CN1510084A - Method for preparing high strength super-toughened nylon alloy - Google Patents
Method for preparing high strength super-toughened nylon alloy Download PDFInfo
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- CN1510084A CN1510084A CNA021587841A CN02158784A CN1510084A CN 1510084 A CN1510084 A CN 1510084A CN A021587841 A CNA021587841 A CN A021587841A CN 02158784 A CN02158784 A CN 02158784A CN 1510084 A CN1510084 A CN 1510084A
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Abstract
A process for preparing the high-strength super-through nylon alloy features that an advanced 'shell-core' copolymer is used as the impact-resistant modifier and the polymer with high-activity function group is used as compatibilizer. Its advantages are excellent properties the nylon has, high toughness, low-temp impact resistance, low-temp flexibility and anticorrosion performance, and low hydroscopicity.
Description
Technical field
The present invention relates to a kind of method for preparing high strength ultra tough nylon alloy.
Technical background
Nylon resin is the universal engineering plastics with excellent comprehensive performance, have excellent mechanical property and advantages such as wear-resisting, anti-solvent, oil resistant, extensively apply to every profession and trade, in the application of machinery manufacturing industry, electronic apparatus and traffic and transport field more and more widely, and receive numerous users' very big concern.Since E.I.Du Pont Company realized industrialization before more than 50 year first, its utilization field constantly enlarged, and becomes the main raw of automobile industry and electronic apparatus, and developed into the first engineering plastics in the world today.In recent years, the main developing direction of macromolecular material more and more develops to high performance.Have obdurability though nylon material is compared with other engineering plastic materials and since the nylon crystallinity cause impact strength decreased and in the winter time under the dry situation shock strength not high, can not satisfy the needs in requirements at the higher level market.Therefore nylon resin exists low temperature and dry state impact property relatively poor, weakness such as the big and poor dimensional stability of water-intake rate.For adapting to the needs of industrial development, in recent years nylon is carried out blending and modifying, make it to HI high impact, directions such as low suction and optimization processing develop.
For not high this weakness of shock strength that overcomes nylon resin self, improve impact property, high-impact super-tough nylon alloy becomes the emphasis of research, and applying for a patent in succession of relevant high-impact nylon occurs.At present, external impact modified main employing polyolefine to nylon 6, α, beta-unsaturated carboxylic acid or its ester, the metal-salt derivative carries out modification by copolymerization, ethylene-propylene rubber(EPR) grafted maleic anhydride modification etc.Nylon 6 alloy shock strength after this property significantly improves, and the utilization field is more extensive: Du Pont company has at first developed Zytel ST series and has had Patent right nylon 6/EPDM blend, and nylon engineering plastic is being a a progressive step aspect the replacement metallic substance.After Du Pont company, West Europe, Japan have also developed the super-tough nylon alloy of the various trades mark, and wherein representative have a Hoechst ﹠amp; Nylon 6000 series of Celanses, the Dexlon 602,603 of Dexter company, the Ultramid KR4209 of BASF AG, the Fosta 1693,1722 of Hoechst company, the Durethan KU2311 of Bayer company, the Maranyl TA510 of ICI/LNP company, the EX-1030 of the outstanding Buddhist nun's contract card company of Japan, Mitsubishi changes into the Naramid ST series product of company.The normal temperature Izod notched Izod impact strength value of these products is generally 800-1000J/M, and-40 ℃ make three times into pure nylon 6 under the normal temperature, and have the characteristics of low water absorption.
The Ni Long11 resin has passed through over half a century since it is born, and compared with the application of other nylon material, the development of Ni Long11 still awaits further developing.Along with market to the performance resins growth of requirement, the application of Ni Long11 also comes into one's own thereupon, is showing good prospects for application aspect high-performance tubing, the high-performance coating.The Ni Long11 resin has shown in many aspects than more excellent performance such as nylon 6 polyamide resins such as grade.As good wear resisting property, low-temperature impact-resistant performance, good electrical property, low water absorbable, stress cracking resistance is excellent when contacting with metal-salt.But when normal temperature, the notched Izod impact strength of Ni Long11 is not high, approaches nylon 6 basically, and to compare nylon 6 resins such as grade lower for the tensile strength of Ni Long11 in addition, and it is necessary especially that the research of its high-strength ultra-toughization just seems.Beijing University of Chemical Technology was studied Ni Long11 since 1996.Develop high strength ultra tough nylon 11 alloy systems, obtained the Ni Long11 alloy of high-strength ultra-tough equally.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthesizing high strength super-tough nylon alloy, present advanced in the world " nuclear-shell " type multipolymer of utilization is as anti-impact modifier, adopting the polymkeric substance of band high reactivity reactive functionality simultaneously is expanding material, prepare the blend alloy material that each component has good consistency and dispersing uniformity, and make alloy material except having all good characteristics of nylon, also have outstanding toughness, low-temperature impact-resistant performance, cold flexibility, chemical resistant properties, environment resistant and lower water-absorbent.
