CN102516761A - Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof - Google Patents
Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof Download PDFInfo
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- CN102516761A CN102516761A CN2011103958305A CN201110395830A CN102516761A CN 102516761 A CN102516761 A CN 102516761A CN 2011103958305 A CN2011103958305 A CN 2011103958305A CN 201110395830 A CN201110395830 A CN 201110395830A CN 102516761 A CN102516761 A CN 102516761A
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Abstract
The invention provides a hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and a preparation method thereof. The hydrolysis-resistant alcoholysis-resistant nylon 66 composite material is characterized by comprising the following ingredients in parts by weight: 51.8 to 84.5 parts of nylon resin, 15 to 40 parts of short-cut glass fibers, 0.1 to 0.6 parts of nucleating agent, 0.1 to 0.6 parts of thermal stabilizer, 0.1 to 1.0 part of alcoholysis-resistant auxiliary agent, 0.1 to 5 parts of barrier material and 0.1 to 1.0 part of lubricant. The manufacturing method comprises the following steps that: the nylon 66 resin, antioxidant, hydrolysis-resistant agent, the barrier material, the nucleating agent and the lubricant, which are previously dried, are uniformly mixed at a high speed; and the mixture and the glass fiber are fed into a double-screw extruder to be extruded and pelleted. The hydrolysis-resistant alcoholysis-resistant nylon 66 composite material not only has good high temperature resistance and high thermal oxidation aging resistance, but also has excellent property for resisting the corrosion of glycol and solution thereof, and can completely satisfy the requirements on manufacturing components such as car heat radiator cooling water tanks, thermostats and charge air coolers.
Description
Technical field
The present invention relates to a kind of hydrolysis alcoholysis nylon 66 composite material, belong to the modified polyamide technical field.
Background technology
(CONH-), the hydrogen bond that forms between its group makes the structure of PA66 be easy to crystallization to nylon 66 (PA66), thereby it is good to make material have mechanical property because of containing strong polar carboxamido-group on its molecular chain; Self lubricity, use temperature is wide, and electrical insulating property is good; The oil-proofness chemicalstability is good; Be easy to characteristics such as processing, thereby be widely used, like automobile component in each field of national economy; High-speed railway fastener, the mechanical part of the various high loadinies such as cam of gear, automatic stamper.Weak point is a poor dimensional stability, and the more high factor of water-intake rate causes product can not satisfy the requirement of high-precision processing, can improve through method of modifying such as enhancing, fillings.In automobile industry; The cry of country's energy-saving and emission-reduction is increasingly high; The automobile light weight changes into the effect of bringing and more and more receives people's attention; Various high performance macromolecular materials have obtained using widely in the light-weighted process of automobile, and glass fiber enhanced nylon 66 alternative metals made automobile radiators water tank becomes a good application direction.
The Working environment of automobile radiators tank parts requires material to have ethylene glycol resistant and the etch of the aqueous solution more than 100 ℃; In assembling and use, do not allow to take place problems of crack simultaneously, common glass fiber enhanced nylon 66 is difficult to satisfy the function test and the actual user demand of this part.At present; MS as making the engine radiator water tank is mainly 30% glass fiber enhanced nylon 66; Because the engine radiator water tank contacts with quench liquid for a long time, and quench liquid staple commonly used in the market is that terepthaloyl moietie and water form according to the 1:1 volume ratio is composite, therefore; The nylon material that is used for preparing the engine water box part must be able to stand quench liquid long-term corrosion at high temperature, and defectives such as cracking can not appear in part.Domestic also have manufacturer to do the radiator water box material to use glass fiber enhanced nylon 66 material; But require because of the physicals of product can not satisfy the TL52062 of Volkswagen standard techniques (promptly under 135 ℃ of constant temperature, in 100% ethylene glycol solution behind the placement 48h, the product surface no change; Do not ftracture); And the technical requirements of General Motors GMW15468 (promptly under 130 ℃ of constant temperature, after corroding according to the composite quench liquid 1000h of 1:1 volume ratio through terepthaloyl moietie and water, the product surface no change; Do not have cracking), it mainly has problems, and to be material or part situation such as cracking or physicals decay be serious occur through quench liquid corrosion back.
