CN104046009A - Nylon 6-polytetrafluoroethylene composition - Google Patents
Nylon 6-polytetrafluoroethylene composition Download PDFInfo
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- CN104046009A CN104046009A CN201410298809.7A CN201410298809A CN104046009A CN 104046009 A CN104046009 A CN 104046009A CN 201410298809 A CN201410298809 A CN 201410298809A CN 104046009 A CN104046009 A CN 104046009A
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- nylon
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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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)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a nylon 6-polytetrafluoroethylene composition which is prepared by the following steps: in a high-pressure reaction kettle, adding pure water and a polymerization inhibitor, adding certain amounts of dispersing agent, initiator, nylon 6 powder, vinylidene fluoride, perfluoromethylvinyl ether and maleic anhydride, heating to reaction temperature, reacting to obtain surface-polymerized nylon 6, filtering the product, drying, mixing with polytetrafluoroethylene in a high-speed mixer, and grinding and crushing in a grinding machine to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method of modification of nylon, particularly the composition of a kind of nylon 6 and tetrafluoroethylene.
Background technology
Nylon (PA) has higher mechanical property, impact property, higher thermotolerance, good wear resistance, self lubricity, there is good processibility, mechanics harmony is good, on household electrical appliance, automotive industry and tool-making, be widely used, its application occupies first of five large-engineering plastics.Pure nylon does not reach roller transport trolley wheel aspect physical strength, the requirement of the products such as gear, mechanical fastener, and common mineral, the fiber-reinforced modified requirement not reaching this series products aspect wear-resisting and toughness.
In nylon matrix, to be dispersed into island shape (diameter 011～1 μ phase dispersed texture m) with modified polyolefin as the polyolefine of impact modifying agent and the blend of nylon, its modified polyolefin just becomes striking energy cartridge, and this type of alloy can improve shock strength and the reduction water absorbability of nylon under low temperature, dry state.Nylon and the blend alloy of the composition such as polyolefine or its elastomeric graft copolymer that contains alkyl can obtain the nylon material of super toughness.
CN101885910 relates to a kind of high wear-resistant PA 66 composite material and preparation method thereof, this matrix material is made up of the raw material of following component and weight percent: nylon 56-82%, anti-wear agent 1#2-5%, anti-wear agent 2#2-5%, glass fiber powder 5-15%, glass microballon 5-15%, graft type plasticized modifier 2-8%, nucleator 0.1-0.5%, oxidation inhibitor 0.1-1%, lubrication dispersing agent 0.1-0.5%.Compared with prior art, the present invention has high abrasion, high heat resistance, the higher advantage such as toughness and high workability.Described anti-wear agent 1# is tetrafluoroethylene, and described anti-wear agent 2# is molybdenumdisulphide.Graft type plasticized modifier is the oligopolymer of the graft polymerization of polyene elastomerics (POE) grafting unsaturated acid or acid anhydrides, is maleic anhydride graft polyene elastomerics.
EPO, 649,738A1 discloses by add poly-glutarimide to polymeric amide, can produce the connection of a kind of power of enforcement locking polymeric amide and fluorinated ethylene propylene.So, for example, by using a step extrusion process to make the veneer sheet (laminate) of pair of lamina and by polymeric amide, gathered the viscosity promotor layer of the compositions of mixtures of glutarimide by polymeric amide, and fluorinated ethylene propylene to make the veneer sheet of three layers by polymeric amide and fluorinated ethylene propylene.
Existing all have complicated components containing PA6 composition known technology, and between high molecular polymer, consistency is poor, mixes the shortcomings such as inhomogeneous, has affected the result of use in full scale plant.
Summary of the invention
For the deficiencies in the prior art, the invention provides the composition of a kind of nylon 6 and tetrafluoroethylene.
In autoclave, squeeze into pure water, stopper, add a certain amount of dispersion agent, initiator, nylon 6 powders, vinylidene, perfluoro methyl vinyl ether, maleic anhydride, be warming up to temperature of reaction, question response finishes, and obtains the nylon 6 of surface aggregate, product after filtration, is dried, and then mixes at high-speed mixer with tetrafluoroethylene, in pulverizing mill, grind again fragmentation, obtain this patent product.