Beijing University of Chemical Technology's macromolecular material state key subject point has been succeeded in developing the super toughness nylon/copolymer blended alloy of " shell-nuclear " type with remarkable over-all properties, makes the Izod notched Izod impact strength index of nylon alloy surpass the ZYTEL ST801 of du pont company exploitation, the impact value of ST901.The room temperature of this alloy product and low temperature impact properties all are higher than external like product, and its mechanical property and thermal characteristics all are better than the import Ni Long11 simultaneously, and chemical resistant properties and water-absorbent are suitable with it.In the super toughness nylon alloy material that each manufacturer developed in the world, this index is in the leading level in the world.
The impact modifying agent of advanced " shell-nuclear " type multipolymer as nylon 6 adopted in this research, and select highly effective reaction type solubilizing agent for use, be prepared from by the reaction extrusion molding, its product notched Izod impact strength and low temperature impact properties are far longer than impact modification nylon-type alloy in the past, and surpass the shock strength of Ni Long11.Aspect over-all properties, meet or exceed the ZYTEL of E.I.Du Pont Company series super-tough nylon alloy, and can become the material that part substitutes Ni Long11, and its cost has good economic benefit far below the Ni Long11 resin.The super toughness nylon alloy of being developed can be widely used in trolley part (as engine parts, electrical component, body part etc.), building pipe, electronic apparatus, the helmet and military industry field become at performance and the high-tech product that can compete mutually with Ni Long11, nylon 22 and thermoplastic polyurethane in price.
At present, the super toughness nylon alloy series of exploitation mainly contains two kinds of universal engineering plastic alloy TY1, TY2 and special material for tube GC1.Wherein the GC1 special material for tube by German automobiles with nylon tube DIN73378 standard testing, and reach the requirement of every index.Our company also can provide ultraviolet resistance wear out type, heat-proof aging type, flame retardant type and other tailored version super-tough nylon alloy engineering plastics according to user's requirement.See Table 1:
Table 1: universal engineering plastic alloy TY1, the performance index of TY2 and special material for tube GCl
| The project indicator | Testing method | Unit | ????TY1 | ??TY2 | ??GC1 |
| Density | ??ASTM?D792 | ????g/cm 2 | ????1.11 | ??1.10 | ??1.11 |
| Fusing point | ??ASTM?D789 | ????℃ | ????210.3 | ??207.0 | ??210.5 |
| Outward appearance | ??- | ????- | Oyster white | Translucent | White |
| Heat-drawn wire | ??ASTM?D648 | ????℃ | ????172.5 | ??170 | ??172.5 |
| Specific heat | ??- | ????KJ/Kg.℃ | ????1.7 | ??1.7 | ??1.7 |
| Melting index | ??ASTM?D1238 | ????g/10min | ????9.5 | ??9.3 | ??15.2 |
| 23 ℃ of water-intake rates, in the water 23 ℃, 50%RH | ??ASTM?D570 | ????％ | ????4.36 ????0.70 | ??4.32 ??0.74 | ??4.35 ??0.71 |
| 20 ℃-40 ℃ of IZOD shock strengths | ??ASTM?D256 | ????J/m | ????1126 ????195 | ??1240 ??206 | ??1080 ??191 |
| Tensile strength | ??ASTM?D638 | ????MPa | ????57.0 | ??55.0 | ??57.5 |
| Elongation at break | ??ASTM?D638 | ??％ | ????174.5 | ??188.0 | ??170.0 |
| Flexural strength | ??ASTM?D790 | ??MPa | ????82.0 | ??80.5 | ??82.0 |
| Modulus in flexure | ??ASTM?D790 | ??MPa | ????2050.0 | ??2000.0 | ??2050.0 |
| Rockwell hardness | ??ASTM?D785 | ??- | ????R60 | ??R57 | ??R57 |
| Body resistivity | ??ASTM?D257 | ??Ω.cm | ????10 15 | ??10 15 | ??10 15 |
| Surface resistivity | ??ASTM?D257 | ??Ω | ????10 12 | ??10 12 | ??10 12 |
| Dielectric strength | ??ASTM?D257 | ??MV/m | ????40 | ??40 | ??40 |
| Use temperature limit short-term 5000 hours 20000 hours | ? ??- | ? ??℃ | ? ????170 ????115-130 ????95-115 | ? ??170 ??115-130 ??95-115 | ??180 ??120-130 ??100-120 |
