CN104109378B - A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) - Google Patents
A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) Download PDFInfo
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- CN104109378B CN104109378B CN201410290602.5A CN201410290602A CN104109378B CN 104109378 B CN104109378 B CN 104109378B CN 201410290602 A CN201410290602 A CN 201410290602A CN 104109378 B CN104109378 B CN 104109378B
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- nylon
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- polytetrafluoroethylene
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention provides a kind of nylon 46 and the composition of polytetrafluoroethylene (PTFE)：In a kettle., pure water, polymerization inhibitor are squeezed into, add a certain amount of dispersant, initiator, nylon 46 powder, acrylic anhydride, γ (methacryloxypropyl) propyl trimethoxy silicane (KH 570), is warming up to reaction temperature, question response terminates, and obtains the nylon 46 of surface aggregate, product is through filtering, drying, then mixed with polytetrafluoroethylene (PTFE) in high-speed mixer, then grind broken in flour mill, obtain this patent product.
Description
Technical field
The present invention relates to a kind of preparation method of modified nylon 46, particularly a kind of nylon 46 and
Composition of polytetrafluoroethylene (PTFE) and preparation method thereof.
Background technology
Nylon 46 (PA46) is the fatty polyamide by butanediamine and adipic acid polycondensation, although have Buddhist nun
Imperial 66 similar molecular structures, but the acid amides group number on the chain of PA46 each given length is more, and chain structure is more symmetrical；And it is high
Spending symmetrical chain structure causes its crystallinity high, and crystallization rate is fast, thus fusing point is higher, and heat distortion temperature is also high, and grows
Phase temperature in use is up to 163 DEG C.These characteristics make PA46 than other engineering plastics such as PA6, PA66, PPA and polyester heat-resisting, high
The lower mechanical strength of temperature, it is wear-resisting in terms of there is technical advantage, and short molding cycle, processing is more economical.
High-performance polyamide 46 has the performance and value for being difficult analogy in automobile and electronic application field, it is possible to provide high temperature
Under the conditions of very good mechanical properties, remarkable wearability and low friction and excellent mobility so that working process is more square
Just, particular design is more flexible.Performance has surmounted PPA, PA6T, PA9T, while generally excellent under the condition of work for needing high temperature
In PPS and LCP materials.
It is to be dispersed into improved polyalkene in nylon matrix as the polyolefin of impact modifying agent and the blend of nylon
The phase dispersed structure of island shape (011~1 μm of diameter), its improved polyalkene is become as impact energy absorber, and such alloy can be carried
Impact strength and reduction hygroscopicity of the high nylon under low temperature, dry state.Nylon with containing the polyolefin of alkyl or its elastomer
The blend alloy of the compositions such as graft copolymer can obtain the nylon material of ultra-tough.
Being related to the composition containing nylon 46 (PA46) has open report：
CN102942785 is related to a kind of nylon 46 composite of the unleaded soldering of resistance to hygrometric state and preparation method thereof.The nylon
46 composites are by weight percentage, composed of the following components：PA46 resins 40.4-89.2%；PPO resins 5-15%；It is compatible
Agent 0-5%；Glass fibre 0-45%；Other auxiliary agents 1-2%.The composite manufacturing technique is as follows：According to above-mentioned weight hundred
Divide ratio to weigh each component, and raw material components are dried with processing；By dried PA46 resins, PPO resins, compatilizer,
Mixed in auxiliary agent input high-speed mixer；Material after mixing is added in double screw extruder, and adds glass fibre
Strengthened, extruding pelletization.It can be applied to prepare the connector and high temperature resistant for the electric equipment products for needing to be subjected to no lead-tin soldering
It is required that the field such as automobile plastic parts.
