high-temperature is 43-
50 DEG C, insulated and stirred 10-20 minutes, above-mentioned 1,2- methylimidazoles are added, insulated and stirred 20-30 minutes, add compound weight
The absolute ethyl alcohol of 17-20% is measured, it is 70-75 DEG C to rise high-temperature, insulated and stirred 30-40 minutes, obtains metatitanic acid ester solution；
（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, add above-mentioned alum, titanate esters molten
Liquid, stirs, and stands 3-5 hours, and suction filtration washs 3-4 times filter cake absolute ethyl alcohol, deionized water, at 30-40 DEG C successively
Lower vacuum drying 2-3 hours, obtains hyperbranched polyarylether ketone；
（3）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；
（4）Above-mentioned calcium ricinoleate, calcium carbonate crystal whisker are mixed, is added in the dimethylformamide of 10-13 times of compound weight, risen
High-temperature is 50-60 DEG C, adds above-mentioned n- salicylanilides, ultrasonic 20-30 minutes, obtains acid amides dispersion liquid；
（5）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27-30 times of its weight, is stirred, added above-mentioned
Acid amides dispersion liquid, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, and suction filtration uses filter cake
Dimethylformamide is washed 3-4 times, is vacuum dried 20-30 hours at 120-130 DEG C, obtains sulfonated polymer modified calcium carbonate；
（6）Above-mentioned sulfonated polymer modified calcium carbonate, 1H, the mixing of 1H, 2H, 2H- perfluoro decyl triethoxysilane are added to
In the absolute ethyl alcohol of 1.6-2 times of compound weight, insulated and stirred 1-2 hours at 70-78 DEG C, suction filtration is each with residue by precipitating
Raw material mixes, and stirs, and sends into extruder, and melting extrusion, cooling is obtained 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.The 1H that the present invention is added, the second of 1H, 2H, 2H perfluoro decyl three
TMOS etc., can effectively improve the water repelling property of finished product, improve the combination property of finished product.
Specific embodiment
A kind of hydrophobic type metal whisker composite, it is made up of the raw material of following weight parts：
Calcium ricinoleate 0.7, polypropylene 100,3 (trifluoromethyl) benzophenone 24, hydroquinones 7, calcium carbonate crystal whisker 10, potassium carbonate
0.4th, sodium carbonate 0.2, sulfolane 100,1H, 1H, 2H, 2H perfluoro decyl triethoxysilane 0.5, hydroxy stearic acid 2, alginic acid
Propylene glycol ester 0.5, butyl titanate 6, the methylimidazole 0.6 of alum 0.8,1,2, n- salicylanilides 0.1.
A kind of preparation method of described hydrophobic type metal whisker composite, comprises the following steps：
（1）Above-mentioned butyl titanate is added in the deionized water of 24 times of its weight, is stirred, it is 43 DEG C to rise high-temperature,
Insulated and stirred 10 minutes, adds above-mentioned 1,2 methylimidazole, and insulated and stirred 20 minutes adds the anhydrous second of compound weight 17%
Alcohol, it is 70 DEG C to rise high-temperature, and insulated and stirred 30 minutes obtains metatitanic acid ester solution；
（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, adds above-mentioned alum, metatitanic acid ester solution, and stirring is equal
It is even, 3 hours are stood, suction filtration washs filter cake absolute ethyl alcohol, deionized water 3 times successively, is vacuum dried 2 hours at 30 DEG C,
Obtain 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, 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；
（4）Above-mentioned calcium ricinoleate, calcium carbonate crystal whisker are mixed, is added in the dimethylformamide of 10 times of compound weight, raised
Temperature is 50 DEG C, adds above-mentioned n salicylanilides, and ultrasound 20 minutes obtains acid amides 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 acid amides
Dispersion liquid, 100 minutes are incubated at 80 DEG C, 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）Above-mentioned sulfonated polymer modified calcium carbonate, 1H, the mixing of 1H, 2H, 2H perfluoro decyl triethoxysilane are added to
In the absolute ethyl alcohol that 1.6 times of compound weight, insulated and stirred 1 hour at 70 DEG C, suction filtration mixes precipitation with remaining each raw material
Close, stir, send into extruder, melting extrusion, cooling is obtained final product.
Performance test：
Tensile strength 31.8MPa；
Elongation at break 305%.
