CN102153860A - Modified nylon material with high weld line strength and preparation method thereof - Google Patents
Modified nylon material with high weld line strength and preparation method thereof Download PDFInfo
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- CN102153860A CN102153860A CN2011101017650A CN201110101765A CN102153860A CN 102153860 A CN102153860 A CN 102153860A CN 2011101017650 A CN2011101017650 A CN 2011101017650A CN 201110101765 A CN201110101765 A CN 201110101765A CN 102153860 A CN102153860 A CN 102153860A
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- high weld
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000004677 Nylon Substances 0.000 title claims abstract description 69
- 229920001778 nylon Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 38
- 238000001125 extrusion Methods 0.000 claims abstract description 35
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- -1 pentaerythritol ester Chemical class 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 21
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 14
- 239000012764 mineral filler Substances 0.000 claims description 13
- 229920002292 Nylon 6 Polymers 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229960004839 potassium iodide Drugs 0.000 claims description 2
- 235000007715 potassium iodide Nutrition 0.000 claims description 2
- HSNCNVVQXXWMDW-UHFFFAOYSA-N prop-1-enylsilicon Chemical compound CC=C[Si] HSNCNVVQXXWMDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims 1
- 239000011256 inorganic filler Substances 0.000 abstract 7
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 7
- 238000005453 pelletization Methods 0.000 description 30
- 238000001816 cooling Methods 0.000 description 15
- 238000005469 granulation Methods 0.000 description 15
- 230000003179 granulation Effects 0.000 description 15
- 239000000523 sample Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- 229920006659 PA12 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a modified nylon material with high weld line strength and a preparation method thereof. The modified nylon material with high weld line strength comprises the following components in percentage by weight: 38.2-94.7% of nylon resin, 5-60% of inorganic filler, 0.1-0.6% of antioxidant, 0.1-0.6% of lubricant and 0.1-0.6% of talcum powder with the particle diameter being smaller than 1 micron, wherein the inorganic filler is chopped alkali-free glass fiber or kaolin processed by using a silane coupling agent. In the invention, the specially appointed inorganic filler processed by using the specially appointed coupling agent is added to the processing formula of the nylon material, thus the dispersity of the inorganic filler in the nylon resin and the interfacial binding force of the inorganic filler with the nylon resin can be effectively modified, and the weld line strength of the nylon material is enhanced. Furthermore, the inorganic filler is fed into an extruder for extrusion processing from a side feed inlet in the form of lateral feeding during the preparation of the nylon material, thus the structure of the inorganic filler can be prevented from being damaged due to long-time mixing, and the further guarantee is provided for the excellent service performance of the nylon material.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of high weld mark strength modified nylon materials and preparation method thereof.
Background technology
Nylon material has higher physical strength, thermotolerance, self lubricity, good barrier property and chemical resistance, excellent combination property.At present, nylon material has been widely used in automobile industry, machinery manufacturing industry, fields such as electronic apparatus and communications and transportation, and its consumption occupy first of the five large-engineering plastics.Nylon material generally comprises PA6(nylon 6), PA66(nylon 66), PA1010, PA11, PA12, PA46, PA6T, PA9T and PA10T etc.Using maximum nylon materials in automobile industry is PA6 and PA66.Because conventional injection moulding process moulded products inevitably can stay weld mark on goods.Though it is indiscoverable that these weld marks are naked eyes, it is a link the weakest on the product strength.For avoiding weld mark to bring infringement for the use of goods, common solution is that product material is carried out modification or the structure design of forming mould is improved, and weld mark is stayed non-stress, non-key position, and these two kinds of methods also can and be used certainly.
Improve at present the existing many publications of method of weld mark, can eliminate the mould and the using method thereof of the porose products appearance weld mark of injection moulding as CN 03139111.7(from the angle of mould), the CN 200720121116.6(injection mold that can eliminate weld mark), the improved injection moulding process of CN 200710037661.1(, install and comprise the adapted to injection system of lid arrangement) and CN 201010161629.6(improve the method for polymkeric substance injection-molded item weld mark mechanical property) etc.But the method for weld mark is eliminated or improved to this angle from injection-moulding device, can drop into by increase equipment undoubtedly.
