CN103113667A - Continuous long glass fiber reinforced polypropylene/nylon composite material with core layer structure and preparation process thereof - Google Patents
Continuous long glass fiber reinforced polypropylene/nylon composite material with core layer structure and preparation process thereof Download PDFInfo
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- CN103113667A CN103113667A CN2012105748382A CN201210574838A CN103113667A CN 103113667 A CN103113667 A CN 103113667A CN 2012105748382 A CN2012105748382 A CN 2012105748382A CN 201210574838 A CN201210574838 A CN 201210574838A CN 103113667 A CN103113667 A CN 103113667A
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Abstract
The invention discloses a continuous long glass fiber reinforced polypropylene/nylon composite material with a core layer structure and a preparation process thereof. According to the composite material and the preparation process of the composite material, polypropylene resin and nylon resin are taken as matrix resin; and the composite material is prepared from the following ingredients in percentage by weight: 38-78% of matrix resin, 2-10% of compatilizer, 0-2% of heat stabilizer and 20-50% of long glass fibers, wherein the weight ratio of the polypropylene resin to the nylon resin is (1-9): 1. The composite material and the preparation process of the composite material have the advantages that the composite material with internal nylon-resin-infiltrated alkali-free long glass fiber master batches and an external polypropylene core layer is finally formed by adopting a production process that a high-temperature melt infiltration tank and a low-temperature melt infiltration tank are connected in series, and the sufficient dispersion of the interior and exterior of the composite material can be realized in a subsequent product injection molding process, so that the defect that the viscosity increase of melt is adverse to infiltration due to the fact that nylon and polypropylene grafts are subjected to premature reaction under the condition of high temperature is effectively overcome. Furthermore, the composite material has the excellent performance of heat resistance, high rigidity and the like, thereby meeting the production requirements of auto parts and components.
Description
Technical field
The present invention relates to a kind of processing technique field of continuous long glass fiber reinforced profax/nylon composite materials, relate in particular to a kind of continuous long glass fiber reinforced profax/nylon composite materials and preparation technology thereof with core structure.
Background technology
development along with automotive industry, long glass fiber reinforced polypropylene is due to its excellent dimensional stability, anti-creep, anti-dynamic fatigue, high rigidity, low density, the performance advantage such as do not absorb water, and the structure design modularization advantage of complex parts structure one step injection moulding, the superiority of effectiveness of general-purpose plastics and the returnability of thermoplastic material, long glass fiber reinforced polypropylene has replaced SMC gradually, thermosetting material is reclaimed in the environmental protection such as BMC, the GMT moulding material of complex forming technology, the PA that price is high, PBT, PC/ABS, SMA thermoplastic engineering plastic and highdensity metallic substance, be widely used in the production of automobile component, significant contribution has been made in development to the automotive light weight technology technology.
But polypropylene material is owing to being general-purpose plastics, melt temperature only has 160-170 ℃, after namely using continuous long glass fiber to strengthen, its thermotolerance and mechanical property are limit by fusing point, can't further improve to satisfy particularly the further develop requirement of engine circumferential component to material of automobile component.
the drawback of bringing in order to solve polypropylene material, this year, add a certain proportion of nylon in polypropylene material, nylon material belongs to dystectic engineering plastics, can be good at satisfying the demand to fluxing point, when add a certain amount of nylon (PA) in continuous long glass fiber reinforced profax (LFTPP) production formula, thereby can realize the high performance of LFTPP, but owing to being the effect of impregnation may of assurance PP to continuous long glass fiber in the LFTPP production process, very high (〉=300 ℃) that the melt temperature of PP arranges usually, under high temperature PP grafts compatilizer easily and PA react and cause the melt viscosity rising, be unfavorable for that melt is to the infiltration of long glass fibres, because nylon and polyacrylic matrix material character are not very good.
Summary of the invention
In order to overcome defects, the invention provides a kind of continuous long glass fiber reinforced profax/nylon composite materials with core structure, this matrix material not only has low water absorption, high workability, but also have excellent thermotolerance, high rigidity, HI high impact, high-dimensional stability, creep resistant and good thermal-oxidative aging property, well satisfied the Production requirement of automobile component.
The present invention for the technical scheme that solves its technical problem and adopt is: a kind of continuous long glass fiber reinforced profax/nylon composite materials with core structure, with acrylic resin and nylon resin as matrix resin, by weight, has following formula: matrix resin 38～78wt%; Compatilizer 2～10wt%; Thermo-stabilizer 0～2wt%; Long glass fibres 20～50wt%;
Wherein, the weight ratio of described acrylic resin and described nylon resin is 1～9:1.
As a further improvement on the present invention, described nylon resin is a kind of in Nylon 6 and Nylon 66.
As a further improvement on the present invention, the viscosity of described nylon resin is 2.0～3.0.
As a further improvement on the present invention, the melt flow rate (MFR) of described acrylic resin is 10～1000g/10min.
As a further improvement on the present invention, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and any one or multiple mixture in calixarene kind.
