CN103214832B - Nylon 46 modified elastomer and preparation method thereof - Google Patents
Nylon 46 modified elastomer and preparation method thereof Download PDFInfo
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- CN103214832B CN103214832B CN201310013620.4A CN201310013620A CN103214832B CN 103214832 B CN103214832 B CN 103214832B CN 201310013620 A CN201310013620 A CN 201310013620A CN 103214832 B CN103214832 B CN 103214832B
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- nylon
- district temperature
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- maleic anhydride
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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 present invention belongs to the technical field of thermoplastic elastomers, and discloses a nylon 46 modified elastomer and a preparation method thereof. The nylon 46 modified elastomer comprises, by weight, 15-70 parts of PA46, 5-15 parts of a nylon toughening compatibilizer, 10-70 parts of SEBS, 15-75 parts of an ultra low density polyethylene, 1-15 parts of calcium stearate, and 1-2 parts of white mineral oil. The nylon 46 modified elastomer has characteristics of high temperature resistance and oil resistance of the PA46, and low specific gravity and excellent toughness of the SEBS and the ultra low density polyethylene, and further has characteristics of good compatibility, suitable 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 nylon 46 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, there is 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, temperature limit wide (-60-150 DEG C), 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, nylon 46 that oil resistant, tensile strength be good.
To achieve these goals, technical scheme of the present invention is as follows:
A modified elastomer for nylon 46, comprises following component by weight: PA4615-70 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.
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 nylon 46 as above, its concrete steps are as follows:
First PA46 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 elastomer material that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon 46.
Twin-screw extrusion process for machining is as follows: a district temperature 240-270 DEG C, two district temperature 250-280 DEG C, three district temperature 255-285 DEG C, four district temperature 260-290 DEG C, five district temperature 265-295 DEG C, six district temperature 270-300 DEG C, seven district temperature 275-305 DEG C, eight district temperature 280-310 DEG C, nine district temperature 280-310 DEG C, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6Mpa.
PA46 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, its fusing point is lower, and Process temperature ranges is wider, and its shock resistance is better than PA6, and its melt temperature is 280-300 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 PA46, ultra-low density polyethylene mixes with SEBS, add toughening nylon compatilizer maleic anhydride graft EPDM simultaneously, obtain mixed system (modified elastomer of nylon 46), make it have the characteristic of the high temperature resistant and oil resistant of PA46, 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 PA46 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 nylon 46 is made to reach high temperature resistant, ageing-resistant, oil resistant, the perfect condition that tensile strength is good.
Embodiment
Below the specific embodiment of the present invention is described in further detail.
In the examples below, maleic anhydride graft EPDM is that Sheyang Ketong Plastic Co., Ltd. produces.
Embodiment 1
A modified elastomer for nylon 46, comprises following component by weight: PA4615 part, maleic anhydride graft EPDM5 part, SEBS 10 parts, 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 nylon 46, comprises the following steps:
First the white mineral oil of PA46 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 240-270 DEG C, two district temperature 250-280 DEG C, three district temperature 255-285 DEG C, four district temperature 260-290 DEG C, five district temperature 265-295 DEG C, six district temperature 270-300 DEG C, seven district temperature 275-305 DEG C, eight district temperature 280-310 DEG C, nine district temperature 280-310 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 nylon 46.
Embodiment 2
A modified elastomer for nylon 46, comprises following component by weight: PA46 45 parts, maleic anhydride graft EPDM10 part, SEBS 40 parts, 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 nylon 46, comprises the following steps:
First the white mineral oil of PA46 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 240-270 DEG C, two district temperature 250-280 DEG C, three district temperature 255-285 DEG C, four district temperature 260-290 DEG C, five district temperature 265-295 DEG C, six district temperature 270-300 DEG C, seven district temperature 275-305 DEG C, eight district temperature 280-310 DEG C, nine district temperature 280-310 DEG C, engine speed 450 revs/min, vacuum-0.06MPa, pressure 6MPa, finally extrude the modified elastomer that namely rear cooling, dehumidifying, pelletizing, drying, packaging obtain nylon 46.