The method of improving weld mark from the angle of material has disclosed patent CN 101735577 A(high weld mark strength reinforced polybutylene terephthalate and preparation method thereof) and CN 101735508 an A(high weld mark strength reinforced polypropylene material and preparation method thereof) etc., they are from the angle from material, carry out optimization of formulation, obtained extraordinary high weld mark strength strongthener.
But this angle from formulation optimization is come the domestic report that yet there are no of the patent of Reinforced Nylon material weld mark strength.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, angle from formulation optimization, a kind of modified nylon materials of high weld mark strength is provided, it can not increase cost and not under the prerequisite of expendable material physicals, the weld mark strength of nylon material is being improved.
The present invention also will provide a kind of preparation method of above-mentioned high weld mark strength modified nylon materials.
For solving above technical problem, the present invention takes following technical scheme:
A kind of high weld mark strength modified nylon materials, by weight percentage, its composition of raw materials comprises:
Nylon resin 38.2% ~ 94.7%;
Mineral filler 5% ~ 60% through coupling agent treatment;
Oxidation inhibitor 0.1% ~ 0.6%;
Lubricant 0.1% ~ 0.6%;
Particle diameter is less than the talcum powder 0.1% ~ 0.6% of 1 μ m;
Described nylon resin is nylon 6 or nylon 66 or the combination of the two, the relative viscosity of described nylon resin between 2.0 ~ 3.4, haze value≤50 μ g/g;
Described mineral filler is glass fibre or kaolin or the combination of these two, and described glass fibre is that the weak point of diameter between 10 μ m ~ 13 μ m cut alkali free glass fibre, and described coupling agent is a silane coupling agent.
The viscosity number of above-mentioned nylon resin is meant the viscosity number according to standard ISO 307 test gained; Haze value is meant according to the standard P V3015 of Volkswagen and tests, 100 ℃ of oil bath temperatures, and the haze value of gained under the condition of test duration 16h.Weak point in the described composition of raw materials is cut alkali free glass fibre can have extraordinary binding ability with nylon after handling through silane coupling agent, and described kaolin also can have good dispersiveness and very strong interface binding power in nylon resin after handling through silane coupling agent.These have played crucial effects through the mineral filler that silane coupling agent is handled for the weld mark strength of improving nylon material.Described particle diameter mainly plays the effect of nucleator in materials processing less than the talcum powder of 1 μ m.
Select as the above-mentioned raw materials optimization of formulation, described oxidation inhibitor can be selected from N, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1089), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) combination of one or more in pentaerythritol ester (antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (oxidation inhibitor 168) and mantoquita composite antioxidant propionic acid); Still more preferably, described oxidation inhibitor is selected from antioxidant 1010 or mantoquita composite antioxidant or the combination of these two, and described mantoquita composite antioxidant can be selected the mixture of 50% ~ 90% potassiumiodide and 10% ~ 40% cuprous iodide for use, or the mixture of 50% ~ 90% Potassium Bromide and 10% ~ 40% cuprous iodide.
Preferably, the combination of one or more in the optional autoxidation polyethylene wax of described lubricant, ethylene vinyl acetate, ethylene acrylic acid co polymer and the Poly Propylene Wax, and most preferably be oxidized polyethlene wax.
Preferably, described silane coupling agent can be one or more the combination in amino silicane coupling agent, epoxy silane coupling, folded amino silicane coupling agent, propenyl silane coupling agent and the vinyl silicane coupling agent, and wherein most preferably is amino silicane coupling agent.
In addition, can also add other common additives of usual amounts in the prescription of the high weld mark strength modified nylon materials of the present invention, give material different performances, as photostabilizer arbitrarily, static inhibitor, tinting material etc.