Patent CN101191015A has announced a kind of nylon 66 (PA66) PP Pipe Compound of making the automobile radiators tank parts, is base material with PA66, adds spun glass; Cuprous halide, the halogenation first, the phenyl Hypophosporous Acid, 50 is received the compsn with Calcium Fluoride (Fluorspan); Materials such as organic antioxidant, the adding of calcium salt destroy the intermolecular ydrogen bonding effect of PA66 easily, reduce the percent crystallinity of material; Cause material compactness to descend, the ability of anti-alcoholysis is had a greatly reduced quality.Patent CN 101613527A has prepared the automobile hydroecium with alcoholysis resistance nylon 66; Phenomenons such as the ethylene bis-fatty acid amides of using in this patent (EBS) is decomposed under the processing temperature window of nylon 66 easily, causes the medium and small molecule content of material produce and moulding process higher, and coal mine gas is more; Situation such as bad order appear in part easily; Patent CN 101760020A has announced that a kind of preparation automobile radiators uses glass fiber enhanced nylon 66 material, and oxidation inhibitor 1098 that uses in the patent and 168 antioxidant effect are limited, the two independent or composite use; Its thermostable effect can't reach the requirement of life-time service at high temperature; In addition, used terpolymer EP rubber in the patent, though can improve the toughness of material as compatilizer; But since the corrosive power of the ethylene glycol resistant of terpolymer EP rubber own a little less than, cause the cold-resistant ability drop of freezing corrosion of material monolithic.
Summary of the invention
The glass fiber enhanced nylon 66 matrix material that the purpose of this invention is to provide a kind of hydrolysis alcoholysis; Performance with excellent long-term ethylene glycol resistant aqueous corrosion; Have anti-preferably long-term thermal-oxidative aging property and mechanical property preferably; Satisfy the automobile radiators water tank, the user demand of thermostat and charge air cooler.
In order to achieve the above object, the invention provides a kind of hydrolysis alcoholysis nylon 66 composite material, it is characterized in that, comprise following raw material in composition by weight:
Nylon resin 51.8-84.5 part;
Short glass fiber 15-40 part;
Nucleator 0.1-0.6 part;
Thermo-stabilizer 0.1-0.6 part;
Anti-pure enzymolysis auxiliary agent 0.1-1.0 part;
Barrier agent 0.1-5 part;
Lubricant 0.1-1.0 part.
Preferably, described nylon resin is a nylon 66, and relative viscosity is 2.4-3.2 (a Ubbelohde viscosimetry).
Further, described nylon 66 compound system that is any single viscosity or two kinds of different viscosity.
Preferably, described short glass fiber is the alkali-free short glass fiber, and filament diameter is 9 μ m-13 μ m.
Further, the filament diameter of described short glass fiber is 10 μ m.
Preferably, described nucleator is inorganic nucleator or organic nucleating agent, and the grain diameter of inorganic nucleator is less than 1 μ m; Organic nucleating agent is the composite nucleating agent of any one or two kinds of compositions in Sodium Benzoate, sorbyl alcohol dibenzyl ester, the montanate.
Further, described nucleator is talcum powder or montanate.
Preferably, described thermo-stabilizer is N, N/-1; 6-dihexyl two (3,5-two (1, the 1-dimethyl ethyl)-4-hydroxybenzene propionyl), four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, N, N
'In-diphenyl-para-phenylene diamine and the mantoquita composite antioxidant (mixture of potassium halide and cuprous halide) any one or two or more combinations.
Further, described thermo-stabilizer is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and mantoquita composite antioxidant.
Preferably, described anti-pure enzymolysis auxiliary agent is the amine stablizer.
Further, described anti-pure enzymolysis auxiliary agent is a polycarbodiimide class stablizer.
Preferably, described barrier agent is inorganic barrier agent, organic barrier agent or its compsn, and inorganic barrier agent is polynite, mica powder or its compsn, and consumption is 0.1-1 part; Organic barrier agent is ethylene-vinyl alcohol copolymer (EVOH), and consumption is 1-5 part.
Preferably, described lubricant is polyethylene wax class, polyol ester class or silicone lubricant.
Short glass fiber adopts the alkali-free short glass fiber; Spun glass is an E glass; The special coupling agent surface treatment of spun glass process, and have interface binding ability preferably between the nylon resin, have small molecules erosive abilities such as better anti-terepthaloyl moietie and water with common glass relatively.
Nucleator can adopt inorganic nucleator, talcum powder for example, polynite, lime carbonate; Or organic nucleating agent, like Sodium Benzoate, sorbyl alcohol dibenzyl ester, the composite nucleating agent of one or both compositions in the montanate.The adding of nucleator further promotes material to form comparatively fine and close spherulitic crystal structure, hinders the erosion of small-molecule substances such as terepthaloyl moietie and water to material.
