CN103113740B - Nylon-66 modified elastomer and preparation method thereof - Google Patents
Nylon-66 modified elastomer and preparation method thereof Download PDFInfo
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- CN103113740B CN103113740B CN201310013675.5A CN201310013675A CN103113740B CN 103113740 B CN103113740 B CN 103113740B CN 201310013675 A CN201310013675 A CN 201310013675A CN 103113740 B CN103113740 B CN 103113740B
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- district temperature
- modified elastomer
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- maleic anhydride
- anhydride graft
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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 thermoplastic elastomer technical field, particularly relate to modified elastomer of a kind of nylon66 fiber for electric wire and cable jacket and automotive pipeline and preparation method thereof.
Background technology
Existingly mostly be styrene analog thermoplastic elastomer (TPE) and Thermoplastic Vulcanizate (TPV) for the material in electric wire and cable jacket and automotive pipeline, TPE is a kind of snappiness with rubber, high resilience, have again the feature of plastic processing, environment-protecting asepsis safety, durometer level is wide, there is excellent tint permanence, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not sulfuration, can recycle and reduce costs, Application Areas is wide, can be used for the enhancing of plastics, toughening modifying; But the poor heat resistance of TPE, along with temperature rising, physical property fall is large, and therefore use range is restricted.TPV is made up of two portions, one is plastics, as external phase, two is rubber, as disperse phase, there is good elasticity and compression deformability, resistance to environment, ageing resistance are equivalent to terpolymer EP rubber, the wide (– 60-150 DEG C of temperature limit), soft durometer applied range (25A-54D), tooling cost is low, reusable, environment-protecting asepsis; But its oil-proofness is general, production technology and equipments requires strict, and product comprehensive cost is higher.Along with the development of modern industry, on the basis of production control cost, stricter to the performance requriements of product, special under some high temperature, oil environment, due to TPE and TPV not oil-proofness or oil-proofness is poor, temperature limit is narrow or production cost is relatively high, limit its use in the industry, the use particularly in electric wire and cable jacket and automotive pipeline.Existing use TPE or the electric wire and cable jacket of TPV material and the normal use temperature of automotive pipeline are scarcely more than 90 DEG C, and oil-proofness is poor.
Polymeric amide (PA, be commonly called as nylon) for toughness horn shape is translucent or creamy white crystals resin, there is 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 in 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 impact resistance is weak, range of application has a definite limitation.Obtain having the engineering product of more good characteristic by polyamide material and strongthener, toughening material or other materials compound, as used glass fibre and other filler filling enhancing modified, improving properties of nylons and expanding 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 synthesized by aromatic dicarboxylic acid and aliphatic chain diamines.Its advantage is proportion optimization by synthesizing nylon and preferably elastomeric, prepares the modified nylon materials that initial impact energy of rupture is large, can effectively avoid cracking in materials'use process, keep 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 mixed in conjunction with polymeric amide and elastomeric advantage, use range industrially both expanding, but the mixing of bi-material, particularly polyamide material and thermoplastic elastomer TPE polarity and structural difference, cause the poor compatibility of bi-material, if do not carry out corresponding modification with the consistency of both raisings to polymeric amide or TPE, the performance of product directly can be had influence on.
Summary of the invention
At present, in the thermoplastic elastomer technical field for electric wire and cable jacket and automotive pipeline, in the urgent need to a kind of high temperature resistant, the oil-proofness both with polyamide material, there is 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 a kind of modified elastomer of high temperature resistant, ageing-resistant, nylon66 fiber that oil resistant, tensile strength be good.
To achieve these goals, technical scheme of the present invention is as follows:
A modified elastomer for nylon66 fiber, 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 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 method for the modified elastomer of nylon66 fiber as above, its concrete steps are as follows:
First PA66 and a white mineral oil are joined in stirrer, after stirring, add calcium stearate wherein again, stir, continue to add maleic anhydride graft terpolymer EP rubber wherein, ultra-low density polyethylene and SEBS, after being stirred, import a twin screw extruder (district temperature 190-220 DEG C, two district temperature 200-230 DEG C, three district temperature 205-235 DEG C, four district temperature 215-245 DEG C, five district temperature 225-255 DEG C, six district temperature 235-265 DEG C, seven district temperature 245-275 DEG C, eight district temperature 250-280 DEG C, nine district temperature 250-280 DEG C, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6MPa), finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon66 fiber.
PA66 is the one in polymeric amide, and being translucent or creamy white crystals shape polymkeric substance, itself is that a kind of temperature tolerance is good, and the material that oil-proofness is excellent, and Process temperature ranges is wider, and its melt temperature is 260-280 DEG C.
