CN103509300B - A kind of ultrafine kaolin filling PTFE composite and preparation method thereof - Google Patents
A kind of ultrafine kaolin filling PTFE composite and preparation method thereof Download PDFInfo
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- CN103509300B CN103509300B CN201310466210.5A CN201310466210A CN103509300B CN 103509300 B CN103509300 B CN 103509300B CN 201310466210 A CN201310466210 A CN 201310466210A CN 103509300 B CN103509300 B CN 103509300B
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- ultrafine kaolin
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 51
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 51
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 44
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 42
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000011049 filling Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052961 molybdenite Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Lubricants (AREA)
Abstract
The present invention provides a kind of ultrafine kaolins to fill PTFE composite and preparation method thereof, and the composite material is mainly made of the following raw material of quality proportioning：80 ~ 95 parts of polytetrafluoroethylene (PTFE), 5 ~ 20 parts of ultrafine kaolin, 0.01 ~ 1 part of filler, 0.005 ~ 0.1 part of surfactant；The ultrafine kaolin filled polytetrafluoroethylene composite material of the present invention, since kaolin is cheap, wide application, matter is soft, can be scattered in water in suspension, with good plasticity and high caking property, excellent electrical insulation capability, therefore composite material preparation process is simple, economical and practical, has the strong market competitiveness.
Description
Technical field
The present invention relates to a kind of ultrafine kaolins to fill PTFE composite and preparation method thereof.
Background technology
Polytetrafluoroethylene (PTFE)（PTFE）Resin have friction coefficient is low, high-low temperature resistant, resistant to chemical etching, ageing-resistant, high insulation,
The advantages that not glutinous, but due to its poor dimensional stability, heat conductivility is poor, creep is big, hardness is low, especially easily grinds under loads
Damage, makes it be restricted in the application in the fields such as mechanical load bearing, friction and wear and sealing lubrication.Therefore in order to expand answering for PTFE
Filler is added in PTFE, using complex effect, reaches and improves PTFE on the basis of holding PTFE original advantages with field
The purpose of comprehensive performance.Glass fibre, carbon fiber, graphite, molybdenum disulfide, cenosphere and various ceramic powders are the most frequently used at present
Filler, but they have shortcoming, if glass fibre is not alkaline-resisting and hydrofluoric acid, not wear-resisting in water, glass fibre meeting
Dual face is damaged, molybdenum disulfide, graphite, bronze powder, various ceramic powder hardness is big, easy to wear, it is, thus, sought for more adduction
Suitable packing material, comes that processability is excellent, the more wide PTFE composite of application.
Kaolin is a kind of cheap layer silicate mineral material, and matter is soft, easy suspended dispersed in water and has
Good plasticity and high caking property, excellent electrical insulation capability, good antiacid dissolubility, very low cation exchange capacity (CEC) etc.
Property.Therefore it is required to have become institute in tens industries such as papermaking, ceramics, rubber, chemical industry, coating, medicine and national defence for kaolin
Raw mineral materials.Kaolin as the filler of plastics and rubber in use, frosting can be kept smooth, improve dimensional accuracy and
It is resistant to chemical etching, and have the advantages that improve tribological properties performance and mechanical property, thus kaolin in plastics and
Aspect is with a wide range of applications in rubber.
Invention content
It is an object of the present invention to provide the preparation sides of a kind of simple, at low cost ultrafine kaolin filling PTFE composite
Method, the ultrafine kaolin filling PTFE composite being prepared using this method are had excellent performance, are had wide range of applications.
The technical solution adopted by the present invention is：
A kind of ultrafine kaolin filling PTFE composite, is mainly made of the following raw material of quality proportioning：
80 ~ 95 parts of polytetrafluoroethylene (PTFE)
5 ~ 20 parts of ultrafine kaolin
0.01 ~ 1 part of filler
0.005 ~ 0.1 part of surfactant；
The grain size of the polytetrafluoroethylene (PTFE) is 20~200 μm；
The grain size of the ultrafine kaolin is 0.02~20 μm；
The filler is one of following：Aluminium oxide, zinc oxide, silica, glass fibre, carbon fiber, graphite, graphene,
MoS2, grain size is 0.02 μm ~ 20 μm, preferably aluminium oxide, graphite or MoS2；
The surfactant is one of following：Perfluoro caprylic acid, perfluorinated sulfonic acid, perfluorooctanoic acid or Nonyl pheno
Ether, preferably perfluoro caprylic acid.