Anti-pure enzymolysis auxiliary agent adopts the amine stablizer, like polycarbodiimide and N, N
'-diphenyl-para-phenylene diamine, the amine stablizer can be effectively with the end carboxyl of nylon and in the course of processing newly-generated acidic-group react, form the long-effective protection effect, improve the erosion of small-molecule substances such as nylon material opposing terepthaloyl moietie and water.
Inorganic barrier agent comprises grain diameter at the polynite of 1-10 μ m, mica powder etc.This inorganic barrier agent has laminar structured; In the course of processing, after screw rod shearing, laminar structured opening; Be scattered in the matrix resin; Played the effect of heterogeneous nucleation, the laminar structured effect of having played prolongation small molecules permeation pathway of dispersive simultaneously delays material to micromolecular absorption; Organic barrier agent is EVOH, and this type of barrier agent self has excellent barrier property to small-molecule substance, adds in the nylon system, can effectively strengthen the force of cohesion of system, reduces material to micromolecular absorptivity.
Component of the present invention can also add additive commonly used, gives material different performances.Addible component also comprises any photostabilizer, static inhibitor, tinting material etc. except that above-mentioned oxidation inhibitor.
The present invention also provides the preparation method of the glass fiber enhanced nylon 66 matrix material of above-mentioned hydrolysis alcoholysis, it is characterized in that concrete steps are following:
The first step: with dry good Nylon 66, inhibitor, hydrolysis agent, barrier agent, nucleator and lubricant mixed at high speed are even in advance;
Second step: the mixture that the first step is obtained feeds 250-280 ℃ with spun glass, and screw speed is in 300-450 rev/min the twin screw extruder, extruding pelletization.
Preferably, described twin screw extruder is provided with an above opening for feed, and each raw material in the first step is divided into arbitrarily more than two groups, adds twin screw extruder from different opening for feeds successively, carries out premix; The barrel of twin screw extruder is provided with an above vacuum extractor.
The barrel of twin screw extruder is provided with one or more vacuum extractors, can in time the small-molecule substance that produces in the material melt blending process be removed.
The present invention is in the glass fiber enhanced nylon 66 matrix material; Add auxiliary agents such as barrier agent, anti-pure enzymolysis auxiliary agent, thermo-stabilizer, nucleator; Through improving material percent crystallinity; Increase the stability of polymeric amide macromole in processing and life-time service process, improve the number of ways such as interface binding power of glass and matrix resin, give long-term preferably ethylene glycol resistant aqueous solution erosive ability of glass fiber enhanced nylon 66 and long term thermal oxidative stability.Satisfy the request for utilization of existing automobile radiators hydroecium and thermostat.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The polyol ester of 84.5kg nylon 66 (relative viscosity 2.4), the anti-pure enzymolysis auxiliary agent of 0.1kg polycarbodiimide class, 0.1kg mantoquita composite thermal stabilizer, 0.3kg talcum powder, 0.1kg polynite, 0.1kg is added in the high mixer, at room temperature mix through the feeding of twin screw extruder master feeder, 15kg spun glass (10 μ m) feeds through twin screw extruder side direction feeder; Carry out extruding pelletization through twin screw extruder; 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; 350 rev/mins of engine speeds.2 minutes residence time, 400 rev/mins of engine speeds; Vacuum tightness is-0.04MPa.
Embodiment 2
To the anti-pure enzymolysis auxiliary agent of benzene diimine class, 0.3kg mantoquita composite thermal stabilizer, 0.3kg antioxidant 1010, the silicone master batch of 0.3kg Sodium Benzoate, 0.3kg polynite, 0.3kg adds in the high mixer with 83kg nylon 66 (relative viscosity 2.4), 0.5kg, at room temperature mixes through twin screw extruder master feeder to feed; 15kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 3
With 82.5kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 1.0kg polycarbodiimide class, 0.3kg oxidation inhibitor 1098,0.3kg oxidation inhibitor 168, the polyol ester of 0.3kg sorbyl alcohol dibenzyl ester, 0.3kg mica powder, 0.3kg adds in the high mixer, at room temperature mixes through twin screw extruder master feeder to feed; 15kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.06MPa.