SEBS take polystyrene as end segment, and the ethylene-butene copolymer obtained with polyhutadiene hydrogenation is the linear three embedding multipolymers of middle spring block, and it containing unsaturated double-bond, does not therefore have satisfactory stability and ageing resistance; Light specific gravity, good temperature tolerance, its catalytic temperature≤-60 DEG C, maximum operation (service) temperature reaches 149 DEG C, good solubility energy, blended characteristic and useful rush oiliness, can be dissolved in many common solvent, both there is plasticity-, again there is snappiness, can use be processed without the need to sulfuration, be widely used in and produce high-grade elastomerics, modifying plastics, tackiness agent, the filler of electric wire and sheath material etc.
SEBS is elastomerics, and hardness own is little, and PA itself is stone, and by being mixed by SEBS and PA, both blended suitable elastomericss of soft or hard of just making, are used in electric wire and cable jacket and automobile pipeline material.Maleic anhydride graft terpolymer EP rubber (i.e. maleic anhydride graft EPDM) is toughening nylon compatilizer, it solves the poor problem of nylon snappiness on the one hand, on the other hand also as compatilizer, play medium effect, solve PA and SEBS due to the interface interaction of bi-material weak, easily to peel off, problem that 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, weaken the formation of crystallizing field on main polymer chain, thus it has the performance of some excellences: such as it has excellent tensile strength, shock strength, tear strength and puncture intensity; Due to the linear crystalline for short-chain branch, fusing point is higher, modulus its good toughness less, softness, good hand touch, also has outstanding thinning performance (reaching 10-12.7um), good insulativity, preferably optical property, resistance to chemical corrosion, oil-proofness, stopping property etc.But it is when some Application Areas uses, and its hardness is not ideal enough.
The present invention has the following advantages and effect relative to prior art tool: by by PA66, ultra-low density polyethylene mixes with SEBS, add toughening nylon compatilizer maleic anhydride graft EPDM simultaneously, obtain mixed system (modified elastomer of nylon66 fiber), make it have the characteristic of the high temperature resistant and oil resistant of PA66, pass through SEBS simultaneously, it is little that ultra-low density polyethylene reaches mixed system proportion, the feature that toughness is excellent, and by maleic anhydride graft EPDM, impel PA66 and ultra-low density polyethylene, SEBS mixing, mixture is made to reach integraty, improve mixed system and easily peel off the problem bad with consistency, the modified elastomer of nylon66 fiber is made to 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 the examples below, maleic anhydride graft EPDM is that Sheyang Ketong Plastic Co., Ltd. produces.
Embodiment 1
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6615 part, maleic anhydride graft EPDM5 part, SEBS10 part, ultra-low density polyethylene 15 parts, calcium stearate 1 part, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 0.8%.
A preparation method for the modified elastomer of above-mentioned nylon66 fiber, comprises the following steps:
First the white mineral oil of PA66 and 1 part is joined in stirrer, after stirring, add calcium stearate wherein again, stir, continue to add maleic anhydride graft EPDM wherein, ultra-low density polyethylene and SEBS, after being stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 DEG C, two district temperature 200-230 DEG C, three district temperature 205-235 DEG C, four district temperature 215-245 DEG C, five district temperature 225-255 DEG C, six district temperature 235-265 DEG C, seven district temperature 245-275 DEG C, eight district temperature 250-280 DEG C, nine district temperature 250-280 DEG C, engine speed 350 revs/min, vacuum-0.06MPa, pressure 3.5MPa, finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon66 fiber.
Embodiment 2
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6645 part, maleic anhydride graft EPDM10 part, SEBS40 part, ultra-low density polyethylene 45 parts, calcium stearate 8 parts, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 1%.
A preparation method for the modified elastomer of above-mentioned nylon66 fiber, comprises the following steps:
First the white mineral oil of PA66 and 1 part is joined in stirrer, after stirring, add calcium stearate wherein again, stir, continue to add maleic anhydride graft EPDM wherein, ultra-low density polyethylene and SEBS, after being stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 DEG C, two district temperature 200-230 DEG C, three district temperature 205-235 DEG C, four district temperature 215-245 DEG C, five district temperature 225-255 DEG C, six district temperature 235-265 DEG C, seven district temperature 245-275 DEG C, eight district temperature 250-280 DEG C, nine district temperature 250-280 DEG C, engine speed 350-450 rev/min, engine speed 450 revs/min, vacuum-0.06MPa, pressure 6MPa, finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon66 fiber.
