CN103113740A - Nylon-66 modified elastomer and preparation method thereof - Google Patents
Nylon-66 modified elastomer and preparation method thereof Download PDFInfo
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- CN103113740A CN103113740A CN2013100136755A CN201310013675A CN103113740A CN 103113740 A CN103113740 A CN 103113740A CN 2013100136755 A CN2013100136755 A CN 2013100136755A CN 201310013675 A CN201310013675 A CN 201310013675A CN 103113740 A CN103113740 A CN 103113740A
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- nylon
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- modified elastomer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention belongs to the technical field of thermoplastic elastomers and discloses a nylon-66 modified elastomer and a preparation method thereof. The nylon-66 modified elastomer comprises the following components in parts by weight: 15-70 parts of PA66, 5-15 parts of nylon toughening compatilizer, 10-70 parts of SEBS, 15-75 parts of ultra-low density polyethylene, 1-15 parts of calcium stearate and 1-2 parts of white mineral oil. The nylon-66 modified elastomer has the characteristics of high temperature resistance and oil resistance, has the characteristics of SEBS, low specific gravity of ultra-low density polyethylene and high toughness and has high compatibility, proper product hardness and low cost.
Description
Technical field
The present invention relates to the thermoplastic elastomer technical field, relate in particular to modified elastomer of a kind of nylon 66 for electric wire and cable jacket and automotive pipeline and preparation method thereof.
Background technology
The existing material that is used for electric wire and cable jacket and automotive pipeline mostly is styrene analog thermoplastic elastomer (TPE) and Thermoplastic Vulcanizate (TPV), and TPE is a kind of snappiness with rubber, high resilience, the feature that has again plastic processing, environment-protecting asepsis safety, durometer level is wide, good tint permanence is arranged, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not vulcanize, can recycle and reduce costs, Application Areas is wide, can be used for enhancing, the toughening modifying of plastics; But the poor heat resistance of TPE, the physical property fall is large along with the temperature rising, so use range is restricted.TPV is comprised of two portions, the one, plastics, as external phase, the 2nd, rubber is as disperse phase, have good elasticity and compression deformability, anti-environment, ageing resistance are equivalent to terpolymer EP rubber, 60-150 ℃ of the wide (– of temperature limit), and the soft durometer applied range (25A-54D), tooling cost is low, reusable, environment-protecting asepsis; But its oil-proofness is general, and production technology and equipments is strict, and the product comprehensive cost is higher.Development along with modern industry, on the basis of production control cost, performance requriements to product is stricter, especially under some high temperature, oil environment, due to the not oil-proofness of TPE and TPV or oil-proofness is poor, temperature limit is narrow or production cost is relatively high, its use in industry, the particularly use in electric wire and cable jacket and automotive pipeline have been limited.The electric wire and cable jacket of the existing TPE of use or TPV material and the normal use temperature of automotive pipeline scarcely surpass 90 ℃, and oil-proofness is relatively poor.
Polymeric amide (PA, be commonly called as nylon) the translucent or oyster white crystalline resin for the toughness horn shape, have excellent mechanical property, electrical property, chemical proofing, self lubricity, good moulding processability, output occupies first of five large-engineering plastics over the years, and with low cost, replacing steady growth always aspect traditional structural metallic materials, be widely used in the fields such as automobile, machinery, electronic apparatus, electric wire and building.But its toughness is poor, and a little less than impact resistance, range of application has certain limitation.By polyamide material and strongthener, toughening material or other materials are compound obtains having the more engineering product of good characteristic, as using glass fibre and other filler filling enhancing modified, improve properties of nylons and enlarge its range of application.Patent CN102627853A discloses a kind of high temperature elastomer nylon material and preparation method thereof, this material component comprises by mass percentage: polymeric amide 72%-83%, maleic anhydride modified EPDM17-28%, auxiliary agent 0-20%, wherein polymeric amide is synthetic by aromatic dicarboxylic acid and aliphatic chain diamines.Its advantage is to prepare the large modified nylon materials of initial impact energy of rupture by the proportion optimization that nylon is synthesized and elastomeric preferred, can effectively avoid cracking in the materials'use process, keeps long-term operational characteristics and the life-span of material.
TPE and TPV and polymeric amide respectively have its relative merits, and restriction use range, as both being mixed in conjunction with polymeric amide and elastomeric advantage, can enlarge both in industrial use range, but the mixing of bi-material, particularly polyamide material and thermoplastic elastomer TPE polarity and structural difference cause the consistency of bi-material poor, if polymeric amide or TPE are not carried out corresponding modification to improve consistency both, can directly have influence on the performance of product.