Embodiment 4
With 40.3kg nylon 66 (relative viscosity 3.2), 40kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg Ursol D class, 0.3kg antioxidant 1010,0.3kg mantoquita composite antioxidant, the silicone master batch of 0.3kg montanate, 3kgEVOH, 0.3kg adds in the high mixer, at room temperature mixes through twin screw extruder master feeder to feed; 15kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 400 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 5
With 67.3kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg polycarbodiimide, 0.3kg mantoquita composite antioxidant, 0.3kg talcum powder, 0.3kg polynite, 1kgEVOH, 0.3kg polyol ester add in the high mixer, at room temperature mix through twin screw extruder master feeder to feed; 30kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 6
With 64.9kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.3kg Ursol D class, 0.3kg antioxidant 1010,0.3kg mantoquita composite antioxidant, 0.3kg Sodium Benzoate, 0.3kg polynite, 3kgEVOH, 0.3kg polyol ester add in the high mixer, at room temperature mix through twin screw extruder master feeder to feed; 30kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 7
With 63.2kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.3kg Ursol D class, 0.3kg oxidation inhibitor 1098,0.3kg oxidation inhibitor 168,0.3kg sorbyl alcohol dibenzyl ester, 5kgEVOH, 0.3kg polyol ester, 0.3kg silicone master batch add in the high mixer, at room temperature mix through twin screw extruder master feeder to feed; 30kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 8
With 65kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg Carbodiimides, 0.3kg oxidation inhibitor 1098,0.3kg oxidation inhibitor 168,0.3kg montanate, 0.3kg mica powder, 3kgEVOH, 0.3kg silicone master batch add in the high mixer, at room temperature mix through twin screw extruder master feeder to feed; 30kg spun glass (10 μ m) carries out extruding pelletization through the feeding of twin screw extruder side direction feeder through twin screw extruder, and 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 9
64.4kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg Carbodiimides, 0.3kg antioxidant 1010,0.3kg mantoquita composite antioxidant, 0.3kg talcum powder, 0.3kg montanate, 0.3kg mica powder, 3kgEVOH, 0.6kg polyol ester are added in the high mixer, at room temperature mix through the feeding of twin screw extruder master feeder, 30kg spun glass (10 μ m) feeds through twin screw extruder side direction feeder; Carry out extruding pelletization through twin screw extruder; 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 10
57.3kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg Ursol D class, 0.3kg mantoquita composite antioxidant, 0.3kg talcum powder, 0.3kg montanate, 0.3kg mica powder, 1kgEVOH, 0.3kg polyol ester are added in the high mixer, at room temperature mix through the feeding of twin screw extruder master feeder, 40kg spun glass (10 μ m) feeds through twin screw extruder side direction feeder; Carry out extruding pelletization through twin screw extruder; 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 11
55kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 0.5kg polycarbodiimide class, 0.3kg antioxidant 1010,0.3kg mantoquita composite antioxidant, 0.3kg montanate, 0.3kg polynite, 3kgEVOH, 0.3kg silicone master batch are added in the high mixer, at room temperature mix through the feeding of twin screw extruder master feeder, 40kg spun glass (10 μ m) feeds through twin screw extruder side direction feeder; Carry out extruding pelletization through twin screw extruder; 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Embodiment 12
51.8kg nylon 66 (relative viscosity 2.7), the anti-pure enzymolysis auxiliary agent of 1kg Ursol D class, 0.3kg oxidation inhibitor 1098,0.3kg oxidation inhibitor 168,0.3kg talcum powder, 0.3kg sorbyl alcohol dibenzyl ester, 5kgEVOH, 1kg silicone master batch are added in the high mixer, at room temperature mix through the feeding of twin screw extruder master feeder, 40kg spun glass (10 μ m) feeds through twin screw extruder side direction feeder; Carry out extruding pelletization through twin screw extruder; 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; 400 rev/mins of engine speeds.2 minutes residence time, 350 rev/mins of engine speeds; Vacuum tightness is-0.08MPa.
