A kind of high fluidity long glass fibres reinforced plastic PA66 composite and its manufacture methodTechnical field
The present invention relates to a kind of high fluidity long glass fibres reinforced plastic PA66 composite and its manufacture method.
Background technology
The conventional engineering plastics of nylon66 fiber (PA66), with good heat resistance, self lubricity, wearability, mechanicalnessCan, workability the advantages of, but the hygroscopicity of nylon is strong, poor dimensional stability shortcoming, limit its in some fields shouldWith in order to improve, nylon dimensional stability is poor, bibulous shortcoming, the mechanical performance of composite is improved, by glassEnhancing can reduce the shrinkage factor and water imbibition of composite, compared to short glass fiber reinforced PA66 composite, long glass fiber reinforcedThe glass tow of PA66 is protected by resin, is difficult to be shredded by screw rod in the injection moulding stage, can make glass in mouldingRetain reservation length more long, so as to ensure composite mechanical performance higher.
Long glass fiber reinforced nylon LGFR-PA66 particles are molten with continuous glass fiber strand using special dipping die headMelt dipping and obtain, long glass fiber reinforced nylon 1956 in American R ＆ D successfully, the major technique of current long glass fiber reinforced nylon byOffshore company controls, the effect of impregnation for glass tow such as resin properties, impregnation technology, glass tow, size, dispersantHave a great impact,
In the preparation process of long glass fiber reinforced nylon LGFR-PA66 materials, the infiltration of glass is to ensure composite powerLearn performance very crucial, in thermoplastic resin, the processing characteristics of PA66 materials is less than the materials such as PA6, PP, and commerciallyThe trade mark of the PA66 of different viscosities is fewer, and minimum relative viscosity common at present is usually 2.4, viscosity too high selectivity, treeThe mobility of fat is too poor, is unfavorable for that long glass fiber reinforced nylon LGFR-PA66 materials fully infiltrate in melt stage to glass tow,The mechanism of modification of the flow ability modifying agent of general improvement PA66 mobility is all the strand that PA66 is reduced during processingObtain the PA66 of high fluidity, although the method can obtain high fluidity PA66 can make glass fiber yarn beam impregnate die head inFully infiltrated, but the reduction of PA66 molecular weight makes its mechanical properties decrease, and one can be produced during the reduction of molecular weightThe composition of a little small molecules, so can raise the VOC of material, and the method occurs chemical change in process of production, reactionProcess is influenceed very big by working condition, and production has floating between this results in different batches, and a kind of modification mode is not influenceingThe PA66 of flowing high is obtained on the premise of properties of product in the long glass fiber reinforced nylon for obtaining excellent mechanical performance and low VOCLGFR-PA66 materials have great importance.
The content of the invention
A kind of long glass fibres reinforced plastic PA66 it is an object of the invention to provide preparation process is simple, excellent in mechanical performance is answeredCondensation material, to overcome prior art to improve glass fiber reinforcement PA66 original in order to improve material caused by Resin FlowThe injured shortcoming of mechanical property, is prepared for the long glass fiber reinforced nylon LGFR-PA66 materials with excellent mechanical performance, can expireThe sufficient technical property requirements as automotive upholstery.
Another object of the present invention is to provide the preparation method of long glass fibres reinforced plastic PA66 material.
The purpose of the present invention is realized by such a way：
A kind of high fluidity long glass fibres reinforced plastic PA66 composite, it is constituted by weight percentage, including 10~60% with composite particles length direction long glass fibres arranged in parallel and 90~40% modified Pa 66.
The resin of the modified Pa 66 is that the PA66 resins of the existing commercialization of in the market are carried out by double screw extruderPrepared by extrusion, raw material of the resin of the modified Pa 66 comprising following percentage by weight meter：
In modified polypropylene resin system,
The relative viscosity 2.4 of described PA66 resins, melt flow rate (MFR) is 22g/10min, test condition is 275 DEG C/0.325kg。
Described flow ability modifying agent CYD 701C are a kind of dissaving polymers, can effectively improve mobility, Ke YiyouThe raising processing characteristics of effect, improves the thickness evenness and dimensional stability of product.
Described antioxidant is three [2.4- di-tert-butyl-phenyls] phosphite esters.
Described lubricant is silicone powder.
A kind of preparation method of high fluidity long glass fibres reinforced plastic PA66 composite：Its step is as follows：
(1) resin of modified Pa 66 is prepared：By PA66, flow ability modifying agent CYD 701C, antioxidant and lubricant in high-speed stirringMix in machine and be well mixed, said mixture is added to extruder by twin-screw extrusion owner's spout；Extrusion processing temperatureIt it is 260~280 DEG C, engine speed is 200~400rpm.
(2) long glass fibres reinforced plastic PA66 composite is prepared：The continuous glass long of melt modification PA66 resin melts dippingFiber, impregnation processability temperature is 270~300 DEG C, and long glass fibres reinforced plastic PA66 material is prepared using pultrude process.
Compound is grown up after entering the continuous glass fibre that dipping head dipping draws from extruder through tank cooling and dicingSpend the long glass fibres reinforced plastic PA66 material granule for 8~15mm.
Compared with prior art, the present invention has the advantages that：Need not individually buy in advance or production has heightThe PA66 resins of mobility, turn avoid traditional flow ability modifying agent and improve PA66 Resin Flows and cause power by way of fractureThe shortcoming of performance reduction is learned, the present invention improves the flowing of PA66 resins by introducing dissaving polymer during productionProperty, dissaving polymer improves its mobility using its unique structure on the premise of PA66 resin mechanical properties are not reduced,So that glass tow can fully be infiltrated in die head is impregnated, so as to obtain good mechanical performance, apparent preferably glass longGlass fiber reinforcement PA66 composites
Specific embodiment
The present invention is further illustrated below by embodiment and comparative example, in the case where spirit of the invention is not violated, the present inventionThe content that following experimental example is specifically expressed should be not limited to.