Claims (2)
1. a kind of hydrophobic type metal whisker composite, it is characterised in that it is made up of the raw material of following weight parts：
Calcium ricinoleate 0.7-2, polypropylene 100-130,3- (trifluoromethyl) benzophenone 24-30, hydroquinones 7-9, calcium carbonate are brilliant
Must 10-13, potassium carbonate 0.4-1, sodium carbonate 0.2-0.5, sulfolane 100-120,1H, 1H, 2H, 2H- perfluoro decyl triethoxy
Silane 0.5-1, hydroxy stearic acid 2-3, propylene glycol alginate 0.5-1, butyl titanate 6-8, alum 0.8-1,1,2-
Methylimidazole 0.6-1, n- salicylanilide 0.1-0.3.
2. a kind of preparation method of hydrophobic type metal whisker composite as claimed in claim 1, it is characterised in that including following step
Suddenly：
（1）Above-mentioned butyl titanate is added in the deionized water of 24-30 times of its weight, is stirred, liter high-temperature is 43-
50 DEG C, insulated and stirred 10-20 minutes, above-mentioned 1,2- methylimidazoles are added, insulated and stirred 20-30 minutes, add compound weight
The absolute ethyl alcohol of 17-20% is measured, it is 70-75 DEG C to rise high-temperature, insulated and stirred 30-40 minutes, obtains metatitanic acid ester solution；
（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, add above-mentioned alum, titanate esters molten
Liquid, stirs, and stands 3-5 hours, and suction filtration washs 3-4 times filter cake absolute ethyl alcohol, deionized water, at 30-40 DEG C successively
Lower vacuum drying 2-3 hours, obtains hyperbranched polyarylether ketone；
（3）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；
（4）Above-mentioned calcium ricinoleate, calcium carbonate crystal whisker are mixed, is added in the dimethylformamide of 10-13 times of compound weight, risen
High-temperature is 50-60 DEG C, adds above-mentioned n- salicylanilides, ultrasonic 20-30 minutes, obtains acid amides dispersion liquid；
（5）Above-mentioned sulfonated poly aryl ether ketone is added in the dimethylformamide of 27-30 times of its weight, is stirred, added above-mentioned
Acid amides dispersion liquid, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, and suction filtration uses filter cake
Dimethylformamide is washed 3-4 times, is vacuum dried 20-30 hours at 120-130 DEG C, obtains sulfonated polymer modified calcium carbonate；
（6）Above-mentioned sulfonated polymer modified calcium carbonate, 1H, the mixing of 1H, 2H, 2H- perfluoro decyl triethoxysilane are added to
In the absolute ethyl alcohol of 1.6-2 times of compound weight, insulated and stirred 1-2 hours at 70-78 DEG C, suction filtration is each with residue by precipitating
Raw material mixes, and stirs, and sends into extruder, and melting extrusion, cooling is obtained final product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061389A (en) * | 2021-03-29 | 2021-07-02 | 青岛科技大学 | Coating for metal and preparation method and application thereof |
| CN114530293A (en) * | 2022-03-01 | 2022-05-24 | 广东新亚光电缆股份有限公司 | Preparation method of 1 KV overhead insulated cable |
| CN116178862A (en) * | 2023-03-14 | 2023-05-30 | 广东硕为科技有限公司 | High-strength PVC composite material and preparation method and application thereof |
-
2016
- 2016-12-15 CN CN201611160756.8A patent/CN106750934A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061389A (en) * | 2021-03-29 | 2021-07-02 | 青岛科技大学 | Coating for metal and preparation method and application thereof |
| CN113061389B (en) * | 2021-03-29 | 2022-04-01 | 青岛科技大学 | Coating for metal and preparation method and application thereof |
| CN114530293A (en) * | 2022-03-01 | 2022-05-24 | 广东新亚光电缆股份有限公司 | Preparation method of 1 KV overhead insulated cable |
| CN114530293B (en) * | 2022-03-01 | 2024-04-05 | 广东新亚光电缆股份有限公司 | Preparation method of 1 kilovolt overhead insulated cable |
| CN116178862A (en) * | 2023-03-14 | 2023-05-30 | 广东硕为科技有限公司 | High-strength PVC composite material and preparation method and application thereof |
| CN116178862B (en) * | 2023-03-14 | 2023-09-26 | 广东硕为科技有限公司 | High-strength PVC composite material and preparation method and application thereof |
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Application publication date: 20170531 |