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CN106566236A - High temperature resistant polyamide composite having biocompatibility, and preparation method and application of high temperature resistant polyamide composite - Google Patents

High temperature resistant polyamide composite having biocompatibility, and preparation method and application of high temperature resistant polyamide composite Download PDF

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Publication number
CN106566236A
CN106566236A CN201610931230.9A CN201610931230A CN106566236A CN 106566236 A CN106566236 A CN 106566236A CN 201610931230 A CN201610931230 A CN 201610931230A CN 106566236 A CN106566236 A CN 106566236A
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CN
China
Prior art keywords
resistant polyamide
heat resistant
biocompatibility
compositionss
high temperature
Prior art date
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Pending
Application number
CN201610931230.9A
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Chinese (zh)
Inventor
杜晓华
陈晓敏
田际波
周淑芬
陈佰全
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nakahiro Junl (shanghai) New Material Co Ltd
Cgn Juner New Materials Co Ltd
Original Assignee
Nakahiro Junl (shanghai) New Material Co Ltd
Cgn Juner New Materials Co Ltd
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Application filed by Nakahiro Junl (shanghai) New Material Co Ltd, Cgn Juner New Materials Co Ltd filed Critical Nakahiro Junl (shanghai) New Material Co Ltd
Priority to CN201610931230.9A priority Critical patent/CN106566236A/en
Publication of CN106566236A publication Critical patent/CN106566236A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/048Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high temperature resistant polyamide composite having biocompatibility, and a preparation method and an application of the high temperature resistant polyamide composite. The high temperature resistant polyamide composite consists of the following components by weight percent, 48-74% of high temperature resistant polyamide, 25-45% of inorganic filler, 1-10% of teflon powder and 0.1-2% of processing agent. The preparation method of the high temperature resistant polyamide composite can be realized by adopting a double screw extrusion machine. The preparation method is simple and facilities industrial mass production. The high temperature resistant polyamide composite is high in cost performance and can be processed and formed easily, can be sterilized in high temperature and high pressure methods, is good in chemical stability, has excellent biocompatibility, can not release substances harmful to a human body, and can be used in the field of surgical operation medical devices.

Description

A kind of heat resistant polyamide compositionss with biocompatibility and preparation method thereof and Using
Technical field
The present invention relates to polyamide material field, and in particular to a kind of combination of the heat resistant polyamide with biocompatibility Thing and its preparation method and application.
Background technology
With social development, the aged tendency of population trend of China is increasingly serious, and the aged is to health care, nursing, guarantor The rigid demand of the resource such as strong is that this country is just actively increasing input to fields such as health care, health cares increasing, and lifts doctor Service level is treated, health management system is improved, so the health care relevant market of following China has a high potential.
In medicine and hygiene fieldses, traditional metal materials such as rustless steel, titanium alloy etc. are because its is corrosion-resistant, satisfactory mechanical property, Good biocompatibility and enjoy favor, but metal material there is also deficiency, such as some Minimally Invasive Surgerys, the apparatus meeting of metal material Cause image to produce artifact, metal material easily causes human allergy, also need to perform the operation from taking-up etc. in vivo after metal parts rehabilitation.
In recent years, with technological innovation, the alternative metal material of some medical polymers is used for medical field, such as polychlorostyrene second Alkene is used for conduit, bags of blood, and functional modification polypropylene is thin for blood storage (Chinese patent CN101831132A), dialysis Film, polyurethane material is used for interposing catheter, et al. Ke product (Chinese patent CN101831132A), and poly-lactic acid material is used for can The interference screw (CN102940908A) for implanting, while the material can slowly be degraded by human body, absorbed.Resistant to elevated temperatures special type PEEK adapts to high temperature, the method for high pressure and carries out disinfection sterilizing, while with biocompatibility, alternative metal Material is used for surgical medical equipment parts.But such special engineering plastics is expensive, processing conditionss are harsh, should to its popularization With causing resistance.