The present invention introduces the vinylidene with fluorine element on a small quantity on nylon 6 particle surfaces, perfluoro methyl vinyl ether, and maleic anhydride is as comonomer, carries out surface modification, can improve the consistency of nylon 6 and PTFE polymkeric substance.
The invention provides the composition of a kind of nylon 6 and tetrafluoroethylene, realize by following steps:
The preparation of step 1. water
By weight, add 1000 parts of water in autoclave, 0.5-2 part emulsifying agent (preferably 1 part), stirs;
The preparation of step 2. oil phase
In reactor, by weight, by 100 parts of nylon 6,0.5-3 part (preferably 1.5 parts) maleic anhydride mixes, then adds 0.05-0.1 part initiator (preferably 0.05 part), stirs.
Step 3. polyreaction
The oil-phase solution that step 2 is prepared is added in step 1 and is equipped with in the reactor of preparing water, pass into 0.5-3 part (preferably 1.5 parts) vinylidene fluoride monomers, 0.05-0.5 part (preferably 0.2 part) perfluoro methyl vinyl ether monomer, then from 70-100 DEG C (preferably 80 DEG C) reaction 8-20h (preferably 10h), reaction finishes rear blowing, product after filtration, is dried.
Step 4. blend
70-95 part step 3 is obtained to nylon 6 powders of surface modification, mix with 5-30 part PTFE powder, mix at high-speed mixer, then grind fragmentation in pulverizing mill, obtain this patent product.
Described chemical dispersant comprises any one in Perfluorocaprylic Acid sylvite or ammonium salt and the pungent sulfonate sodium of perfluor alkane or ammonium salt.Preferably Potassium perfluorooctanoate.
The preferred Potassium Persulphate of described initiator, ammonium persulphate.
Described high-speed mixer is commercially available prod, if Nanjing wheat is to the high-speed mixer product of mechanical major production.
Described pulverizing mill can be used to preparation/mixed powder or other materials, and described equipment can comprise, without limitation, for example: multiple agitator, comprise revolving stirrer, and multiple pulverizing mill, comprise ball mill, electromagnetic ball grinding machine, disc flour mill, needle mill, high energy impact shredder, stream energy impact mill, reversal nozzle jet mill, fluidised-bed spray grinding machine, beater grinder, tumbling mill, mechanic diffusion handler, or impact mill.In described pulverizing mill, at a high speed and high strength can be employed or be applied on dry powder material, to realize high-shear or HI high impact is applied to dry powder material, be preferably fluidised-bed spray grinding machine.For commercially available prod, as the product of Mianyang Liuneng Powder Equipment Co., Ltd.'s production.
Described vinylidene is commercially available prod, as the product of Shandong Huaxia Shenzhou New Material Co., Ltd.'s production.
Described perfluoro methyl vinyl ether is commercially available prod, as the product of Zhong Lan morning twilight Chemical Co., Ltd. production.
Described nylon 6 is commercially available prod, as 1013G30 trade mark nylon 6 products of 1013G30 Mitsubishi engineering.
Beneficial effect of the present invention:
Nylon 6 is through maleic anhydride and vinylidene fluoride monomers, and perfluoro methyl vinyl ether monomer carries out surface modification, has improved and the consistency of tetrafluoroethylene, can be being pulverized and mixed contact fully in process, and dispersion more even.Fluoropolymer is coated at nylon 6 particle surfaces, has reduced the surface energy of nylon 6 particles, has improved the scratch resistance of particle surface, and the frictional coefficient of composition is reduced.
Embodiment
Following examples are only to further illustrate the present invention, are not restriction the scope of protection of the invention.
The invention provides the composition of a kind of nylon 6 and tetrafluoroethylene, realize by following steps:
Embodiment 1
The preparation of step 1. water
In in 2000L autoclave, add 1000Kg water, 1Kg Potassium perfluorooctanoate, stirs.