Above-mentioned is the solid material for preparing the composite material, does not include water used in preparation process.
The invention further relates to the method for preparing the ultrafine kaolin filling PTFE composite, the method is as follows：
（1）The surfactant of formula ratio is soluble in water, it is made into the solution of mass concentration 0.05 ~ 1%；
（2）Toward step（1）Polytetrafluoroethylene (PTFE), ultrafine kaolin ultrasonic disperse are sequentially added in solution, are added filler, are stirred
It mixes uniformly, obtains mixture；
（3）Step（2）Gained mixture is dried, the cold moudling under 30~40MPa pressure, pressurize 3~10 minutes；
（4）Step（3）Gained molding is put into high temperature sintering furnace, and 200~380 DEG C keep the temperature 0.5~4 hour；
（5）Step（4）Gained sintered product is cooled to room temperature, and obtains the ultrafine kaolin filling PTFE composite.
Step（4）Method can be as follows：Step（3）Gained molding is put into high temperature sintering furnace, with 30~100 DEG C/h
Heating rate heating, when temperature reach 250~320 DEG C when keep the temperature 1~2 time, each soaking time be 20~40 minutes；Then
Continue to be heated to 350~380 DEG C with 30~100 DEG C/min of heating rate, keeps the temperature 0.5~2 hour；
Step（5）Method can be as follows：Step（4）The sintered product of gained is cooled to 250~320 with 30~100 DEG C/h
DEG C when keep the temperature 20~40 minutes, then cooled to room temperature obtains ultrafine kaolin filling PTFE composite.
PTFW composite materials are filled using the ultrafine kaolin that the method for the present invention is prepared, by national standard GB/T-3960-
1983 detections, abrasion loss≤2.5mg, friction coefficient≤0.2 are detected by national standard GB-T2411-1980, and shore hardness >=
58.0, it is detected by ASTMD955, shrinking percentage≤2.5%.
Ultrafine kaolin of the present invention fills PTFE composite, can prepare the delivery pipe of conveying corrosive gas, exhaust pipe,
Steam pipe and rolling mill high-pressure oil pipe, plane hydraulic system and the senior middle school's low pressure pipeline, rectifying column, the heat exchanger that are cold-pressed system
And the chemical industry equipments such as lining valve of kettle, tower, slot；The support slipper of structure roof truss, large-size chemical pipeline, storage tank, Yi Jiqiao
Beam support and the equipment such as swivel of building bridge.
The beneficial effects are mainly as follows：The ultrafine kaolin filled polytetrafluoroethylene composite material of the present invention,
Since kaolin is cheap, wide application, matter is soft, can disperse to suspend in water, and is ground with polymer friction is improved
The advantages of damaging performance and mechanical property, therefore composite material preparation process is simple, it is economical and practical, there is stronger market competition
Power.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
Raw material：
PTFE （50 μm of granularity）, 85 mass parts；
Kaolin（0.2 μm of granularity）, 15 mass parts；
Al2O3 （Granularity 60nm）, 0.05 mass parts；
Perfluoro caprylic acid, 0.05 mass parts；
Method：
（1）Perfluoro caprylic acid is soluble in water, it is made into the solution of mass concentration 0.5%；
（2）Toward step（1）Polytetrafluoroethylene (PTFE), ultrafine kaolin are sequentially added in solution, ultrasound（250W, 26KHz）Dispersion
10 minutes, filler is added, is stirred evenly, mixture is obtained；
（3）Mixture is put into blender high speed and stirs evenly, and then suppresses lower cold moudling in 38Mpa（That is, at room temperature
Compression moulding）, the cold pressing time is 5 minutes；
（4）Step（3）Gained molding is put into high temperature sintering furnace, is heated with 80 DEG C/h of heating rate, is worked as temperature
30 minutes are kept the temperature when reaching 330 DEG C；It then proceedes to be heated to 370 DEG C with 60 DEG C/h of heating rates, keeps the temperature 0.5 hour；
（5）Step（4）Sintered product keeps the temperature 24 minutes when being cooled to 330 DEG C with 60 DEG C/h of rate, then natural cooling
To room temperature, ultrafine kaolin filling PTFE composite is obtained.