Summary of the invention
At present, the thermoplastic elastomer technical field being used for electric wire and cable jacket and automotive pipeline in the urgent need to a kind of high temperature resistant, oil-proofness that had both had polyamide material, has again the flexible material of thermoplastic elastomer.For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide the modified elastomer of a kind of high temperature resistant, ageing-resistant, oil resistant, nylon 66 that tensile strength is good.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6615-70 part, toughening nylon compatilizer 5-15 part, SEBS10-70 part, ultra-low density polyethylene 15-75 part, calcium stearate 1-15 part, white mineral oil 1-2 part.
Preferably, described toughening nylon compatilizer is the maleic anhydride graft terpolymer EP rubber.
Preferably, the percentage of grafting of described maleic anhydride graft terpolymer EP rubber is 0.8%-2%; The percentage of grafting of preferred maleic anhydride graft terpolymer EP rubber is 1%-1.5%.
A kind of method of modified elastomer of nylon as above 66, its concrete steps are as follows:
first PA66 and a white mineral oil are joined in stirrer, after stirring, add wherein again calcium stearate, stir, continue to add wherein the maleic anhydride graft terpolymer EP rubber, ultra-low density polyethylene and SEBS, after it is stirred, import (a district temperature 190-220 ℃ of twin screw extruder, two district temperature 200-230 ℃, three district temperature 205-235 ℃, four district temperature 215-245 ℃, five district temperature 225-255 ℃, six district temperature 235-265 ℃, seven district temperature 245-275 ℃, eight district temperature 250-280 ℃, nine district temperature 250-280 ℃, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6MPa), extrude at last the modified elastomer that rear cooling, dehumidifying, pelletizing, drying, packing namely get nylon 66.
PA66 is a kind of in polymeric amide, for translucent or oyster white crystallization shape polymkeric substance, itself is that a kind of temperature tolerance is good, and the good material of oil-proofness, and technological temperature a wider range, and its melt temperature is 260-280 ℃.
SEBS is take polystyrene as end segment, the ethylene-butene copolymer that obtains take the polyhutadiene hydrogenation as in the middle of the linearity three embedding multipolymers of elastomeric block, it does not contain unsaturated double-bond, therefore has satisfactory stability and ageing resistance; Light specific gravity, temperature tolerance preferably, its catalytic temperature≤-60 ℃, maximum operation (service) temperature reaches 149 ℃, and good solubility energy, blended characteristic and the useful oiliness of rushing can be dissolved in many common solvent, both had plasticity-, have again snappiness, need not sulfuration and can process use, be widely used in the filler of producing high-grade elastomerics, modifying plastics, tackiness agent, electric wire and sheath material etc.
SEBS is elastomerics, and hardness own is little, and PA itself is stone, and by SEBS is mixed with PA, both blend just can be made the suitable elastomerics of soft or hard, uses in electric wire and cable jacket and automobile pipeline material.Maleic anhydride graft terpolymer EP rubber (being maleic anhydride graft EPDM) is the toughening nylon compatilizer, it solves the relatively poor problem of nylon snappiness on the one hand, on the other hand also as compatilizer, play the medium effect, a little less than having solved PA and the SEBS interface interaction due to bi-material, the problem of easily peel off, consistency is bad.
Ultra-low density polyethylene, be called for short U/VLDPE, it is linear structure, there is no long chain branches, its molecular weight distribution is narrower, weakened the formation of crystallizing field on the main polymer chain, thereby it has some excellent performances: for example it has excellent tensile strength, shock strength, tear strength and puncture intensity; Due to the line style crystallization that is short-chain branch, fusing point is higher, less its good toughness of modulus, softness, good hand touch, also has outstanding attenuate performance (reaching 10-12.7um), good insulativity, optical property, resistance to chemical corrosion, oil-proofness, stopping property etc. preferably.But when it used in some Application Areas, its hardness was not ideal enough.
the present invention has following advantage and effect with respect to prior art: by with PA66, ultra-low density polyethylene mixes with SEBS, add simultaneously toughening nylon compatilizer maleic anhydride graft EPDM, obtain mixed system (modified elastomer of nylon 66), make it have the characteristic of the high temperature resistant and oil resistant of PA66, pass through simultaneously SEBS, it is little that ultra-low density polyethylene reaches mixed system proportion, the characteristics that toughness is excellent, and by maleic anhydride graft EPDM, impel PA66 and ultra-low density polyethylene, the SEBS mixing, make mixture reach integraty, improve mixed system and easily peel off the problem bad with consistency, make the modified elastomer of nylon 66 reach high temperature resistant, ageing-resistant, oil resistant, the perfect condition that tensile strength is good.