The content of the invention
It is an object of the invention to provide a kind of heat resistant polyamide compositionss with biocompatibility and preparation method thereof And application, said composition cost performance is high, be easily worked molding, adapt to high temperature and high pressure method carries out disinfection sterilizing, chemically stable Property it is good, while with excellent biocompatibility, harmful material will not be discharged, can be used for surgical medical equipment neck Domain.
For achieving the above object, the technical scheme that the present invention takes is as follows:
A kind of heat resistant polyamide compositionss with biocompatibility, are made up of the component of following percetage by weight:
In the present invention, polytetrafluoroethylene powder as biocompatibility function ingredients, and using based on heat resistant polyamide Material is wanted, and adds inorganic filler and processing aid so that heat resistant polyamide compositionss of the present invention with biocompatibility With excellent mechanical property and heat resistance, adapt to high temperature and high pressure method and carry out disinfection sterilizing, meanwhile, with excellent life The thing compatibility, is conducive to biological cell in the growth on heat resistant polyamide composite material surface.
It is following as the preferred technical solution of the present invention:
Described heat resistant polyamide, refers to p-phthalic acid and semiaromatic that fats diamidogen is main polymerized monomer Type polyamide, fusing point is 305-320 DEG C, preferred copolymerization PA6T.
Described inorganic filler, including fibrous inorganic filler, powdered inorganic filler and combinations thereof, described is inorganic Filler is fibrous inorganic matters, diameter at 1-50 μm, described fibrous inorganic matters be glass fibre, carbon fiber, attapulgite, More than the one or two kinds of in wollastonite, whisker (including two kinds).Still more preferably, described inorganic filler is diameter 1- 15 μm of glass fibre.The fibrous inorganic matters of addition can improve the mechanical property and thermostability of heat resistant polyamide composite material Energy.
Polytetrafluoroethylene powder as biocompatibility function ingredients, using the excellent polymer of biocompatibility, polytetrafluoro Ethylene micropowder.Polytetrafluoroethylene powder is introduced and is conducive to biological cell in the growth on heat resistant polyamide composite material surface, is improved Its biocompatibility, and can also ensure that the excellent mechanical property of material.
Described processing aid is one or two in antioxidant, lubricant.
Described antioxidant, selected from phenols, one or several mixture of phosphite ester apoplexy due to endogenous wind, phenolic antioxidant is excellent Select H161,1010,1098, phosphite ester kind antioxidant preferably 168, PEPQ.Antioxidant energy and peroxide reactions, prevent polymerization Thing molecule chain break, delays the aging hydraulic performance decline for causing of heat resistant polyamide composite material, extends its service life.
Described lubricant, one or several the mixture in silicone powder, silicone master batch, zinc stearate is excellent Select silicone powder.Lubricant can form lubricating layer in polymer and metal die surface, improve processing, the molding of heat resistant polyamide Performance.
Further preferably, the described heat resistant polyamide compositionss with biocompatibility, by following percetage by weight Component composition:
Still more preferably, the described heat resistant polyamide compositionss with biocompatibility, by following weight percent Several component compositions:
Most preferably, the described heat resistant polyamide compositionss with biocompatibility, by the group of following percetage by weight It is grouped into:
Described heat resistant polyamide adopts the A-6000 types of Su Wei companies, and fusing point is 308 DEG C;
Described inorganic filler adopts the 568H short glass fibers of Jushi Group Co., Ltd., 10 μm of diameter;
Polytetrafluoroethylene powder adopts the ptfe micropowder Polymist F-5A-EX of Su Wei companies;
Described processing aid is made up of the antioxidant of percetage by weight 0.4% and the lubricant of percetage by weight 0.5%, described Lubricant be silicone powder.
The preparation method of the described heat resistant polyamide compositionss with biocompatibility, comprises the following steps:
1) it is, that heat resistant polyamide resin is predrying;
2), by through the heat resistant polyamide resin of pre-dried, polytetrafluoroethylene powder and processing aid, fed by main Material mouth enters double screw extruder;And inorganic filler enters double screw extruder by side spout;
3) the high temperature resistant polyamides with biocompatibility is obtained after double screw extruder melting extrusion, cooling, pelletizing Amine composition.
Preparation process keeps whole production scene cleaning, without obvious dust.