Embodiment raw materials are as follows：
PA66EPR24：Melt index 22g/10min, 275 DEG C of * 0.325kg of test condition；
Continuous glass fibre；PPG companies EC I7-4588；
L flow ability modifying agent CYD 701C：Analysis is pure, commercially available.
Maleic anhydride：Technical grade, it is commercially available.
Antioxidant：Hinered phenols antioxidant 1010, CIBA companies of Switzerland；
Antioxidant：Three [2.4- di-tert-butyl-phenyls] phosphite esters 168, it is commercially available.
Lubricant：Silicone powder, technical grade is commercially available；
Properties of product method of testing：
Melt mass flow index (melt index)：By the methods of ISO 1133, at 275 DEG C, tested under 0.325kg load.
Tensile property：By ISO 527-2 methods, batten size：170*10*4mm, test speed 5mm/min.
Bending property：By the methods of ISO 178, batten size：80*10*4mm, test speed 2mm/min.
Notched impact properties：By the methods of ISO 180, batten size：80*10*4mm.
Apparent property：The model for preparing 150*100*3.2 by injection machine observes surface floating fiber situation.
Embodiment 1
By PA66 resin 9.88kg, flow ability modifying agent CYD-701C 20g, antioxidant 1010 25g, the 25g of antioxidant -168,Lubricant-silicone powder 50g is well mixed using homogenizer, by above-mentioned material from TE-35 (draw ratio L/D=48) twin-screwExtruder main spout is added.Processing temperature (from spout to die head) is respectively：240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280DEG C, 280 DEG C, 300 DEG C, 300 DEG C, engine speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1.
Embodiment 2
By PA66 resin 9.85kg, flow ability modifying agent CYD-701C 50g, antioxidant 1010 25g, the 25g of antioxidant -168,Lubricant-silicone powder 50g is well mixed using homogenizer, by above-mentioned material from TE-35 (draw ratio L/D=48) twin-screwExtruder main spout is added.Processing temperature (from spout to die head) is respectively：240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280DEG C, 280 DEG C, 300 DEG C, 300 DEG C, engine speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1.
Embodiment 3
By PA66 resin 9.82kg, flow ability modifying agent CYD-701C 80g, antioxidant 1010 25g, the 25g of antioxidant -168,Lubricant-silicone powder 50g is well mixed using homogenizer, by above-mentioned material from TE-35 (draw ratio L/D=48) twin-screwExtruder main spout is added.Processing temperature (from spout to die head) is respectively：240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280DEG C, 280 DEG C, 300 DEG C, 300 DEG C, engine speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1.
Embodiment 4
By PA66 resin 9.85kg, flow ability modifying agent CYD-701C 50g, antioxidant 1010 25g, the 25g of antioxidant -168,Lubricant-silicone powder 50g is well mixed using homogenizer, by above-mentioned material from TE-35 (draw ratio L/D=48) twin-screwExtruder main spout is added.Processing temperature (from spout to die head) is respectively：240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280DEG C, 280 DEG C, 300 DEG C, 300 DEG C, engine speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1.
Embodiment 5
By PA66 resin 9.85kg, flow ability modifying agent CYD-701C 50g, antioxidant 1010 25g, the 25g of antioxidant -168,Lubricant-silicone powder 50g is well mixed using homogenizer, by above-mentioned material from TE-35 (draw ratio L/D=48) twin-screwExtruder main spout is added.Processing temperature (from spout to die head) is respectively：240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280DEG C, 280 DEG C, 300 DEG C, 300 DEG C, engine speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1.
Comparative example 1
PA66 resin 9.9kg, antioxidant 1010 25g, the 25g of antioxidant -168, lubricant-silicone powder 50g are used at a high speedMixer is well mixed, and above-mentioned material is added from TE-35 (draw ratio L/D=48) twin-screw extrusion owner spout.ProcessingTemperature (from spout to die head) is respectively：It is 240 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 300 DEG C, 300 DEG C, mainMachine rotating speed is 350rpm.
The compound of extruded machine frit reaction uses pultrude process with continuous glass fibre, and impregnation processability temperature is 300DEG C, the cooling and dicing after impregnating head is made fibre weight percentage composition for 50% and its length and resin granular material length phaseSame long glass fiber reinforced PA66 particulate materials, prepare standard mechanics test sample, in 23 DEG C of environment of 50%RH using injection machineIts mechanical property is tested after regulation 8h, test result is shown in Table 1..
Table 1：The performance test results.
As seen from the above table, when the PA66 resins directly using commercialization prepare long glass fibres increasing as impregnating resin bodyDuring strong PA66 materials, the mechanical property of material is poor, and this is the poor fluidity due to material so that PA66 resins can not be in dippingCaused by die head fully infiltrates to glass.
The present invention carries out reaction and squeezes to the PA66 resins of commercialization by dissaving polymer using double screw extruderGo out, prepare the resin of modified Pa 66 of melting means high, and long glass fibres enhancing Pa66 materials are prepared for using process of melt impregnationMaterial.Compared with prior art, the present invention has the advantages that：Need not individually buy in advance or production has high fluidityPA66 resins, turn avoid traditional flow ability modifying agent and improve PA66 Resin Flows and cause mechanical property by way of fractureThe shortcoming of reduction, not only makes the long glass fiber reinforced PA66 excellent in mechanical performance of acquisition, and obtain preferable outward appearance.