CN102604382A discloses the PA alloy materials and preparation method of a kind of high thermal resistance, high-rigidity high torque.It is main former
Expect that weight percentages of components is：PA46*PA66: 45-75%, PPS: 10-35%, POE-g-MAH: 3-10%, glass fibre 8-
25%, carbon fiber f10%, coupling agent 0.5-1.5%.The invention is condensed together by a variety of high polymer materials is made a kind of conjunction
Metal working engineering plastics, make the superior function of various high polymer materials carry out complementation, so as to obtain a kind of high heat-resisting, height based on PA
Rigidity, the new material of high torque.
The existing known technology of composition containing PA46 all has poor compatibility between complicated components, high molecular polymer, mixing
Uneven the shortcomings of, it have impact on the using effect in commercial plant.
The content of the invention
In view of the shortcomings of the prior art, the invention provides the combination of a kind of nylon 46 and polytetrafluoroethylene (PTFE)
Thing.
In a kettle., pure water is squeezed into, polymerization inhibitor adds a certain amount of dispersant, initiator, nylon 46 powder
Body, acrylic anhydride, γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) is warming up to reaction temperature, question response knot
Beam, obtains the nylon 46 of surface aggregate, product is through filtering, drying, then with polytetrafluoroethylene (PTFE) in high-speed mixer
Mixing, then grind broken in flour mill, obtain this patent product.The present invention is introduced on nylon 46 particle surface
The a small amount of acrylic anhydride with double bond and Third monomer KH570 carry out surface modification, can improve poly hexamethylene adipamide fourth as comonomer
The compatibility of diamines and PTFE polymer.
The present invention provides the composition of a kind of nylon 46 and polytetrafluoroethylene (PTFE), is realized by following steps：
The preparation of step 1. aqueous phase
By weight, interior in a kettle. to add 1000 parts of water, 0.5-2 parts of emulsifying agents (preferably 1 part) stir；
The preparation of step 2. oil phase
By weight, by 100 parts of nylon 46 powders, 0.5-2 parts of (preferably 1 part) KH570 monomers, 0.5-2
Part (preferably 1.5 parts) acrylic anhydride mixing, adds 0.05-0.1 parts of initiators (preferably 0.05 part), stirs.
Step 3. polymerisation
The oil-phase solution that step 2 is prepared is added in step 1 equipped with the reactor for having prepared aqueous phase, is passed through, Ran Houcong
70-100 DEG C (preferably 90 DEG C) reaction 8-20h (preferably 10h), reaction terminates rear blowing, and product is through filtering, drying.
Step 4. is blended
70-90 parts of steps 3 are obtained to the nylon 46 powder of surface modification, mixed with 10-30 parts of PTFE powders,
Grind broken in high-speed mixer mixing, then in flour mill, obtain this patent product.
The chemical dispersant includes anion emulsifier, is ammonium lauryl sulfate, neopelex, 16
The chain alkyl types such as sodium alkyl benzene sulfonate, B-53, polyoxyethylene alkyl ether sodium sulphate and paraffin sulfonate are cloudy
Any one in ionic emulsifying agent, perfluoro caprylic acid sylvite or ammonium salt and the pungent sulfonate sodium of perfluor alkane or ammonium salt.It is preferred that 12
Alkylsurfuric acid ammonium.
The preferred potassium peroxydisulfate of initiator, ammonium persulfate.
The high-speed mixer is commercially available prod, the high-speed mixer product that such as Nanjing wheat produces to mechanical major.
The flour mill can be used for preparation/mixed powder or other materials, and the equipment may include, without limitation,
For example：A variety of agitators, including Stirring device, and a variety of flour mills, including ball mill, electromagnetism ball mill, disc flour mill,
Needle mill, high energy impact grinder, stream can impact grinder, reversal nozzle jet mill, fluidized bed jet mill, hammer type crushing
Machine, tumbling mill, mechanic diffusion processor, or impact grinder.In the flour mill, can be employed with high intensity at a high speed or
It is applied on dry powder material, to realize that high shear or HI high impact are applied to dry powder material, preferably fluidized bed jet mill.For city
Sell the product of product, such as Mianyang Liuneng Powder Equipment Co., Ltd.'s production.
The γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) is commercially available prod, such as Qingdao rising sun sunrise
The product of work Co., Ltd production.
The nylon 46 powder is commercially available prod, such as the product of Guangzhou Hong Shi trade Co., Ltds production.
Beneficial effects of the present invention：
Nylon 46 is through acrylic anhydride and γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570)
Surface modification is carried out, the compatibility with polytetrafluoroethylene (PTFE) is improved, can sufficiently be contacted during being pulverized and mixed, it is scattered
Evenly.γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) is under free radical initiation, and C=C double bonds easily occur
Polycondensation is easily hydrolyzed in alkoxy in polymerisation, its molecular structure at room temperature, forms cross-linked network, is conducive in blending
Middle raising and the adhesion of ptfe micropowder.
Embodiment
Following examples are only to further illustrate the present invention, are not limitation the scope of protection of the invention.
The present invention provides the composition of a kind of nylon 46 and polytetrafluoroethylene (PTFE), is realized by following steps：
Embodiment 1
The preparation of step 1. aqueous phase
1000Kg water is added in 2000L autoclaves, 1Kg ammonium lauryl sulfates stir.Step 2. oil
The preparation of phase
In 200L reactors, by 100Kg nylon 46 powders, 1Kg acrylic anhydrides, 1Kg γ-(metering system
Acyl-oxygen) propyl trimethoxy silicane (KH-570), add 0.08Kg potassium peroxydisulfate initiators, stir.
Step 3. polymerisation
The oil-phase solution that step 2 is prepared is added in step 1 equipped with the reactor for having prepared aqueous phase, then anti-from 90 DEG C
14h is answered, reaction terminates rear blowing, through filtering, dries, obtains the nylon 46 powder of surface grafting.
Step 4. blending is crushed
80Kg steps 3 are obtained to the nylon 46 powder of surface grafting, then mixed with 20KgPTFE powders,
500L high-speed mixers are mixed, then grind broken in fluidized bed jet mill, obtain this patent product.Numbering is SX-1.
Embodiment 2
The preparation of step 1. aqueous phase
1000Kg water is added in 2000L autoclaves, 0.5Kg ammonium lauryl sulfates stir.
The preparation of step 2. oil phase
In 200L reactors, by 100Kg nylon 46s, 0.5Kg acrylic anhydrides, 0.5Kg γ-(metering system
Acyl-oxygen) mixing of propyl trimethoxy silicane (KH-570) monomer, add 0.05Kg potassium peroxydisulfate initiators, stir.
Step 3. polymerisation
The oil-phase solution that step 2 is prepared is added in step 1 equipped with the reactor for having prepared aqueous phase, then anti-from 70 DEG C
20h is answered, reaction terminates rear blowing, through filtering, dries, obtains the nylon 46 powder of surface grafting.
Step 4. blending is crushed
70Kg steps 3 are obtained to the nylon 46 powder of surface grafting, then with 30KgPTFE powders in 300L
High-speed mixer is mixed, then grinds broken in fluidized bed jet mill, obtains this patent product.Numbering is SX-2.
Embodiment 3
The preparation of step 1. aqueous phase
1000Kg water is added in 2000L autoclaves, 2Kg cetyl benzenesulfonic acid sodiums stir.
The preparation of step 2. oil phase
In 200L reactors, by 100Kg nylon 46s, 2Kg acrylic anhydrides, 2Kg γ-(methacryloxypropyl)
Propyl trimethoxy silicane (KH-570) monomer is mixed, and is added 0.1Kg ammonium persulfate initiators, is stirred.
Step 3. polymerisation
The oil-phase solution that step 2 is prepared is added in step 1 equipped with the reactor for having prepared aqueous phase, then from 100 DEG C
10h is reacted, reaction terminates rear blowing, through filtering, dries, obtains the nylon 46 powder of surface grafting.