As a further improvement on the present invention, described compatilizer is the polar monomer graft polymkeric substance, and the matrix of this polar monomer graft polymkeric substance is any one or the two kinds of mixtures in multipolymer, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, ethylene-acrylate copolymer and the ethylene-acrylate-glycidyl methacrylate copolymer of polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, vinylbenzene and divinyl; The polar monomer of this polar monomer graft polymkeric substance is any one or the multiple mixture in maleic anhydride and analogue and acrylicacidandesters analog derivative.
As a further improvement on the present invention, described long glass fibres is the alkali-free long glass fibres.
The present invention also provides a kind of described preparation technology with continuous long glass fiber reinforced profax/nylon composite materials of core structure, and described technique comprises the steps:
(1) will be fed in single screw extrusion machine by the nylon resin of recipe ratio, and be transported in the high-temperature fusant immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the temperature in this high-temperature fusant immersion slot is 260～360 ℃;
(2) will jointly be fed in single screw extrusion machine by acrylic resin, thermo-stabilizer and the compatilizer of recipe ratio, and be transported in the low-temperature melt immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the temperature in this low-temperature melt immersion slot is 180～220 ℃;
(3) long glass fibres moved through successively with the pulling speed of 20～100m/min and immerse in high-temperature fusant immersion slot and the low-temperature melt immersion slot in step (2) in step (1); after the long glass fibres complete wetting, utilize dicing machine that continuous long glass fiber is cut into length and be the particle of 12mm.
the invention has the beneficial effects as follows: the present invention adopts the production technique of high-temperature fusant immersion slot and the series connection of low-temperature melt immersion slot, at first utilize nylon resin that the alkali-free long glass fibres is once infiltrated in the high-temperature fusant immersion slot, and then utilize acrylic resin to carry out the secondary infiltration to the alkali-free long glass fibres in the low-temperature melt immersion slot, the final inside that forms is the alkali-free long glass fibres master batch that infiltrates through nylon resin, the outside is the matrix material of polypropylene sandwich layer, abundant dispersion can be realized in the inside and outside of this matrix material in later stage product injection moulding process, thereby efficiently solve nylon and Graft Polypropylene premature reaction under the condition of high temperature and cause melt viscosity to raise being unfavorable for the defective that infiltrates.In addition, this matrix material also has thermotolerance, high rigidity, HI high impact, high-dimensional stability, creep resistant and the good thermal-oxidative aging property of low water absorption, high workability, excellence, has well satisfied the Production requirement of automobile component.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details, but the invention is not restricted to these embodiment.
When embodiment 1～4 provides nylon resin described in the present invention to adopt Nylon 6, prepare a kind of method with continuous long glass fiber reinforced profax/nylon 6 composite material of core structure.
Embodiment 1～4 all accounts for the processing condition of process unit in the weight content umber of continuous long glass fiber reinforced profax/nylon 6 composite material and table 2 according to the raw material described in table 1, prepare continuous long glass fiber reinforced profax/nylon 6 composite material according to following steps:
(1) at first will be fed into by the Nylon 6 of recipe ratio in the single screw extrusion machine of length-to-diameter ratio 20:1, and be transported in the high-temperature fusant immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the length of this high-temperature fusant immersion slot is 2m, and the temperature in this high-temperature fusant immersion slot is 260～360 ℃;
(2) then will jointly be fed into by acrylic resin, thermo-stabilizer and the compatilizer of recipe ratio in the single screw extrusion machine of length-to-diameter ratio 20:1, and be transported in the low-temperature melt immersion slot by the mouth mould after the single screw extrusion machine plasticizing, this low-temperature melt immersion slot length is 1m, and the temperature in this low-temperature melt immersion slot is 180～220 ℃;
(3) at last long glass fibres moved through successively with the pulling speed of 20～100m/min and immerse in high-temperature fusant immersion slot and the low-temperature melt immersion slot in step (2) in step (1); after the long glass fibres complete wetting, utilize dicing machine that continuous long glass fiber is cut into length and be the particle of 12mm.
Table 1: the component of continuous long glass fiber reinforced profax/nylon 6 composite material embodiment
Unit: wt%
Table 2: the processing condition of process unit
When embodiment 5～8 provides nylon resin described in the present invention to adopt Nylon 66, prepare a kind of method with continuous long glass fiber reinforced profax/nylon 66 composite material of core structure.