Under 120 ℃ of the pellets that embodiment 1-12 is made, behind the baking 4h, carry out following performance test:
The tensile property test is undertaken by national standard ISO 527-2, and specimen size is 150 * 10 * 4mm, and draw speed does
5mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80 * 10 * 4mm, and rate of bending is 2mm/min, and span is 64mm; The simple beam notched Izod impact strength is undertaken by ISO 179, and specimen size is 80 * 10 * 4mm; ISO188 is pressed in the thermal-oxidative aging property test, and test condition is 150 ℃ * 1000h, and ethylene glycol resistant is tested according to the standard TL52062 of Volkswagen, and test condition is 135 ℃ * 48h.Anti-long-term aging or alcoholysis performance are assessed with the property retention rate, like tensile strength/original tensile strength * 100% after tensile strength performance conservation rate=aging (or alcoholysis).Test result is as shown in the table:
By visible in the last table; The hydrolysis alcoholysis nylon 66 composite material that embodiment 1-12 makes has higher physical and mechanical properties; The ability that possesses good long term heat oxygen aging resistance effect and ethylene glycol resistant and aqueous corrosion thereof simultaneously; Can be widely used in and make automobile radiators cooling water tank, parts such as thermostat and charge air cooler.
Claims (15)
1. a hydrolysis alcoholysis nylon 66 composite material is characterized in that, by following raw material in composition by weight:
Nylon resin 51.8-84.5 part;
Short glass fiber 15-40 part;
Nucleator 0.1-0.6 part;
Thermo-stabilizer 0.1-0.6 part;
Anti-pure enzymolysis auxiliary agent 0.1-1.0 part;
Barrier agent 0.1-5 part;
Lubricant 0.1-1.0 part.
2. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described nylon resin is a nylon 66, and relative viscosity is 2.4-3.2.
3. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 2 is characterized in that described nylon 66 is the compound system of any single viscosity or two kinds of different viscosity.
4. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described short glass fiber is the alkali-free short glass fiber, and filament diameter is 9 μ m-13 μ m.
5. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 4 is characterized in that the filament diameter of described short glass fiber is 10 μ m.
6. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described nucleator is inorganic nucleator or organic nucleating agent, and the grain diameter of inorganic nucleator is less than 1 μ m; Organic nucleating agent is the composite nucleating agent of any one or two kinds of compositions in Sodium Benzoate, sorbyl alcohol dibenzyl ester, the montanate.
7. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 6 is characterized in that described inorganic nucleator is a talcum powder; Organic nucleating agent is a montanate.
8. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described thermo-stabilizer is N; N/-1, (3,5-two (1 for 6-dihexyl two; The 1-dimethyl ethyl)-4-hydroxybenzene propionyl), four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, N, N
'In-diphenyl-para-phenylene diamine and the mantoquita composite antioxidant (mixture of potassium halide and cuprous halide) any one or two or more combinations.
9. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that, described thermo-stabilizer is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and mantoquita composite antioxidant.
10. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described anti-pure enzymolysis auxiliary agent is the amine stablizer.
11. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described anti-pure enzymolysis auxiliary agent is a polycarbodiimide class stablizer.
12. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described barrier agent is inorganic barrier agent, organic barrier agent or its compsn, inorganic barrier agent is polynite, mica powder or its compsn, and consumption is 0.1-1 part; Organic barrier agent is ethylene-vinyl alcohol copolymer (EVOH), and consumption is 1-5 part.
13. a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 1 is characterized in that described lubricant is polyethylene wax class, polyol ester class or silicone lubricant.
14. the preparation method of the glass fiber enhanced nylon 66 matrix material of the described a kind of hydrolysis alcoholysis of claim 1 is characterized in that concrete steps are following:
The first step: with dry good Nylon 66, inhibitor, hydrolysis agent, barrier agent, nucleator and lubricant mixed at high speed are even in advance;
Second step: the mixture that the first step is obtained feeds 250-280 ℃ with spun glass, and screw speed is in 300-450 rev/min the twin screw extruder, extruding pelletization.
15. the preparation method of a kind of hydrolysis alcoholysis nylon 66 composite material as claimed in claim 14; It is characterized in that; Described twin screw extruder is provided with an above opening for feed; Each raw material in the first step is divided into arbitrarily more than two groups, adds twin screw extruder from different opening for feeds successively, carries out premix; The barrel of twin screw extruder is provided with an above vacuum extractor.