The ultrafine kaolin is filled PTFE composite and is detected by GB/T-3960-1983, and bold and unconstrained gram of abrasion loss≤2.5 are rubbed
Wipe coefficient≤0.19；It is detected by GB-T2411-1980, wherein shore hardness >=61.0；It is detected by ASTM D955, shrinking percentage
≤2.2%；Respectively in the concentrated sulfuric acid and sodium hydroxide（Concentration 40%, w/w）It is placed 24 hours in solution, ultrafine kaolin filling is multiple
Condensation material does not corrode.
Embodiment 2：
Raw material：
PTFE （65 μm of granularity）, 85 mass parts；
Kaolin（0.1 μm of granularity）, 15 mass parts；
Graphite（30μm）, 0.05 mass parts；
Perfluoro caprylic acid, 0.05 mass parts；
Method：
（1）Perfluoro caprylic acid is soluble in water, it is made into the solution of mass concentration 0.5%；
（2）Toward step（1）Polytetrafluoroethylene (PTFE), ultrafine kaolin are sequentially added in solution, ultrasound（250W, 26KHz）Dispersion
10 minutes, filler is added, is stirred evenly, mixture is obtained；
（3）Mixture is put into blender high speed and stirs evenly, then again 110 DEG C dry 2 hours, it is then strong in 35Mpa
Depress cold moudling（That is, compression moulding at room temperature）, the cold pressing time is 8 minutes；
（4）Molding is put into high temperature sintering furnace, is heated with 80 DEG C/h of heating rate, when temperature reaches 290 oWhen C
Heat preservation 30 minutes；It then proceedes to be heated to 380 with 60 DEG C/h of heating ratesoC keeps the temperature 0.5 hour；
（5）Sintered product keeps the temperature 30 minutes when being cooled to 290 DEG C with 60 DEG C/h of rate, then cooled to room temperature,
It obtains ultrafine kaolin and fills PTFE composite.
The ultrafine kaolin is filled PTFE composite and is detected by GB/T-3960-1983, and bold and unconstrained gram of abrasion loss≤2.5 are rubbed
Wipe coefficient≤0.18；It is detected by GB-T2411-1980, wherein shore hardness >=60.0；It is detected by ASTM D955, shrinking percentage
≤2.2%；Respectively in the concentrated sulfuric acid and sodium hydroxide（Concentration 40%）It is placed 24 hours in solution, the ultrafine kaolin filled composite material
Material does not corrode.
Embodiment 3：
Raw material：
PTFE （65 μm of granularity）, 90 mass parts；
Kaolin（0.1 μm of granularity）, 9 mass parts；
MoS2 （0.06μm）, 1 mass parts；
Perfluorinated sulfonic acid, 0.05 mass parts；
Method：
（1）Perfluoro caprylic acid is soluble in water, it is made into the solution of mass concentration 0.5%；
（2）Toward step（1）Polytetrafluoroethylene (PTFE), ultrafine kaolin are sequentially added in solution, ultrasound（250W, 26KHz）Dispersion
10 minutes, filler is added, is stirred evenly, mixture is obtained；
（3）Mixture is put into blender high speed and stirs evenly, then again 100 DEG C dry 2 hours, it is then strong in 35Mpa
Depress cold moudling（That is, compression moulding at room temperature）, the cold pressing time is 5 minutes；
（4）Molding is put into high temperature sintering furnace, is heated with 80 DEG C/h of heating rate, when temperature reaches 290 DEG C
Shi Baowen 30 minutes；It then proceedes to be heated to 380 DEG C with 60 DEG C/h of heating rates, keeps the temperature 0.5 hour；
（5）Sintered product keeps the temperature 30 minutes when being cooled to 290 DEG C with 60 DEG C/h of rate, then naturally cools to room
Temperature obtains ultrafine kaolin filling PTFE composite.