Embodiment
Be described in further detail below in conjunction with embodiment.
In following examples, maleic anhydride graft EPDM is that logical plastic cement company limited of Shenyang section produces.
Embodiment 1
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6615 part, maleic anhydride graft EPDM5 part, SEBS10 part, 15 parts of ultra-low density polyethylenes, 1 part of calcium stearate, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 0.8%.
A kind of preparation method of modified elastomer of above-mentioned nylon 66 comprises the following steps:
first the white mineral oil with PA66 and 1 part joins in stirrer, after stirring, add wherein again calcium stearate, stir, continue to add wherein maleic anhydride graft EPDM, ultra-low density polyethylene and SEBS, after it is stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 ℃, two district temperature 200-230 ℃, three district temperature 205-235 ℃, four district temperature 215-245 ℃, five district temperature 225-255 ℃, six district temperature 235-265 ℃, seven district temperature 245-275 ℃, eight district temperature 250-280 ℃, nine district temperature 250-280 ℃, 350 rev/mins of engine speeds, vacuum-0.06MPa, pressure 3.5MPa, extrude at last the modified elastomer that rear cooling, dehumidifying, pelletizing, drying, packing namely get nylon 66.
Embodiment 2
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6645 part, maleic anhydride graft EPDM10 part, SEBS40 part, 45 parts of ultra-low density polyethylenes, 8 parts of calcium stearates, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 1%.
A kind of preparation method of modified elastomer of above-mentioned nylon 66 comprises the following steps:
first the white mineral oil with PA66 and 1 part joins in stirrer, after stirring, add wherein again calcium stearate, stir, continue to add wherein maleic anhydride graft EPDM, ultra-low density polyethylene and SEBS, after it is stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 ℃, two district temperature 200-230 ℃, three district temperature 205-235 ℃, four district temperature 215-245 ℃, five district temperature 225-255 ℃, six district temperature 235-265 ℃, seven district temperature 245-275 ℃, eight district temperature 250-280 ℃, nine district temperature 250-280 ℃, engine speed 350-450 rev/min, 450 rev/mins of engine speeds, vacuum-0.06MPa, pressure 6MPa, extrude at last the modified elastomer that rear cooling, dehumidifying, pelletizing, drying, packing namely get nylon 66.
Embodiment 3
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6670 part, maleic anhydride graft EPDM15 part, SEBS70 part, 75 parts of ultra-low density polyethylenes, 15 parts of calcium stearates, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.5%.
A kind of preparation method of modified elastomer of above-mentioned nylon 66 comprises the following steps:
first the white mineral oil with PA66 and 1 part joins in stirrer, after stirring, add wherein again calcium stearate, stir, continue to add wherein maleic anhydride graft EPDM, ultra-low density polyethylene and SEBS, after it is stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 ℃, two district temperature 200-230 ℃, three district temperature 205-235 ℃, four district temperature 215-245 ℃, five district temperature 225-255 ℃, six district temperature 235-265 ℃, seven district temperature 245-275 ℃, eight district temperature 250-280 ℃, nine district temperature 250-280 ℃, 400 rev/mins of engine speeds, vacuum-0.06MPa, pressure 5MPa, extrude at last the modified elastomer that rear cooling, dehumidifying, pelletizing, drying, packing namely get nylon 66.
Embodiment 4
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6665 part, maleic anhydride graft EPDM10 part, SEBS60 part, 60 parts of ultra-low density polyethylenes, 5 parts of calcium stearates, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.2%.
The preparation method of the modified elastomer of this nylon 66 is with the preparation method shown in embodiment 3.
Embodiment 5
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6635 part, maleic anhydride graft EPDM10 part, SEBS30 part, 30 parts of ultra-low density polyethylenes, 5 parts of calcium stearates, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.4%.
The preparation method of the modified elastomer of this nylon 66 is with the preparation method shown in embodiment 2.
Embodiment 6
A kind of modified elastomer of nylon 66 comprises following component by weight: PA6640 part, maleic anhydride graft EPDM12 part, SEBS35 part, 30 parts of ultra-low density polyethylenes, 10 parts of calcium stearates, 1 part of white mineral oil, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.3%.
The preparation method of the modified elastomer of this nylon 66 is with the preparation method shown in embodiment 1.
Above-described embodiment is preferred embodiment of the present invention, is not to limit the scope of the present invention, thus all equivalence variation or modifications of being done with the described structure of claim of the present invention, feature and principle, within all should being included in claim scope of the present invention.
Performance test:
The modified elastomer of getting the nylon 66 of above-described embodiment 1-6 gained carries out performance test, detection method in testing method such as following table, and the test result of one of them embodiment is as shown in the table.