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| CN105949763A (en) * | 2016-05-16 | 2016-09-21 | 上海日之升科技有限公司 | Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition |
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| CN108587151A (en) * | 2017-12-27 | 2018-09-28 | 浙江普利特新材料有限公司 | It is a kind of to apply in automobile cooling system alcoholysis resistance nylon material and preparation method thereof |
| CN108624040A (en) * | 2018-05-10 | 2018-10-09 | 南京跃贝新材料科技有限公司 | A kind of motor intake manifold composite material and preparation method |
| CN108948738A (en) * | 2018-07-25 | 2018-12-07 | 宁波伊德尔新材料有限公司 | The modified nylon 66 material and preparation method thereof of automobile water chamber hydrolysis-resistant alcoholysis-resistant |
| CN110041700A (en) * | 2019-05-17 | 2019-07-23 | 金旸（厦门）新材料科技有限公司 | A kind of carbon fiber reinforced nylon material and prepare raw material and its preparation method and application |
| CN110041695A (en) * | 2018-01-15 | 2019-07-23 | 朗盛德国有限责任公司 | HR glass fibre in vibration component |
| CN112409783A (en) * | 2020-10-27 | 2021-02-26 | 东莞市鑫塑源塑胶科技有限公司 | Hydrolysis-resistant nylon composite material for automobiles and preparation method thereof |
| CN112592583A (en) * | 2020-11-16 | 2021-04-02 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
| CN112694748A (en) * | 2020-12-15 | 2021-04-23 | 江苏金发科技新材料有限公司 | High-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and preparation method thereof |
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| CN113881076A (en) * | 2021-11-02 | 2022-01-04 | 南京聚隆科技股份有限公司 | High-temperature-aging-resistant glass fiber reinforced nylon material and preparation method thereof |
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| CN102863786A (en) * | 2012-09-13 | 2013-01-09 | 江苏安格特新材料科技有限公司 | Low-water-absorption reinforced polyamide compound and preparation method thereof |
| CN102863782A (en) * | 2012-09-28 | 2013-01-09 | 合肥杰事杰新材料股份有限公司 | Reinforced and toughened nylon composite used for high-speed railways and preparation method for composite |
| CN103788630B (en) * | 2012-10-29 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of composite nucleating agent Reinforced Nylon resin combination and preparation method thereof |
| CN103788630A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | A nylon resin composition reinforced by a composite nucleating agent and a preparation method of the nylon resin composition |
| CN103044903A (en) * | 2012-12-26 | 2013-04-17 | 安徽科聚新材料有限公司 | Hydrolysis-resistant nylon composite material and preparation method thereof |
| CN103289391A (en) * | 2013-06-21 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Hydrolysis resistance PA 66 composition |
| CN103450678A (en) * | 2013-08-28 | 2013-12-18 | 宁波伊德尔新材料有限公司 | Waterproof alcoholysis high-temperature resistant renewable nylon 66 composite material and preparation method thereof |
| CN103450678B (en) * | 2013-08-28 | 2016-04-13 | 宁波伊德尔新材料有限公司 | The preparation method of water-fast alcoholysis is high temperature resistant regeneration nylon 66 composite material |
| CN104448813A (en) * | 2014-11-25 | 2015-03-25 | 浙江俊尔新材料股份有限公司 | Glass fiber reinforced polyamide 66 composite material, and preparation method and application thereof |
| CN104592749A (en) * | 2015-02-03 | 2015-05-06 | 上海日之升新技术发展有限公司 | Low-moisture-absorption long-term heat-resistant aging-resistant polyamide composition and preparation method thereof |
| CN104761894A (en) * | 2015-04-22 | 2015-07-08 | 合肥康龄养生科技有限公司 | Nylon composite material with high transparency and glossiness and preparation method of nylon composite material |
| CN105385153A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | Reinforced composite for car heat radiator |
| CN105949763A (en) * | 2016-05-16 | 2016-09-21 | 上海日之升科技有限公司 | Environment-friendly polyamide composition with good appearance and hot water stability and preparation method of polyamide composition |
| CN107057337A (en) * | 2017-05-12 | 2017-08-18 | 佛山市合宏泰业科技有限公司 | A kind of high-strength high just glass fiber reinforced nylon material and preparation method thereof |