Step 1) in, described pre-dried condition is:In being positioned over 100 DEG C~120 DEG C of air dry oven, 3- is dried 8 hours;Further preferably, described pre-dried condition is:In being positioned over 110 DEG C of air dry oven, 4-6 is dried individual little When.
Step 3) in, in described double screw extruder, 300 DEG C -340 DEG C of the temperature of melting extrusion, engine speed: 200rpm/min-500rpm/min。
The heat resistant polyamide compositionss with biocompatibility of the present invention, said composition is easily worked molding, adapts to High temperature and high pressure method carries out disinfection sterilizing, chemical stability well, while with excellent biocompatibility, it is right to discharge The harmful material of human body, is highly suitable for preparing surgical medical equipment or inserts internal medical apparatus and instruments.
Compared with prior art, the invention has the advantages that:
Heat resistant polyamide compositionss with biocompatibility of the present invention, polytetrafluoroethylene powder is used as biofacies Capacitive function ingredients, and heat resistant polyamide is adopted for main material, and add inorganic filler and processing aid so that this The bright heat resistant polyamide compositionss with biocompatibility have excellent mechanical property and heat resistance, adapt to high temperature and height Pressure method carries out disinfection sterilizing, meanwhile, with excellent biocompatibility, be conducive to biological cell compound in heat resistant polyamide The growth of material surface.
The heat resistant polyamide compositionss with biocompatibility of the present invention, said composition is easily worked molding, adapts to High temperature and high pressure method carries out disinfection sterilizing, chemical stability well, while with excellent biocompatibility, it is right to discharge The harmful material of human body, is highly suitable for preparing surgical medical equipment or inserts internal medical apparatus and instruments.
Heat resistant polyamide preparation method of composition of the present invention with biocompatibility is simple, it is easy to which industrialization is extensive Production, and its cost only has the 18%-25% of special engineering plastics, therefore with wide market application foreground.
Description of the drawings
Fig. 1 is heat resistant polyamide composite material cell growth assay result schematic diagram.
Specific embodiment
Below in conjunction with specific embodiment and experimental data, the invention will be further described, but should not be construed as limiting this Bright protection domain.
The raw material adopted in embodiment:
The A-6000 types of heat resistant polyamide PA6T Shi Su prestige company, fusing point is 308 DEG C;
Inorganic filler glass fibre is the 568H short glass fibers of Jushi Group Co., Ltd., 10 μm of diameter;
The ptfe micropowder Polymist F-5A-EX of biocompatibility function ingredients Shi Su prestige company;
Antioxidant is the PEPQ of the Thanox 1010 of Li Anlong Chemical Co., Ltd.s and Clariant companies;
Lubricant is silicone powder GM-100 of Zhonglan Chenguang Chemical Inst.
Embodiment 1
First by heat resistant polyamide Resin A -6000 in 110 DEG C of air dry oven, 5 hours, moisture content weight are dried Percentage composition is less than 0.15%.By through the heat resistant polyamide resin of pre-dried, biocompatibility function ingredients poly- four Fluorothene micropowder Polymist F-5A-EX, antioxidant Thanox1010, antioxidant PEPQ and lubricant GM-100, are separately added into During corresponding independent feeding weightlessness claims, double screw extruder is entered eventually through main spout, short glass fiber 568H is added In the weightless title of side feeding, double screw extruder is entered by side spout.According still further to component shown in the embodiment 1 shown in table 1 Proportioning, sets each weightless feeding capacity parameter for claiming, and each section temperature of the double screw extruder from feed zone to head is set as:340 DEG C, 340 DEG C, 330 DEG C, 320 DEG C, 320 DEG C, 310 DEG C, 300 DEG C, 300 DEG C, 300 DEG C, 330 DEG C, the main frame of double screw extruder turns Speed is 400rpm/min, and screw slenderness ratio is 40 in double screw extruder:1, through melt blending extrusion, cooling and pelletizing work Sequence, is obtained heat resistant polyamide composite material (heat resistant polyamide compositionss i.e. of the present invention).
Embodiment 2
Step is with embodiment 1, and constituent content is different from embodiment 1, according to matching somebody with somebody for component shown in the embodiment 2 shown in table 1 Than.