The preparation method of the high weld mark strength modified nylon materials of the present invention is as follows: the high weld mark strength modified nylon materials of the present invention is extruded by screw extrusion press and is processed to form; Described screw extrusion press has the main opening for feed that lays respectively at two ends and discharge port, between described main opening for feed and discharge port and one or more side opening for feeds at the described discharge port of distance 3/10 ~ 7/10 screw extrusion press length place; When extruding, earlier the nylon resin of formula ratio, the oxidation inhibitor of formula ratio, the lubricant of formula ratio, the talcum powder of formula ratio and/or the mineral filler of part formula ratio are mixed in mixing device together, to mix the gained material then and feed the screw extrusion press, the mineral filler of formula ratio or remainder formula ratio will be fed the screw extrusion presss from described one or more side opening for feeds from main opening for feed; In the extrusion process, the temperature of extruding processing is controlled between 210 ℃ ~ 300 ℃, and the time that the material that feeds from main opening for feed stops screw extrusion press is controlled at 2 ~ 3 minutes, and the barrel vacuum degree control-0.04MPa of screw extrusion press ~-0.08MPa.Control vacuum tightness is in order in time the small-molecule substance that produces in the extrusion to be removed, to be beneficial to processing.
Further improvement as above-mentioned preparation method, described screw extrusion press evenly is divided into nine sections from main opening for feed to discharge port, respectively corresponding nine temperature ranges, and the temperature relation of each temperature range is: district's temperature＜two district's temperature≤three district's temperature≤four district's temperature, six district's temperature 〉=seven district's temperature 〉=eight district's temperature 〉=nine district's temperature, described one or more side opening for feeds communicate with four districts, five districts or six districts respectively.
Because the enforcement of above technical scheme, the present invention compared with prior art has plurality of advantages:
The present invention is by adding the specific mineral filler through specific coupling agent treatment in the processing formula of nylon material, can effectively improve mineral filler dispersed in nylon resin and with the interface binding power of nylon resin, improve the weld mark strength of material, do not influence other use propertieies of material simultaneously again; Prepare in the process of described high weld mark strength nylon material, make part or all of mineral filler send into forcing machine from the side opening for feed and extrude processing with the form of side direction feeding, the structure that can avoid mineral filler mixing destruction when long, simultaneously extrude temperature, time and the vacuum tightness of processing, do not provide further assurance for the use properties of material is destroyed according to the working properties control of nylon material.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
Embodiment 1
With 64 weight part nylon 6(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 2
With 64 weight part nylon 6(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (13 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 3
With 64 weight part nylon 6(viscosity 2.7), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 4
With 64 weight part nylon 66(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 5
With 64 weight part nylon 66(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (13 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 6
With 64 weight part nylon 66(viscosity 2.7), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 35 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 7
With 59 weight part nylon 6(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 8
With 59 weight part nylon 6(viscosity 2.7), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 9
With 59 weight part nylon 66(viscosity 2.4), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 10
With 59 weight part nylon 66(viscosity 2.7), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 11
With 59 weight part nylon 66(viscosity 3.2), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 12
With 49 weight part nylon 66(viscosity 3.2), 10 weight part nylon 6(viscosity 2.7), 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder add in the high mixer, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 40 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated kaolin through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 13
With 69 weight part nylon 6(viscosity 2.4), 20 weight parts add in the high mixer through amino silicane coupling agent surface-treated kaolin, 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 10 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 220 ℃ of district's temperature, 230 ℃ of two district's temperature, 240 ℃ of three district's temperature, 240 ℃ of four district's temperature, 250 ℃ of five district's temperature, 250 ℃ of six district's temperature, 245 ℃ of seven district's temperature, 235 ℃ of eight district's temperature, 220 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 14
With 59 weight part nylon 66(viscosity 2.7), 25 weight parts add in the high mixer through amino silicane coupling agent surface-treated kaolin, 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 15 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
Embodiment 15
With 59 weight part nylon 66(viscosity 2.7), 20 weight parts add in the high mixer through amino silicane coupling agent surface-treated kaolin, 0.3 weight part mantoquita composite antioxidant, 0.3 weight part oxidized polyethlene wax and 0.4 weight part talcum powder, at room temperature mix, main opening for feed through twin screw extruder feeds in the forcing machine again, and 20 weight parts are fed in the forcing machine through the side opening for feed of amino silicane coupling agent surface-treated glass fibre (10 μ m) through twin screw extruder; Utilize twin screw extruder to carry out extruding pelletization, the processing conditions of extruding pelletization is: 240 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 280 ℃ of four district's temperature, 275 ℃ of five district's temperature, 275 ℃ of six district's temperature, 275 ℃ of seven district's temperature, 270 ℃ of eight district's temperature, 270 ℃ of nine district's temperature; The residence time of material screw extrusion press that feeds from main opening for feed is 2 minutes, 350 rev/mins of engine speeds; Vacuum tightness is-0.04～-0.08MPa.Extrude the material of processing after the granulation and promptly get high weld mark strength nylon material product through cooling, oven dry.