| CN107778850A (en) * | 2017-11-02 | 2018-03-09 | 雪龙集团股份有限公司 | A kind of high-strength water-resistance solution nylon is without wheel hub fan material and preparation method thereof |
| CN108034243A (en) * | 2017-12-27 | 2018-05-15 | 宁波伊德尔新材料有限公司 | A kind of auxiliary agent of the special resistance to automotive antifreeze corrosion of nylon and preparation method thereof |
| CN108587151A (en) * | 2017-12-27 | 2018-09-28 | 浙江普利特新材料有限公司 | It is a kind of to apply in automobile cooling system alcoholysis resistance nylon material and preparation method thereof |
| CN110041695A (en) * | 2018-01-15 | 2019-07-23 | 朗盛德国有限责任公司 | HR glass fibre in vibration component |
| EP3511366B1 (en) | 2018-01-15 | 2021-05-26 | LANXESS Deutschland GmbH | Hr glass fibres in pivoting components |
| CN110041695B (en) * | 2018-01-15 | 2021-09-10 | 朗盛德国有限责任公司 | HR glass fiber in vibrating component |
| EP3514198B1 (en) | 2018-01-15 | 2021-06-09 | LANXESS Deutschland GmbH | Hr glass fibres in pivoting components |
| US11021605B2 (en) | 2018-01-15 | 2021-06-01 | Lanxess Deutschland Gmbh | Vibration components for motor vehicles |
| CN108624040A (en) * | 2018-05-10 | 2018-10-09 | 南京跃贝新材料科技有限公司 | A kind of motor intake manifold composite material and preparation method |
| CN108948738A (en) * | 2018-07-25 | 2018-12-07 | 宁波伊德尔新材料有限公司 | The modified nylon 66 material and preparation method thereof of automobile water chamber hydrolysis-resistant alcoholysis-resistant |
| CN110041700B (en) * | 2019-05-17 | 2021-05-25 | 金旸（厦门）新材料科技有限公司 | Carbon fiber reinforced nylon material, preparation raw material, preparation method and application thereof |
| CN110041700A (en) * | 2019-05-17 | 2019-07-23 | 金旸（厦门）新材料科技有限公司 | A kind of carbon fiber reinforced nylon material and prepare raw material and its preparation method and application |
| CN113348209A (en) * | 2019-12-06 | 2021-09-03 | 株式会社Lg化学 | Thermoplastic molding composition and automobile parts comprising molded article thereof |
| CN112409783A (en) * | 2020-10-27 | 2021-02-26 | 东莞市鑫塑源塑胶科技有限公司 | Hydrolysis-resistant nylon composite material for automobiles and preparation method thereof |
| CN114507344A (en) * | 2020-11-16 | 2022-05-17 | 华峰集团有限公司 | Alcoholysis-resistant polyamide resin and preparation method and application thereof |
| CN112592583A (en) * | 2020-11-16 | 2021-04-02 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
| CN114507344B (en) * | 2020-11-16 | 2024-01-23 | 华峰集团有限公司 | Alcoholysis-resistant polyamide resin and preparation method and application thereof |
| CN112592583B (en) * | 2020-11-16 | 2023-03-10 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant enhanced PA6T material and preparation method thereof |
| CN112694748A (en) * | 2020-12-15 | 2021-04-23 | 江苏金发科技新材料有限公司 | High-temperature alcoholysis-resistant laser transmission-enhanced PA66 composite material and preparation method thereof |
| CN113881076B (en) * | 2021-11-02 | 2023-10-27 | 南京聚隆科技股份有限公司 | High-temperature aging resistant glass fiber reinforced nylon material and preparation method thereof |
| CN113881076A (en) * | 2021-11-02 | 2022-01-04 | 南京聚隆科技股份有限公司 | High-temperature-aging-resistant glass fiber reinforced nylon material and preparation method thereof |
| CN113980459A (en) * | 2021-11-12 | 2022-01-28 | 安徽中鼎橡塑制品有限公司 | High-rigidity glass fiber reinforced nylon composite material and preparation method thereof |
| CN114716821A (en) * | 2022-03-21 | 2022-07-08 | 江苏博云塑业股份有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN114716821B (en) * | 2022-03-21 | 2024-02-02 | 江苏博云塑业股份有限公司 | Glass fiber reinforced nylon material and preparation method thereof |
| CN115584126A (en) * | 2022-10-09 | 2023-01-10 | 山东龙腾新材料有限公司 | Ethylene glycol-resistant glass fiber reinforced PA66 thermoplastic composite material and preparation method thereof |
| CN115584126B (en) * | 2022-10-09 | 2023-08-08 | 山东龙腾新材料有限公司 | Ethylene glycol-resistant glass fiber reinforced PA66 thermoplastic composite material and preparation method thereof |
| CN115710429A (en) * | 2022-10-11 | 2023-02-24 | 青岛国恩科技股份有限公司 | Hydrolysis-resistant alcoholysis-resistant reinforced nylon material and preparation method thereof |
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Application publication date: 20120627 |