The ultrafine kaolin is filled PTFE composite and is detected by GB/T-3960-1983, and bold and unconstrained gram of abrasion loss≤2.5 are rubbed
Wipe coefficient≤0.19；It is detected by GB-T2411-1980, wherein shore hardness >=59.0；It is detected by ASTM D955, shrinking percentage
≤2.2%；Respectively in the concentrated sulfuric acid and sodium hydroxide（Concentration 40%）It is placed 24 hours in solution, the ultrafine kaolin filled composite material
Material does not corrode.
Claims (1)
1. a kind of ultrafine kaolin fills PTFE composite, mainly it is made of the following raw material of quality proportioning：
The grain size of the polytetrafluoroethylene (PTFE) is 20~200 μm；
The grain size of the ultrafine kaolin is 0.02~20 μm；
The filler is one of following：Aluminium oxide, zinc oxide, silica, glass fibre, carbon fiber, graphite, graphene, MoS2,
Grain size is 0.02 μm~20 μm；
The surfactant is one of following：Perfluoro caprylic acid, perfluorinated sulfonic acid, perfluorooctanoic acid or nonylphenol polyoxyethylene ether；
The ultrafine kaolin filling PTFE composite comprises the following steps：
(1) surfactant of formula ratio is soluble in water, it is made into the solution of mass concentration 0.05~1%；
(2) polytetrafluoroethylene (PTFE), ultrafine kaolin ultrasonic disperse are sequentially added into step (1) solution, adds filler, stirring is equal
It is even, obtain mixture；
(3) mixture drying, the cold moudling under 30~40MPa pressure, pressurize 3~10 minutes obtained by step (2)；
(4) molding obtained by step (3) is put into high temperature sintering furnace, and 200~380 DEG C keep the temperature 0.5~4 hour；
(5) sintered product obtained by step (4) is cooled to room temperature, and obtains the ultrafine kaolin filling PTFE composite.
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| CN201310466210.5A CN103509300B (en) | 2013-10-09 | 2013-10-09 | A kind of ultrafine kaolin filling PTFE composite and preparation method thereof |
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| CN103897308A (en) * | 2014-03-27 | 2014-07-02 | 安徽卧龙泵阀有限责任公司 | Process for forming strong-acid resistant composite material for anticorrosive lining of chemical process pump |
| CN103897305A (en) * | 2014-03-27 | 2014-07-02 | 安徽卧龙泵阀有限责任公司 | Strong alkali-resisting composite material of chemical process pump anticorrosion liner |
| CN105860378A (en) * | 2015-12-21 | 2016-08-17 | 无锡科莱欣机电制造有限公司 | Antioxidant plastic stent for solar cell panel |
| CN106243588A (en) * | 2016-08-23 | 2016-12-21 | 安徽海德石油化工有限公司 | A kind of alkylation acid hydrocarbon separation coalescent pack |
| CN107987435A (en) * | 2017-11-21 | 2018-05-04 | 浙江德清科赛塑料制品有限公司 | kaolin filled polytetrafluoroethylene material |
| CN107936425A (en) * | 2017-11-25 | 2018-04-20 | 郑州莉迪亚医药科技有限公司 | A kind of high-strength material and its preparation method and application |
| CN109021471B (en) * | 2018-08-09 | 2019-10-29 | 燕山大学 | Molybdenum disulfide-nickel phosphorus-ptfe composite preparation method |
| CN114989547B (en) * | 2022-06-24 | 2024-01-02 | 佛山科学技术学院 | Polymer composite material with abrasion in-situ repair function and preparation method and application thereof |
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| CN102731941A (en) * | 2012-06-13 | 2012-10-17 | 浙江大学 | Preparation method of teflon composite material |
| CN103289260B (en) * | 2013-05-07 | 2015-11-04 | 浙江大学 | The preparation method of ultrafine zeolite powder Filled PTEF matrix material |
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