The structure of Ni Long11 is different from other polymeric amide, and long methylene radical flexible chain is arranged between its adjacent amide group, and it is very ineffective to be used for Ni Long11 for nylon 6 very effective toughened systems.The present invention adopts novel metallocene catalyst synthetic novel elastomer ethene-1-octene polymer (POE) and exploitation nylon to strengthen the purpose that masterbatch reaches plasticizing enhancement nylon 11, finally obtained the Ni Long11 alloy of high-strength ultra-tough (tensile strength is greater than 50Mpa, and notched Izod impact strength is greater than 800J/m).From the Economic development of present China, the demand of high performance material, high value added product is constantly increased.Ni Long11 such scale and tempo, developmental level now is far from being enough, so carry out the research and development of Ni Long11 and tough-increased and reinforced modification thereof energetically, break away from the dependence of Ni Long11 as early as possible to import, be the thing that urgently will do, will fill up the blank (table 2) of China at the Ni Long11 area research.
Table 2: the technical indicator of high strength ultra tough nylon alloy
| Project | Unit | The Ni Long11 alloy | External Ni Long11 |
| Tensile strength | MPa | 50.1 | ?41 |
| Elongation at break | ％ | 197 | ?150 |
| Flexural strength | MPa | 57 | ?45 |
| The IZOD notched Izod impact strength | J/m | 951 | ?80 |
| Heat-drawn wire | ℃ | 123 | ?80 |
At present, also very not comprehensive to the systematic study of Ni Long11 both at home and abroad.External research to Ni Long11 mainly concentrates on before the seventies, and main direction is the basic crystalline structure of research Ni Long11 and the basic theory of crystalline texture.Though abroad in the applied research of Ni Long11 matrix material, done a lot of work, in depth and systematically to Ni Long11 and alloy research exploitation thereof and to its sub-micro phase and with the research of property relationship almost be blank.
The high-performance novel material is the developing direction in current material field, the raising of science and technology development and economic base makes people's idea also change, and the thought of former high price lattice and lightweight is replaced by the heavy good performance and the thought of reasonable price.Beijing University of Chemical Technology's polymer state key subject has been done a large amount of research and has been attempted in this field, believe that this high performance material can have more vast potential for future development.The appearance of high strength ultra tough nylon alloy makes the Application Areas of nylon obtain great expansion, and is specific as follows:
1, auto industry field: the alternative part nonferrous materials of universal nylon alloy engineering plastics, be used to make engine parts, comprise air filter, synchronous belt, fuel filter, jar, heat radiation case, oil reservoir etc.Electric component: comprise electric wiring, connector, lamp switch, fusible link cover etc.; Body part comprises various regulator handles, gas pedal, brake axle fuel tank, variable velocity zone, cylinder, various gears, axle class, packing ring, collision bumper etc.
2, conduit and line of pipes: GC1 can partly substitute Ni Long11 and nylon 12, is used to make automobile and comprises transition pipeline with various line of pipes, brake oil pipe, lubricating pipe etc.; Also can be used for making underground petroleum, Sweet natural gas, gas line.
3, machinery manufacturing industry field: can be used for making various gears, bearing, transmission shaft, shock-resistant part such as anchor clamps also can be made the pipeline that is used for chemical industry equipment, valve, bend pipe, stopping valve, the first-class corrosion resistant spare and accessory parts of cross.