Can find out by upper table contrast, under same test condition, tensile strength of the present invention and 100% stretching property surely is better than TPE and TPV, and thermotolerance and oil-proofness approach good, are far superior to TPE and TPV.
Claims (6)
1. the modified elastomer of a nylon 66, is characterized in that, comprises by weight: PA6615-70 part, toughening nylon compatilizer 5-15 part, SEBS10-70 part, ultra-low density polyethylene 15-75 part, calcium stearate 1-15 part, white mineral oil 1-2 part.
2. the modified elastomer of nylon 66 according to claim 1, it is characterized in that: described toughening nylon compatilizer is the maleic anhydride graft terpolymer EP rubber.
3. the modified elastomer of nylon 66 according to claim 2, it is characterized in that: the percentage of grafting of described maleic anhydride graft terpolymer EP rubber is 0.8%-2%.
4. the modified elastomer of nylon 66 according to claim 2, it is characterized in that: the percentage of grafting of described maleic anhydride graft terpolymer EP rubber is 1%-1.5%.
5. a method for preparing the modified elastomer of nylon 66 claimed in claim 1, is characterized in that, concrete steps are as follows:
First PA66 and a white mineral oil are joined in stirrer, after stirring, then add wherein calcium stearate, stir, continue to add wherein maleic anhydride graft terpolymer EP rubber, ultra-low density polyethylene and SEBS, after it is stirred, import twin screw extruder; Extrude at last the modified elastomer that rear cooling, dehumidifying, pelletizing, drying, packing namely get described nylon 66.
6. the preparation method described according to claim 5, is characterized in that described twin screw extruder, complete processing is as follows: a district temperature 190-220 ℃, and two district temperature 200-230 ℃, three district temperature 205-235 ℃, four district temperature 215-245 ℃, five district temperature 225-255 ℃, six district temperature 235-265 ℃, seven district temperature 245-275 ℃, eight district temperature 250-280 ℃, nine district temperature 250-280 ℃, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6MPa.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665861A (en) * | 2013-11-21 | 2014-03-26 | 安徽师范大学 | Light polyolefin modified nylon material for automobile plastic parts |
| CN103788636A (en) * | 2014-02-20 | 2014-05-14 | 安安(中国)有限公司 | High polymer blending system for manufacturing high-fineness high-strength non-figured PA6 superfine fibers |
| CN104371242A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic and preparation method |
| CN104371243A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic formula and preparation method |
| CN104371200A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic formula |
| CN104371240A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic |
| CN104371241A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | Formula of thermoplastic elastomer |
| CN104725846A (en) * | 2014-10-27 | 2015-06-24 | 深圳市欧龙优新材料科技有限公司 | New nylon-66 elastomer material with good flexibility |
| CN106750825A (en) * | 2017-01-20 | 2017-05-31 | 成都新硕新材料有限公司 | A kind of resistance to 125 DEG C of halogen-free flame-retardant composite materials and its preparation method and application |
| CN107057335A (en) * | 2016-12-30 | 2017-08-18 | 中广核三角洲（苏州）新材料研发有限公司 | Transparent nylon elastomer and preparation method thereof |
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| CN103665861A (en) * | 2013-11-21 | 2014-03-26 | 安徽师范大学 | Light polyolefin modified nylon material for automobile plastic parts |
| CN103788636A (en) * | 2014-02-20 | 2014-05-14 | 安安(中国)有限公司 | High polymer blending system for manufacturing high-fineness high-strength non-figured PA6 superfine fibers |
| CN103788636B (en) * | 2014-02-20 | 2016-08-24 | 安安(中国)有限公司 | A kind of polymer blends manufactured for high fineness high intensity non-figured type PA6 superfine fibre |
| CN104725846A (en) * | 2014-10-27 | 2015-06-24 | 深圳市欧龙优新材料科技有限公司 | New nylon-66 elastomer material with good flexibility |
| CN104371242A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic and preparation method |
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| CN104371200A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic formula |
| CN104371240A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | TPE (thermoplastic elastomer) plastic |
| CN104371241A (en) * | 2014-10-29 | 2015-02-25 | 苏州新区枫盛塑料制品厂 | Formula of thermoplastic elastomer |
| CN107057335A (en) * | 2016-12-30 | 2017-08-18 | 中广核三角洲（苏州）新材料研发有限公司 | Transparent nylon elastomer and preparation method thereof |
| CN106750825A (en) * | 2017-01-20 | 2017-05-31 | 成都新硕新材料有限公司 | A kind of resistance to 125 DEG C of halogen-free flame-retardant composite materials and its preparation method and application |
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