To the product sample preparation of the various embodiments described above gained nylon material and carry out following performance test:
Tensile property: test by ISO527-2, specimen size is 150 * 10 * 4mm
3, draw speed is 5mm/min, probe temperature is 23 ℃.
The weld mark performance: test with reference to ISO527-2, specimen size is 150 * 10 * 4mm
3, draw speed is 5mm/min, probe temperature is 23 ℃.
Each Example formulations and material properties test the results are shown in table 1, table 2, table 3.
Table 1 embodiment 1～6 prescription and the prepared sample performance test result of each embodiment
Table 2 embodiment 7～12 prescription and the prepared sample performance test results of each embodiment
Table 3 embodiment 13～15 prescription and the prepared sample performance test results of each embodiment
Data from table 1, table 2 and table 3 as can be seen, the high weld mark strength nylon material that obtains according to the present invention has not only obtained high weld mark strength, also mechanical property preferably can be obtained, the making of the component of motor car engine periphery (as intake manifold, engine bonnet, valve chamber cover, scatterer, air door or the like) and other industry can be widely used in.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. one kind high weld mark strength modified nylon materials, by weight percentage, its composition of raw materials comprises:
Nylon resin 38.2% ~ 94.7%;
Mineral filler 5% ~ 60% through coupling agent treatment;
Oxidation inhibitor 0.1% ~ 0.6%;
Lubricant 0.1% ~ 0.6%;
Particle diameter is less than the talcum powder 0.1% ~ 0.6% of 1 μ m;
Described nylon resin is nylon 6 or nylon 66 or the combination of the two, the relative viscosity of described nylon resin between 2.0 ~ 3.4, haze value≤50 μ g/g;
Described mineral filler is glass fibre or kaolin or the combination of these two, and described glass fibre is that the weak point of diameter between 10 μ m ~ 13 μ m cut alkali free glass fibre, and described coupling agent is a silane coupling agent.
2. high weld mark strength modified nylon materials according to claim 1; it is characterized in that: described oxidation inhibitor is N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine, four (β-(3 propionyl); the 5-di-tert-butyl-hydroxy phenyl) combination of one or more in pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and mantoquita composite antioxidant propionic acid).
3. high weld mark strength modified nylon materials according to claim 1 is characterized in that: described oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester or mantoquita composite antioxidant or combination of the two.
4. according to claim 1 or 2 or 3 described high weld mark strength modified nylon materials, it is characterized in that: described mantoquita composite antioxidant is the mixture of 50% ~ 90% potassiumiodide and 10% ~ 40% cuprous iodide, or the mixture of 50% ~ 90% Potassium Bromide and 10% ~ 40% cuprous iodide.
5. high weld mark strength modified nylon materials according to claim 1 is characterized in that: described lubricant is one or more the combination in oxidized polyethlene wax, ethylene vinyl acetate, ethylene acrylic acid co polymer and the Poly Propylene Wax.