Step 4. blending is crushed
90 parts of steps 3 are obtained to the nylon 46 powder of surface grafting, then with 10 parts of PTFE powders in 300L
High-speed mixer is mixed, then grinds broken in fluidized bed jet mill, obtains this patent product.Numbering is SX-3.
Comparative example 1
Nylon 46 only carries out the blending of step 4, without step 1-3 reaction, Qi Tatong without grafting
Embodiment 1.Products obtained therefrom numbering is SX-4.
Comparative example 2
It is one-component only with nylon 46, production code member is SX-5.
Embodiment 4
Obtained micro mist in embodiment 1-3 and comparative example 1-2,
Heat distortion temperature is tested by ASTM-D648 standards, is loaded as I.82MPa, specimen size (mm)：(127±2)
X(12.7±0.2)X(3.20±0.2)；Maximum deformation quantity is 0.254mm.
Notch impact strength is tested by by ASTM-D256 standards, and specimen types are V breach types, specimen size (mm)：
63.5X(12.7±0.2)X(3.2±0.2)；Breach type is V mouthfuls of classes, breach residual thickness 10.16mm.
| Embodiment sample | Heat distortion temperature DEG C | Notch impact strength KJ/m2 |
| SX-1 | 289 | 17 |
| SX-2 | 287 | 15 |
| SX-3 | 293 | 19 |
| SX-4 | 252 | 11 |
| SX-5 | 188 | 4.9 |
Claims (1)
1. the composition of a kind of nylon 46 and polytetrafluoroethylene (PTFE), it is characterised in that comprise the following steps：
The preparation of step 1. aqueous phase
By weight, 1000 parts of water are added in a kettle., and 0.5-2 parts of emulsifying agents stir；
The preparation of step 2. oil phase
By weight, by 100 parts of nylon 46 powders, 0.5-3 parts of KH570 monomers, 0.5-3 parts of acrylic anhydrides are mixed
Close, add 0.05-0.1 parts of initiators, stir；
Step 3. polymerisation
The oil-phase solution prepared in step 2 is added in step 1 equipped with the reactor for having prepared aqueous phase, then from 70-100 DEG C
8-20h is reacted, reaction terminates rear blowing, and product is through filtering, drying；
Step 4. is blended
70-90 parts of steps 3 are obtained to the nylon 46 powder of surface modification, mixed with 10-30 parts of PTFE powders, in height
Fast mixer mixing, then grind broken in fluidized bed jet mill, obtain this product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410290602.5A CN104109378B (en) | 2014-06-20 | 2014-06-20 | A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410290602.5A CN104109378B (en) | 2014-06-20 | 2014-06-20 | A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) |
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| Publication Number | Publication Date |
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| CN104109378A CN104109378A (en) | 2014-10-22 |
| CN104109378B true CN104109378B (en) | 2017-08-22 |
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| CN201410290602.5A Active CN104109378B (en) | 2014-06-20 | 2014-06-20 | A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) |
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| CN116978636B (en) * | 2023-08-10 | 2023-12-26 | 芜湖航飞科技股份有限公司 | Preparation method of composite insulation lapped wire for aviation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1241361A (en) * | 1969-03-11 | 1971-08-04 | Ici Ltd | Thermoplastic polymer blends |
| JPH0420312A (en) * | 1990-05-15 | 1992-01-23 | Japan Synthetic Rubber Co Ltd | Kitchen utensils |
| CN101885910B (en) * | 2009-05-12 | 2013-03-13 | 上海日之升新技术发展有限公司 | High wear-resistant PA66 composite material and preparation method thereof |
| CN103304994A (en) * | 2013-06-21 | 2013-09-18 | 苏州新区佳合塑胶有限公司 | Wearable and hydrolysis-resistant enhanced nylon 66 composite material |
| CN103756396B (en) * | 2013-12-14 | 2015-05-20 | 衢州市中通化工有限公司 | Preparation method for mixed wax capable of enhancing smoothness of coating |
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