The preparation of step 2. oil phase
In 200L reactor, 6,1.5 parts of maleic anhydrides of 100 parts of nylon are mixed, then add 0.08 part of ammonium persulphate, stir.
Step 3. polyreaction
The oil-phase solution that step 2 is prepared is added in step 1 and is equipped with in the reactor of preparing water, passes into 1.5Kg vinylidene fluoride monomers, 0.2Kg perfluoro methyl vinyl ether monomer, then from 90 DEG C of reaction 14h, reaction finishes rear blowing, after filtration, be dried, obtain nylon 6 powders of surface grafting.
Step 4. blend is pulverized
Nylon 6 powders that 80Kg step 3 obtained to surface grafting, then mix with 20KgPTFE powder, mix, then grind fragmentation at 500L high-speed mixer in fluidised-bed spray grinding machine, obtain this patent product.Be numbered SX-1.
Embodiment 2
The preparation of step 1. water
In in 2000L autoclave, add 1000Kg water, the pungent sodium sulfonate of 0.5Kg perfluor alkane, stirs.
The preparation of step 2. oil phase
In 200L reactor, by 100Kg nylon 6,0.5Kg maleic anhydride body mixes, then adds 0.05Kg Potassium Persulphate, stirs.
Step 3. polyreaction
The oil-phase solution that step 2 is prepared is added in step 1 and is equipped with in the reactor of preparing water, passes into 0.5Kg vinylidene fluoride monomers, 0.05Kg perfluoro methyl vinyl ether monomer, then from 70 DEG C of reaction 20h, reaction finishes rear blowing, after filtration, be dried, obtain nylon 6 powders of surface grafting.
Step 4. blend is pulverized
70Kg step 3 is obtained to the nylon 6 of surface grafting, mix at 300L high-speed mixer with 30KgPTFE powder, then grind fragmentation in fluidised-bed spray grinding machine, obtain this patent product.Be numbered SX-2.
Embodiment 3
The preparation of step 1. water
In in 2000L autoclave, add 1000Kg water, the pungent ammonium sulphonate of 2Kg perfluor alkane, stirs.
The preparation of step 2. oil phase
In 200L reactor, by 100Kg nylon 6,3Kg maleic anhydride, mixes, then adds 0.1Kg Potassium Persulphate, stirs.
Step 3. polyreaction
The oil-phase solution that step 2 is prepared is added in step 1 and is equipped with in the reactor of preparing water, passes into 2Kg vinylidene fluoride monomers, 0.5Kg perfluoro methyl vinyl ether monomer, then from 100 DEG C of reaction 10h, reaction finishes rear blowing, after filtration, be dried, obtain the nylon 6 of surface grafting.
Step 4. blend is pulverized
90 parts of steps 3 are obtained to nylon 6 powders of surface grafting, then mix at 300L high-speed mixer with 10 parts of PTFE powders, then grind fragmentation in fluidised-bed spray grinding machine, obtain this patent product.Be numbered SX-3.
Comparative example 1
Nylon 6 does not carry out grafting, only carries out the blend of step 4, does not carry out the reaction of step 1-3, the other the same as in Example 1.Products obtained therefrom is numbered SX-4.
Comparative example 2
Only adopt nylon 6 for one-component, production code member is SX-5.
Embodiment 4
The micro mist making in embodiment 1-3 and comparative example 1-2, frictional coefficient is tested by GB3960-83 standard.Test load 20Kg.
| Embodiment sample | Frictional coefficient |
| SX-1 | 0.17 |
| SX-2 | 0.19 |
| SX-3 | 0.12 |
| SX-4 | 0.32 |
| SX-5 | 0.59 |
Claims (3)
1. a composition for nylon 6 and tetrafluoroethylene, is characterized in that comprising the following steps:
The preparation of step 1. water
By weight, add 1000 parts of water in autoclave, 0.5-2 part emulsifying agent, stirs;
The preparation of step 2. oil phase
In reactor, by weight, by 100 parts of nylon 6,0.5-3 part maleic anhydride mixes, then adds 0.05-0.1 part initiator, stirs.