6. high weld mark strength modified nylon materials according to claim 1 is characterized in that: described lubricant is an oxidized polyethlene wax.
7. high weld mark strength modified nylon materials according to claim 1 is characterized in that: described silane coupling agent is one or more the combination in amino silicane coupling agent, epoxy silane coupling, folded amino silicane coupling agent, propenyl silane coupling agent and the vinyl silicane coupling agent.
8. high weld mark strength modified nylon materials according to claim 1 is characterized in that: described silane coupling agent is an amino silicane coupling agent.
9. the preparation method of a high weld mark strength modified nylon materials as claimed in claim 1, it is characterized in that: described high weld mark strength modified nylon materials is extruded by screw extrusion press and is processed to form; Described screw extrusion press has the main opening for feed that lays respectively at two ends and discharge port, between described main opening for feed and discharge port and one or more side opening for feeds at the described discharge port of distance 3/10 ~ 7/10 screw extrusion press length place; When extruding, earlier the nylon resin of formula ratio, the oxidation inhibitor of formula ratio, the lubricant of formula ratio, the talcum powder of formula ratio and/or the mineral filler of part formula ratio are mixed in mixing device together, to mix the gained material then and feed the screw extrusion press, the mineral filler of formula ratio or remainder formula ratio will be fed the screw extrusion presss from described one or more side opening for feeds from main opening for feed; In the extrusion process, the temperature of extruding processing is controlled between 210 ℃ ~ 300 ℃, and the time that the material that feeds from main opening for feed stops screw extrusion press is controlled at 2 ~ 3 minutes, and the barrel vacuum degree control of screw extrusion press-0.04MPa ~-0.08MPa.
10. the preparation method of high weld mark strength modified nylon materials according to claim 9, it is characterized in that: described screw extrusion press evenly is divided into nine sections from main opening for feed to discharge port, respectively corresponding nine temperature ranges, and the temperature relation of each temperature range is: district's temperature＜two district's temperature≤three district's temperature≤four district's temperature, six district's temperature 〉=seven district's temperature 〉=eight district's temperature 〉=nine district's temperature, described one or more side opening for feeds communicate with four districts, five districts or six districts respectively.
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| WO2012103747A1 (en) * | 2011-01-31 | 2012-08-09 | 上海金发科技发展有限公司 | Highly fatigue-resistant glass fiber reinforced nylon material and preparation method therefor |
| CN102732010A (en) * | 2012-06-15 | 2012-10-17 | 苏州宇度医疗器械有限责任公司 | Scented nylon composite material |
| CN102786793A (en) * | 2012-07-25 | 2012-11-21 | 金发科技股份有限公司 | Modified nylon material and its preparation method |
| CN103642208A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Nanometer kaolin modified nylon 6 material for automobile plastic members |
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| WO2012103747A1 (en) * | 2011-01-31 | 2012-08-09 | 上海金发科技发展有限公司 | Highly fatigue-resistant glass fiber reinforced nylon material and preparation method therefor |
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| CN103642208A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Nanometer kaolin modified nylon 6 material for automobile plastic members |
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| CN105419316A (en) * | 2015-12-08 | 2016-03-23 | 广州市合诚化学有限公司 | High weld mark strength enhanced polyamide material, preparation method thereof and application |
| CN109438979A (en) * | 2018-11-22 | 2019-03-08 | 浙江华谊胜德材料科技有限公司 | A kind of high smooth engineering plastic alloy and preparation method thereof |
| CN111621151A (en) * | 2020-07-09 | 2020-09-04 | 东莞市奥能工程塑料有限公司 | High-rigidity high-bonding-strength nylon reinforced material and preparation method thereof |
| CN112625435A (en) * | 2020-12-24 | 2021-04-09 | 天津柯文实业股份有限公司 | High-temperature-resistant PA material for vehicle electric appliance box and preparation method thereof |
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Application publication date: 20110817 |