CN106832565A - A kind of silane-modified metal whisker composite and preparation method thereof - Google Patents
A kind of silane-modified metal whisker composite and preparation method thereof Download PDFInfo
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- CN106832565A CN106832565A CN201611160162.7A CN201611160162A CN106832565A CN 106832565 A CN106832565 A CN 106832565A CN 201611160162 A CN201611160162 A CN 201611160162A CN 106832565 A CN106832565 A CN 106832565A
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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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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Abstract
The invention discloses a kind of silane-modified 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, polyvinyl alcohol 34, silane coupler kh5600.6 1, benzyl triphenyl phosphonium chloride phosphine 23, calcium lactate 12, butyl oleate 0.5 1, dibasic lead phosphite 0.03 0.1, trimethyl hydroxyethylammonium ethylenediamine 0.7 1, bentonite 10 13, zinc acetylacetonate 0.6 1.The present invention uses silane-modified treatment, effectively raises the water-resistance and stability of finished composite material.
Description
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of silane-modified 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 silane-modified metal whisker composite and its
Preparation method.
The present invention is achieved by the following technical solutions：
A kind of silane-modified 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, polyvinyl alcohol 3-4, silane coupler kh5600.6-1, benzyltriphenyl phosphonium
Phosphonium chloride 2-3, calcium lactate 1-2, butyl oleate 0.5-1, dibasic lead phosphite 0.03-0.1, trimethyl hydroxyethylammonium ethylenediamine
0.7-1, bentonite 10-13, zinc acetylacetonate 0.6-1.
A kind of preparation method of described silane-modified metal whisker composite, comprises the following steps：
（1）Above-mentioned benzyl triphenyl phosphonium chloride phosphine is added in the absolute ethyl alcohol of 10-14 times of its weight, liter high-temperature is 60-70
DEG C, above-mentioned butyl oleate, dibasic lead phosphite are added, insulated and stirred 20-30 minutes, obtain alcohol dispersion liquid；
（2）Above-mentioned trimethyl hydroxyethylammonium ethylenediamine is added in 20-35 times of its weight, 47-50% ethanol solution, is stirred
Uniformly, above-mentioned zinc acetylacetonate is added, it is 70-75 DEG C to rise high-temperature, insulated and stirred 10-20 minutes, adds above-mentioned polypropylene weight
The 10-14% of amount, is sent in 130-140 DEG C of oil bath, insulated and stirred 20-30 minutes, obtains modified polypropene dispersion liquid；
（3）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, by filter cake nothing
Water-ethanol, deionized water are washed 3-4 times successively, are vacuum dried 2-3 hours at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（4）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；
（5）Above-mentioned alcohol dispersion liquid, modified polypropene dispersion liquid are mixed, is stirred, add above-mentioned bentonite, calcium lactate, surpassed
Sound 20-30 minutes, precipitation absolute ethyl alcohol, deionized water were washed 3-4 times in filtering successively, and 1- is vacuum dried at 40-50 DEG C
2 hours, obtain modification infusorial earth；
（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, modification infusorial earth, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, taken out
Filter, filter cake is washed 3-4 times with dimethylformamide, is vacuum dried 20-30 hours at 120-130 DEG C, is obtained sulfonated polymer and is 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, and the present invention uses silane-modified treatment, effectively raises
The water-resistance and stability of finished composite material.
Specific embodiment
A kind of silane-modified 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, polyvinyl alcohol 3, silane coupler kh560 0.6, benzyl triphenyl phosphonium chloride phosphine 2, calcium lactate 1, butyl oleate
0.5th, dibasic lead phosphite 0.03, trimethyl hydroxyethylammonium ethylenediamine 0.7, bentonite 10, zinc acetylacetonate 0.6.