Comparative example 1
Step does not add biocompatibility function ingredients ptfe micropowder, according to shown in table 1 with embodiment 1 The proportioning of component shown in comparative example 1.
Comparative example 2
Step does not add biocompatibility function ingredients ptfe micropowder and short glass fiber with embodiment 1, According to the proportioning of component shown in the comparative example 2 shown in table 1.
Table 1 is the composition and composite property of each component weight percent of embodiment 1-2 and comparative example 1-2.
Table 1
Embodiment 1-2 and comparative example 1~2 are obtained into heat resistant polyamide composite material particle, in 120 DEG C of forced air drying It is dried in case after 4 hours, the standard size batten needed for properties test, injection temperature 330 is molded into by injection machine DEG C, 130 DEG C of mold temperature.Then according to the national standard shown in table 2 carries out properties detection, testing result is as shown in table 1.
The national standard that the detection of the properties of table 2 is followed
Test event Testing standard
Tensile strength GB/T 1040.2-2006
Bending strength GB/T 9341-2008
Bending moduluses GB/T 9341-2008
Simply supported beam unnotched impact strength GB/T 1043.1-2008
1.8MPa heat distortion temperature GB/T 1634.2-2004
Water absorption rate GB/T 1034-2008
As shown in table 1, the tensile strength of the heat resistant polyamide resin of comparative example 2, bending strength, bending moduluses and thermal deformation Temperature all than relatively low, it is difficult to meet practical application request.Relative to comparative example 2, comparative example 1, embodiment 1 and embodiment 2 are used Heat resistant polyamide composite material mechanical property after 35% glass fiber reinforcement increases obvious, and embodiment 1 and embodiment 2 are brighter Aobvious, tensile strength improves 160%, bending strength and improves 130%, bending moduluses and improves 280%, and thermostability is also improved very Many, heat distortion temperature improves 150% under 1.8MPa load, increases to 280 DEG C or so, the notable drop while water absorption rate has been got back It is low, have dropped more than 50%, it can be ensured that the dimensional stability of compression molding parts.
Compare the ptfe micropowder addition as can be seen that certain content by embodiment 1,2 and comparative example 1, not only Can cooperate with and improve the mechanical property of composite, and make its water absorption rate lower.The high temperature resistant of this high comprehensive performance is gathered Amide composite adapts to completely the method for high temperature and high pressure and carries out disinfection sterilizing, can be used for zero of surgical machinery Part.
Growth experiment of the biocompatibility of heat resistant polyamide composite material by cell attachment after sheet surface come Judge, experimental result is as shown in Figure 1.Cell type used is the stronger HeLa cells of adherence quality, and sheet material used is by resistance to height Warm polyamide compoiste material is molded into the thick lamellars of 1.2mm by injection machine.Experimental technique:By 4 × 104Individual HeLa cells inoculation To sheet surface growth, liquid is changed daily, the cell quantity on sheet material is counted after three days.
It will be seen from figure 1 that being not changed in before and after the cell quantity experiment of the sheet surface of comparative example 2, it may be possible to due to HeLa cells are weaker to sticking for the sheet material of comparative example 2, are lost during liquid is changed, or the sheet material of comparative example 2 is inhibited The division of cell, growth.And the cell quantity of sheet surface rises substantially after embodiment 1,2 and the cell growth assay of comparative example 1, Illustrate that these three materials can maintain the normal growth of cell, the addition of glass fibre to improve HeLa cells and stick to sheet material Property.The cell quantity of sheet surface rises more than 1 times than comparative example 1 after embodiment 1 and the cell growth assay of embodiment 2, says Bright HeLa cells are easier in the division of the sheet surface containing ptfe micropowder, growth.The cell growth assay of embodiment 1 As a result illustrate that its biocompatibility is more preferable.