Embodiment 3
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6670 part, maleic anhydride graft EPDM15 part, SEBS70 part, ultra-low density polyethylene 75 parts, calcium stearate 15 parts, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.5%.
A preparation method for the modified elastomer of above-mentioned nylon66 fiber, comprises the following steps:
First the white mineral oil of PA66 and 1 part is joined in stirrer, after stirring, add calcium stearate wherein again, stir, continue to add maleic anhydride graft EPDM wherein, ultra-low density polyethylene and SEBS, after being stirred, import twin screw extruder, complete processing is as follows: a district temperature 190-220 DEG C, two district temperature 200-230 DEG C, three district temperature 205-235 DEG C, four district temperature 215-245 DEG C, five district temperature 225-255 DEG C, six district temperature 235-265 DEG C, seven district temperature 245-275 DEG C, eight district temperature 250-280 DEG C, nine district temperature 250-280 DEG C, engine speed 400 revs/min, vacuum-0.06MPa, pressure 5MPa, finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon66 fiber.
Embodiment 4
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6665 part, maleic anhydride graft EPDM10 part, SEBS60 part, ultra-low density polyethylene 60 parts, calcium stearate 5 parts, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.2%.
The preparation method of the modified elastomer of this nylon66 fiber is with the preparation method shown in embodiment 3.
Embodiment 5
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6635 part, maleic anhydride graft EPDM10 part, SEBS30 part, ultra-low density polyethylene 30 parts, calcium stearate 5 parts, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.4%.
The preparation method of the modified elastomer of this nylon66 fiber is with the preparation method shown in embodiment 2.
Embodiment 6
A modified elastomer for nylon66 fiber, comprises following component by weight: PA6640 part, maleic anhydride graft EPDM12 part, SEBS35 part, ultra-low density polyethylene 30 parts, calcium stearate 10 parts, white mineral oil 1 part, wherein the percentage of grafting of maleic anhydride graft EPDM is 1.3%.
The preparation method of the modified elastomer of this nylon66 fiber is with the preparation method shown in embodiment 1.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Performance test:
The modified elastomer getting the nylon66 fiber of above-described embodiment 1-6 gained carries out performance test, and testing method is as detection method in following table, and the test result of one of them embodiment is as shown in the table.
Can be found out by upper table contrast, under the same testing conditions, tensile strength of the present invention and 100% surely stretching property is better than TPE and TPV, and thermotolerance and oil-proofness, close to good, are far superior to TPE and TPV.
Claims (3)
1. a modified elastomer for nylon66 fiber, is characterized in that, comprises by weight: PA6615-70 part, toughening nylon compatilizer 5-15 part, SEBS 10-70 part, ultra-low density polyethylene 15-75 part, calcium stearate 1-15 part, white mineral oil 1-2 part; Described toughening nylon compatilizer is maleic anhydride graft terpolymer EP rubber;
The percentage of grafting of described maleic anhydride graft terpolymer EP rubber is 1%-1.5%.
2. prepare a method for the modified elastomer of nylon66 fiber according to claim 1, it is characterized in that, concrete steps are as follows:
First PA66 and a white mineral oil are joined in stirrer, after stirring, then add calcium stearate wherein, stir, continue to add maleic anhydride graft terpolymer EP rubber, ultra-low density polyethylene and SEBS wherein, after being stirred, import twin screw extruder; Finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain described nylon66 fiber.
3. according to the preparation method described in claim 2, it is characterized in that, described twin screw extruder, complete processing is as follows: a district temperature 190-220 DEG C, two district temperature 200-230 DEG C, three district temperature 205-235 DEG C, four district temperature 215-245 DEG C, five district temperature 225-255 DEG C, six district temperature 235-265 DEG C, seven district temperature 245-275 DEG C, eight district temperature 250-280 DEG C, nine district temperature 250-280 DEG C, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6MPa.
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| CN103665861B (en) * | 2013-11-21 | 2016-03-23 | 安徽师范大学 | The polyolefin modified nylon material of a kind of automotive plastic parts lightweight |
| 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 |
| 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 |
| 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 |
| 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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Effective date of registration: 20220811 Address after: Unit 01, Building 3, No. 1, Fu'an West Road, Dajiang Town, Taishan City, Jiangmen City, Guangdong Province, 529259 Patentee after: Guangdong Mingju New Material Technology Co.,Ltd. Address before: 523000 the third industrial zone, Chung Chung, Dongguan, Guangdong. Patentee before: DONGGUAN MINGJU PLASTICS Co.,Ltd. |