Step 3. polyreaction
The oil-phase solution that step 2 is prepared is added in step 1 and is equipped with in the reactor of preparing water, passes into 0.5-3 part vinylidene fluoride monomers, 0.05-0.5 part perfluoro methyl vinyl ether monomer, then from 70-100 DEG C of reaction 8-20h, reaction finishes rear blowing, and product after filtration, is dried.
Step 4. blend
70-95 part step 3 is obtained to nylon 6 powders of surface modification, mix with 5-30 part PTFE powder, mix at high-speed mixer, then grind fragmentation in pulverizing mill, obtain this patent product.
2. a composition for nylon 6 and tetrafluoroethylene, is characterized in that, uses maleic anhydride in step 2, vinylidene fluoride monomers, and perfluoro methyl vinyl ether monomer carries out surface aggregate to nylon 6.
3. a composition for nylon 6 and tetrafluoroethylene, is characterized in that, in step 4, the nylon of surface modification 6 is mixed with PTFE, mixes, then in pulverizing mill, grind fragmentation and obtain this patent product at high-speed mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298809.7A CN104046009B (en) | 2014-06-20 | 2014-06-20 | A kind of nylon 6 and the compositions of politef |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298809.7A CN104046009B (en) | 2014-06-20 | 2014-06-20 | A kind of nylon 6 and the compositions of politef |
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| Publication Number | Publication Date |
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| CN104046009A true CN104046009A (en) | 2014-09-17 |
| CN104046009B CN104046009B (en) | 2016-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410298809.7A Active CN104046009B (en) | 2014-06-20 | 2014-06-20 | A kind of nylon 6 and the compositions of politef |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751751A (en) * | 2016-11-22 | 2017-05-31 | 袁洁 | A kind of hydrophobic enhancing nylon composite materials |
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| CN1234476A (en) * | 1998-02-28 | 1999-11-10 | 联合莫古尔威斯巴登有限公司 | Overlay material and composite multilayer material |
| CN1236341A (en) * | 1997-08-12 | 1999-11-24 | 北美埃尔夫爱托化学股份有限公司 | Polyamide and polyvinylidene fluoride resin powder coatings |
| US6072001A (en) * | 1997-12-26 | 2000-06-06 | Industrial Technology Research Institute | Long-term antistatic composition |
| CN101302338A (en) * | 2008-05-21 | 2008-11-12 | 深圳市科聚新材料有限公司 | High-toughness, wear-resistant, self-lubricating polyamide material and preparation thereof |
| CN101790453A (en) * | 2007-06-27 | 2010-07-28 | 阿克马法国公司 | Use of nanotubes, especially carbon nanotubes, to improve the high temperature mechanical properties of a polymeric matrix |
| CN101885910A (en) * | 2009-05-12 | 2010-11-17 | 上海日之升新技术发展有限公司 | High wear-resistant PA66 composite material and preparation method thereof |
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2014
- 2014-06-20 CN CN201410298809.7A patent/CN104046009B/en active Active
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| CN1236341A (en) * | 1997-08-12 | 1999-11-24 | 北美埃尔夫爱托化学股份有限公司 | Polyamide and polyvinylidene fluoride resin powder coatings |
| US6072001A (en) * | 1997-12-26 | 2000-06-06 | Industrial Technology Research Institute | Long-term antistatic composition |
| CN1234476A (en) * | 1998-02-28 | 1999-11-10 | 联合莫古尔威斯巴登有限公司 | Overlay material and composite multilayer material |
| CN101790453A (en) * | 2007-06-27 | 2010-07-28 | 阿克马法国公司 | Use of nanotubes, especially carbon nanotubes, to improve the high temperature mechanical properties of a polymeric matrix |
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| CN101942162A (en) * | 2009-06-18 | 2011-01-12 | 日立电线精密技术株式会社 | Modified fluorocarbon resin composition and molded products |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751751A (en) * | 2016-11-22 | 2017-05-31 | 袁洁 | A kind of hydrophobic enhancing nylon composite materials |
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| CN104046009B (en) | 2016-09-14 |
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