4, traffic and transport field: can be used for insulating pad, packing ring, rail brace nylon seat in the railway traffic, apron block etc., and can be used for making the inside and outside various component of passenger and freight train; Also can make the turbine of using on the steamer, turboshaft, spiral propeller, axle, seawater pump and shell component.
5, construction industry field: this product can be used for the component of automatic elevator, automatically-controlled door horizontal bar, window frame, door guide roller, various nail spares and confinement apparatus.
6, electric field: can be used for fabricator electrical appliance, electrical instrumentation spare and accessory parts, power tool parts and shell etc.
7, sports equipment field: can be used for making the helmet of motorcycle helmet and other type of protection, sled, slide plate, surfboard, sailing boat and parts and other sports equipments.
8, other: this material also can be used for making various toys for children such as plastic pattern, telecar, ship, aircraft etc.; Also can be used for the medical device aspect.Aspect military project, can be used for making the gun stock in the firearms, handguard, cartridge clip; The component of cannon, tank, panzer and other equipments.
Description of drawings
Fig. 1: preparation technology's flow process of high strength ultra tough nylon alloy
Fig. 2: the twisted blade pattern of high strength ultra tough nylon alloy section
Fig. 3: the orientation fibers bundle on the high strength ultra tough nylon alloy section lamella perpendicular to impact direction
Fig. 4: watt rib shape crimped edge of high strength ultra tough nylon alloy fracture lamella
Embodiment
Embodiment 1:
With Nylon 6 800 grams, nuclear multipolymer MBS15 gram, compatilizer Resins, epoxy 3 grams, nano-calcium carbonate 40 grams, photoaging agent 1 gram is pre-mixed even back feeding twin screw extruder, and the screw axial temperature of forcing machine is divided 6 sections controls, and the temperature of screw rod holds head to be respectively 180 ℃ from material, 200 ℃, 230 ℃, 240 ℃, 240 ℃, 240 ℃, 235 ℃.The screw rod revolution is 120 rev/mins, and nylon alloy per os mould is extruded, and after the water-cooled granulated and dried, forms batten ergometry performance.Its tensile strength is 53MPa, and the IZOD notched Izod impact strength is 1000J/m.
Embodiment 2:
With nylon 1212 resin 750 grams, nuclear multipolymer MBS13 gram, compatilizer Resins, epoxy 1 gram, nano-calcium carbonate 40 grams, photoaging agent 1 gram is pre-mixed even back feeding twin screw extruder, and the screw axial temperature of forcing machine is divided 6 sections controls, and the temperature of screw rod holds head to be respectively 180 ℃ from material, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 240 ℃, 235 ℃.The screw rod revolution is 120 rev/mins, and nylon alloy per os mould is extruded, and after the water-cooled granulated and dried, forms batten ergometry performance.Its tensile strength is 50MPa, and the IZOD notched Izod impact strength is 750J/m.
Embodiment 3:
With Nylon 66 900 grams, nuclear multipolymer MBS14 gram, compatilizer Resins, epoxy 5 grams, nano-calcium carbonate 50 grams, photoaging agent 0.9 gram is pre-mixed even back feeding twin screw extruder, and the screw axial temperature of forcing machine is divided 6 sections controls, and the temperature of screw rod holds head to be respectively 180 ℃ from material, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 245 ℃, 235 ℃.The screw rod revolution is 120 rev/mins, and nylon alloy per os mould is extruded, and after the water-cooled granulated and dried, forms batten ergometry performance.Its tensile strength is 55MPa, and notched Izod impact strength is 850J/m.
Embodiment 4:
With nylon 12 resins 1000 grams, nuclear multipolymer MBS20 gram, compatilizer Resins, epoxy 7 grams, nano-calcium carbonate 50 grams, photoaging agent 1 gram is pre-mixed even back feeding twin screw extruder, and the screw axial temperature of forcing machine is divided 6 sections controls, and the temperature of screw rod holds head to be respectively 180 ℃ from material, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 240 ℃, 235 ℃.The screw rod revolution is 120 rev/mins, and nylon alloy per os mould is extruded, and after the water-cooled granulated and dried, forms batten ergometry performance.Its tensile strength is 45MPa, and the IZOD notched Izod impact strength is 650J/m.