Embodiment 3
A modified elastomer for nylon 46, comprises following component by weight: PA4 670 parts, maleic anhydride graft EPDM15 part, SEBS 70 parts, 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 nylon 46, comprises the following steps:
First the white mineral oil of PA46 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 240-270 DEG C, two district temperature 250-280 DEG C, three district temperature 255-285 DEG C, four district temperature 260-290 DEG C, five district temperature 265-295 DEG C, six district temperature 270-300 DEG C, seven district temperature 275-305 DEG C, eight district temperature 280-310 DEG C, nine district temperature 280-310 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 nylon 46.
Embodiment 4
A modified elastomer for nylon 46, comprises following component by weight: PA4665 part, maleic anhydride graft EPDM10 part, SEBS 60 parts, 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 nylon 46 is with the preparation method shown in embodiment 3.
Embodiment 5
A modified elastomer for nylon 46, comprises following component by weight: PA4635 part, maleic anhydride graft EPDM10 part, SEBS 30 parts, 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 nylon 46 is with the preparation method shown in embodiment 2.
Embodiment 6
A modified elastomer for nylon 46, comprises following component by weight: PA4640 part, maleic anhydride graft EPDM12 part, SEBS 35 parts, 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 nylon 46 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 nylon 46 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 (6)
1. a modified elastomer for nylon 46, is characterized in that, comprises by weight: PA46 15-70 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.
2. the modified elastomer of nylon 46 according to claim 1, is characterized in that: described toughening nylon compatilizer is maleic anhydride graft terpolymer EP rubber.
3. the modified elastomer of nylon 46 according to claim 2, 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 46 according to claim 2, is characterized in that: the percentage of grafting of described maleic anhydride graft terpolymer EP rubber is 1%-1.5%.
5. prepare a method for the modified elastomer of nylon 46 according to claim 1, it is characterized in that, concrete steps are as follows:
First PA46 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 nylon 46.
6. according to the preparation method described in claim 5, it is characterized in that, described twin screw extruder, complete processing is as follows: a district temperature 240-270 DEG C, two district temperature 250-280 DEG C, three district temperature 255-285 DEG C, four district temperature 260-290 DEG C, five district temperature 265-295 DEG C, six district temperature 270-300 DEG C, seven district temperature 275-305 DEG C, eight district temperature 280-310 DEG C, nine district temperature 280-310 DEG C, engine speed 350-450 rev/min, vacuum-0.06MPa, pressure 3.5-6MPa.
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| CN201310013620.4A CN103214832B (en) | 2013-01-14 | 2013-01-14 | Nylon 46 modified elastomer and preparation method thereof |
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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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278233A (en) * | 1990-06-14 | 1994-01-11 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
| CN1257528A (en) * | 1997-04-25 | 2000-06-21 | 罗狄亚塑料工程股份有限责任公司 | Polyamide composition for a method for making articles by extrusion blow-moulding and resulting articles |
| CN101255263A (en) * | 2008-03-17 | 2008-09-03 | 深圳市盛嘉伦橡塑工业有限公司 | Thermoplastic elastomer for nylon material secondary injection adhering |
-
2013
- 2013-01-14 CN CN201310013620.4A patent/CN103214832B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5278233A (en) * | 1990-06-14 | 1994-01-11 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
| CN1257528A (en) * | 1997-04-25 | 2000-06-21 | 罗狄亚塑料工程股份有限责任公司 | Polyamide composition for a method for making articles by extrusion blow-moulding and resulting articles |
| CN101255263A (en) * | 2008-03-17 | 2008-09-03 | 深圳市盛嘉伦橡塑工业有限公司 | Thermoplastic elastomer for nylon material secondary injection adhering |
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Denomination of invention: A Modified Elastomer of Nylon 46 and Its Preparation Method Effective date of registration: 20230523 Granted publication date: 20150318 Pledgee: Guangfa Bank Co.,Ltd. Taishan Branch Pledgor: Guangdong Mingju New Material Technology Co.,Ltd. Registration number: Y2023980041387 |
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