Embodiment 5～8 all accounts for the processing condition of process unit in the weight content umber of continuous long glass fiber reinforced profax/nylon 66 composite material and table 4 according to the raw material described in table 3, prepare continuous long glass fiber reinforced profax/nylon 66 composite material according to following steps:
(1) at first will be fed into by the Nylon 66 of recipe ratio in the single screw extrusion machine of length-to-diameter ratio 20:1, and be transported in the high-temperature fusant immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the length of this high-temperature fusant immersion slot is 2m, and the temperature in this high-temperature fusant immersion slot is 260～360 ℃;
(2) then will jointly be fed into by acrylic resin, thermo-stabilizer and the compatilizer of recipe ratio in the single screw extrusion machine of length-to-diameter ratio 20:1, and be transported in the low-temperature melt immersion slot by the mouth mould after the single screw extrusion machine plasticizing, this low-temperature melt immersion slot length is 1m, and the temperature in this low-temperature melt immersion slot is 180～220 ℃;
(3) at last long glass fibres moved through successively with the pulling speed of 20～100m/min and immerse in high-temperature fusant immersion slot and the low-temperature melt immersion slot in step (2) in step (1); after the long glass fibres complete wetting, utilize dicing machine that continuous long glass fiber is cut into length and be the particle of 12mm.
Table 3: the component of continuous long glass fiber reinforced profax/nylon 66 composite material embodiment
Unit: wt%
Table 4: the processing condition of process unit
According to industry standard, respectively the above-mentioned continuous long glass fiber reinforced profax/nylon 6 composite material with core structure that makes and continuous long glass fiber reinforced profax/nylon 66 composite material with core structure are carried out multinomial basic physical properties test, get its mean value.Test result is as follows:
Table 5: the basic physical properties test result with continuous long glass fiber reinforced profax/nylon 6 composite material of core structure
Table 6: the basic physical properties test result with continuous long glass fiber reinforced profax/nylon 66 composite material of core structure
As seen from Table 5, the water-intake rate of the continuous long glass fiber reinforced profax/nylon 6 composite material with core structure that the present invention makes≤0.5%, spiral linear flow length 〉=800mm, tensile strength 〉=100MPa, tensile modulus 〉=5500MPa, notched Izod impact strength 〉=25KJ/m
2, heat-drawn wire (HDT) 〉=160 ℃, thermo-oxidative ageing back draft strength retention 〉=95%;
As seen from Table 6, the water-intake rate of the continuous long glass fiber reinforced profax/nylon 66 composite material with core structure that the present invention makes≤0.5%, spiral linear flow length 〉=800mm, tensile strength 〉=110MPa, tensile modulus 〉=6000MPa, notched Izod impact strength 〉=20KJ/m
2, heat-drawn wire (HDT) 〉=165 ℃, thermo-oxidative ageing back draft strength retention 〉=95%.
Therefore, compared to industry standard, the matrix material that the present invention makes has excellent physicals.Above the present invention has been done detailed description; its purpose is to allow those of ordinary skill in the art can understand content of the present invention and be implemented; can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (8)
1. continuous long glass fiber reinforced profax/nylon composite materials with core structure, is characterized in that: by weight, have following formula: matrix resin 38～78wt% as matrix resin with acrylic resin and nylon resin; Compatilizer 2～10wt%; Thermo-stabilizer 0～2wt%; Long glass fibres 20～50wt%;
Wherein, the weight ratio of described acrylic resin and described nylon resin is 1～9:1.
2. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1 is characterized in that: described nylon resin is a kind of in Nylon 6 and Nylon 66.
3. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1, it is characterized in that: the viscosity of described nylon resin is 2.0～3.0.
4. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1, it is characterized in that: the melt flow rate (MFR) of described acrylic resin is 10～1000g/10min.
5. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1 is characterized in that: described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and any one or multiple mixture in calixarene kind.
6. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1, it is characterized in that: described compatilizer is the polar monomer graft polymkeric substance, the matrix of this polar monomer graft polymkeric substance is polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, the multipolymer of vinylbenzene and divinyl, polyethylene-polystyrene-polypropylene terpolymer, ethylene-propylene-butadiene terpolymer, any one in ethylene-acrylate copolymer and ethylene-acrylate-glycidyl methacrylate copolymer or two kinds of mixtures, the polar monomer of this polar monomer graft polymkeric substance is any one or the multiple mixture in maleic anhydride and analogue and acrylicacidandesters analog derivative.
7. continuous long glass fiber reinforced profax/the nylon composite materials with core structure according to claim 1, it is characterized in that: described long glass fibres is the alkali-free long glass fibres.
8. the described preparation technology with continuous long glass fiber reinforced profax/nylon composite materials of core structure of any one according to claim 1-7, it is characterized in that: described technique comprises the steps:
(1) will be fed in single screw extrusion machine by the nylon resin of recipe ratio, and be transported in the high-temperature fusant immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the temperature in this high-temperature fusant immersion slot is 260～360 ℃;
(2) will jointly be fed in single screw extrusion machine by acrylic resin, thermo-stabilizer and the compatilizer of recipe ratio, and be transported in the low-temperature melt immersion slot by the mouth mould after the single screw extrusion machine plasticizing, the temperature in this low-temperature melt immersion slot is 180～220 ℃;
(3) long glass fibres moved through successively with the pulling speed of 20～100m/min and immerse in high-temperature fusant immersion slot and the low-temperature melt immersion slot in step (2) in step (1); after the long glass fibres complete wetting, utilize dicing machine that continuous long glass fiber is cut into length and be the particle of 12mm.
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