A kind of preparation method of described silane-modified metal whisker composite, comprises the following steps：
（1）Above-mentioned benzyl triphenyl phosphonium chloride phosphine is added in the absolute ethyl alcohol of 10 times of its weight, it is 60 DEG C to rise high-temperature, is added
Above-mentioned butyl oleate, dibasic lead phosphite, insulated and stirred 20 minutes, obtain alcohol dispersion liquid；
（2）Above-mentioned trimethyl hydroxyethylammonium ethylenediamine is added in 20 times of its weight, 47% ethanol solution, is stirred, plus
Enter above-mentioned zinc acetylacetonate, it is 70 DEG C to rise high-temperature, and insulated and stirred 10 minutes adds the 10% of above-mentioned polypropylene weight, is sent to
In 130 DEG C of oil bath, insulated and stirred 20 minutes obtains modified polypropene dispersion liquid；
（3）Above-mentioned 3 (trifluoromethyl) benzophenone, hydroquinones, potassium carbonate, sodium carbonate are mixed, is added in sulfolane, be passed through
Nitrogen, at 200 DEG C react 8 hours, be added in deionized water, stand 3 hours, suction filtration, by filter cake absolute ethyl alcohol, go from
Sub- water is washed 3 times successively, is vacuum dried 2 hours at 30 DEG C, obtains 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 alcohol dispersion liquid, modified polypropene dispersion liquid are mixed, is stirred, add above-mentioned bentonite, calcium lactate, surpassed
Sound 20 minutes, filtering, precipitation absolute ethyl alcohol, deionized water are washed 3 times successively, are vacuum dried 1 hour at 40 DEG C, must be changed
Property diatomite；
（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, modification infusorial earth, 100 minutes are incubated at 80 DEG C, are passed through nitrogen, and constant temperature is stirred 4 hours, and filter cake is used two by suction filtration
Methyl nitrosourea is washed 3 times, 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 31.4MPa；
Elongation at break 301%.
Claims (2)
1. a kind of silane-modified 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, polyvinyl alcohol 3-4, silane coupler kh5600.6-1, benzyltriphenyl phosphonium
Phosphonium chloride 2-3, calcium lactate 1-2, butyl oleate 0.5-1, dibasic lead phosphite 0.03-0.1, trimethyl hydroxyethylammonium ethylenediamine
0.7-1, bentonite 10-13, zinc acetylacetonate 0.6-1.
2. a kind of preparation method of silane-modified metal whisker composite as claimed in claim 1, it is characterised in that including following
Step：
（1）Above-mentioned benzyl triphenyl phosphonium chloride phosphine is added in the absolute ethyl alcohol of 10-14 times of its weight, liter high-temperature is 60-70
DEG C, above-mentioned butyl oleate, dibasic lead phosphite are added, insulated and stirred 20-30 minutes, obtain alcohol dispersion liquid；
（2）Above-mentioned trimethyl hydroxyethylammonium ethylenediamine is added in 20-35 times of its weight, 47-50% ethanol solution, is stirred
Uniformly, above-mentioned zinc acetylacetonate is added, it is 70-75 DEG C to rise high-temperature, insulated and stirred 10-20 minutes, adds above-mentioned polypropylene weight
The 10-14% of amount, is sent in 130-140 DEG C of oil bath, insulated and stirred 20-30 minutes, obtains modified polypropene dispersion liquid；
（3）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, by filter cake nothing
Water-ethanol, deionized water are washed 3-4 times successively, are vacuum dried 2-3 hours at 30-40 DEG C, obtain hyperbranched polyarylether ketone；
（4）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；
（5）Above-mentioned alcohol dispersion liquid, modified polypropene dispersion liquid are mixed, is stirred, add above-mentioned bentonite, calcium lactate, surpassed
Sound 20-30 minutes, precipitation absolute ethyl alcohol, deionized water were washed 3-4 times in filtering successively, and 1- is vacuum dried at 40-50 DEG C
2 hours, obtain modification infusorial earth；
（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, modification infusorial earth, 100-120 minutes is incubated at 80-85 DEG C, is passed through nitrogen, and constant temperature is stirred 4-5 hours, taken out
Filter, filter cake is washed 3-4 times with dimethylformamide, is vacuum dried 20-30 hours at 120-130 DEG C, is obtained sulfonated polymer and is 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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| CN201611160162.7A CN106832565A (en) | 2016-12-15 | 2016-12-15 | A kind of silane-modified metal whisker composite and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330611A (en) * | 2018-10-11 | 2019-10-15 | 中国林业科学研究院林产化学工业研究所 | Silanization silicon whisker system and its preparation method and application |
| CN112920520A (en) * | 2021-01-27 | 2021-06-08 | 刘赛萍 | Heat-insulating nano plastic for floor and preparation method thereof |
-
2016
- 2016-12-15 CN CN201611160162.7A patent/CN106832565A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330611A (en) * | 2018-10-11 | 2019-10-15 | 中国林业科学研究院林产化学工业研究所 | Silanization silicon whisker system and its preparation method and application |
| CN112920520A (en) * | 2021-01-27 | 2021-06-08 | 刘赛萍 | Heat-insulating nano plastic for floor and preparation method thereof |
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Application publication date: 20170613 |