Embodiment 5:
With Ni Long11 resin 1600 grams, nuclear multipolymer MBS10 gram, compatilizer Resins, epoxy 1 gram, nano-calcium carbonate 60 grams, photoaging agent 1 gram is pre-mixed even back feeding twin screw extruder, and the screw axial temperature of forcing machine is divided 6 sections controls, and the temperature of screw rod holds head to be respectively 180 ℃ from material, 200 ℃, 220 ℃, 240 ℃, 240 ℃, 240 ℃, 235 ℃.The screw rod revolution is 120 rev/mins, and nylon alloy per os mould is extruded, and after the water-cooled granulated and dried, forms batten ergometry performance.Its tensile strength is 45MPa, and the IZOD notched Izod impact strength is 600J/m.
Claims (12)
1. method for preparing high strength ultra tough nylon alloy is characterized in that:
(1) composition of alloy: nylon resin is an external phase, and " nuclear-shell " type multipolymer is an anti-impact modifier, and the polymkeric substance of band high reactivity reactive functionality is an expanding material.
(2) preparation technology: after mixing by certain prescription, enter in the twin screw extruder, the control extruder temperature is 210 ℃-260 ℃, and screw speed is to make by blend under the processing condition of 200rpm-260rpm.
2. method according to claim 1 is characterized in that: the kind of nylon resin is nylon 6, Ni Long11, nylon 1212, nylon 66, nylon 12, liquid crystal type aramid fiber etc.
3. method according to claim 1 is characterized in that: the kind of " nuclear-shell " type multipolymer is MBS.
4. method according to claim 1 is characterized in that: the kind of compatilizer is a Resins, epoxy.
5. method according to claim 1 is characterized in that: the content of nylon resin is 20-90% (weight ratio), and optimum controling range is 80-90%.
6. method according to claim 1 is characterized in that: the content of core-shell copolymerized thing is 20-90% (weight ratio), and it is 10-20% that optimum control is equipped with scope.
7. method according to claim 1 is characterized in that: the content of compatilizer is 1-10% (weight ratio).
8. according to the method for claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterized in that: can add auxiliary agent and other various increase-volume reinforced fillings such as anti-light aging agent, thermo-stabilizer as required.
9. according to the method for claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterized in that: can add auxiliary agent and other various increase-volume reinforced fillings such as anti-light aging agent, thermo-stabilizer as required.
10. according to the method for claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterized in that: forcing machine is a double-screw type.
11. the preparation method according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 is characterized in that: the length-to-diameter ratio of screw rod is (25-60): 1.
12. the preparation method according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 is characterized in that: the temperature distribution along screw axial is the 5-12 section, and temperature range is 100-320 ℃, and the rotating speed of screw rod is 5-500 rev/min, and head pressure is 5-300 kilogram/square centimeter.
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| CNA021587841A CN1510084A (en) | 2002-12-25 | 2002-12-25 | Method for preparing high strength super-toughened nylon alloy |
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| CNA021587841A CN1510084A (en) | 2002-12-25 | 2002-12-25 | Method for preparing high strength super-toughened nylon alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812231A (en) * | 2010-04-16 | 2010-08-25 | 北京化工大学 | Halogen free flame retardant nylon 6 composite with high CTI value and preparation method thereof |
| CN101760999B (en) * | 2010-01-08 | 2012-08-01 | 株洲时代工程塑料制品有限责任公司 | Modified nylon gauge apron matched with railway elastic rod type fastener |
| CN106280434A (en) * | 2016-08-30 | 2017-01-04 | 聚威工程塑料(上海)有限公司 | A kind of PA66/ tremolite/MBS composite and preparation method thereof |
-
2002
- 2002-12-25 CN CNA021587841A patent/CN1510084A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760999B (en) * | 2010-01-08 | 2012-08-01 | 株洲时代工程塑料制品有限责任公司 | Modified nylon gauge apron matched with railway elastic rod type fastener |
| CN101812231A (en) * | 2010-04-16 | 2010-08-25 | 北京化工大学 | Halogen free flame retardant nylon 6 composite with high CTI value and preparation method thereof |
| CN106280434A (en) * | 2016-08-30 | 2017-01-04 | 聚威工程塑料(上海)有限公司 | A kind of PA66/ tremolite/MBS composite and preparation method thereof |
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