Claims (10)

1. a kind of heat resistant polyamide compositionss with biocompatibility, it is characterised in that by the group of following percetage by weight It is grouped into:
2. heat resistant polyamide compositionss with biocompatibility according to claim 1, it is characterised in that by following The component composition of percetage by weight:
3. heat resistant polyamide compositionss with biocompatibility according to claim 2, it is characterised in that by following The component composition of percetage by weight:
4. heat resistant polyamide compositionss with biocompatibility according to claim 1, it is characterised in that described The fusing point of heat resistant polyamide is 305-320 DEG C.
5. heat resistant polyamide compositionss with biocompatibility according to claim 1, it is characterised in that described Inorganic filler is fibrous inorganic matters, and at 1-50 μm, described fibrous inorganic matters are glass fibre, carbon fiber, concavo-convex to diameter It is more than the one or two kinds of in rod soil, wollastonite, whisker;
Described processing aid is one or two in antioxidant, lubricant.
6. heat resistant polyamide compositionss with biocompatibility according to claim 1, it is characterised in that described Inorganic filler is the glass fibre of 1-15 μm of diameter.
7. the preparation side of the heat resistant polyamide compositionss with biocompatibility according to any one of claim 1~6 Method, it is characterised in that comprise the following steps:
1) it is, that heat resistant polyamide resin is predrying;
2), by through the heat resistant polyamide resin of pre-dried, polytetrafluoroethylene powder and processing aid, by main spout Into double screw extruder;And inorganic filler enters double screw extruder by side spout;
3) the heat resistant polyamide group with biocompatibility is obtained after double screw extruder melting extrusion, cooling, pelletizing Compound.
8. the preparation method of the heat resistant polyamide compositionss with biocompatibility according to claim 7, its feature It is, step 1) in, described pre-dried condition is:In being positioned over 100 DEG C~120 DEG C of air dry oven, 3-8 is dried Hour.
9. the preparation method of the heat resistant polyamide compositionss with biocompatibility according to claim 7, its feature It is, step 3) in, in described double screw extruder, 300 DEG C -340 DEG C of the temperature of melting extrusion, engine speed:200rpm/ min-500rpm/min。
10. the heat resistant polyamide compositionss with biocompatibility according to any one of claim 1~6 are outside preparing Application in section's surgical medical apparatus.
CN201610931230.9A 2016-10-31 2016-10-31 High temperature resistant polyamide composite having biocompatibility, and preparation method and application of high temperature resistant polyamide composite Pending CN106566236A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107815100A (en) * 2017-11-02 2018-03-20 雪龙集团股份有限公司 A kind of preparation method of Nylon for Automobile fan material
CN111117231A (en) * 2019-12-31 2020-05-08 会通新材料(上海)有限公司 Halogen-free polyamide 56 composition capable of resisting long-term aging of hot air and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343409A (en) * 2008-08-27 2009-01-14 毛惠敏 Carbon fiber reinforced composite and preparation thereof
CN101550272A (en) * 2008-04-03 2009-10-07 惠州市华聚塑化科技有限公司 High strength wear resistant nylon resin and method for preparing same
US20110196080A1 (en) * 2007-08-01 2011-08-11 Kuraray Co., Ltd. Polyamide composition
CN103450673A (en) * 2013-09-10 2013-12-18 南京鸿瑞塑料制品有限公司 Pumping rod centralizer reinforcement material with high wear resistance and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110196080A1 (en) * 2007-08-01 2011-08-11 Kuraray Co., Ltd. Polyamide composition
CN101550272A (en) * 2008-04-03 2009-10-07 惠州市华聚塑化科技有限公司 High strength wear resistant nylon resin and method for preparing same
CN101343409A (en) * 2008-08-27 2009-01-14 毛惠敏 Carbon fiber reinforced composite and preparation thereof
CN103450673A (en) * 2013-09-10 2013-12-18 南京鸿瑞塑料制品有限公司 Pumping rod centralizer reinforcement material with high wear resistance and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107815100A (en) * 2017-11-02 2018-03-20 雪龙集团股份有限公司 A kind of preparation method of Nylon for Automobile fan material
CN111117231A (en) * 2019-12-31 2020-05-08 会通新材料(上海)有限公司 Halogen-free polyamide 56 composition capable of resisting long-term aging of hot air and application thereof

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Application publication date: 20170419