CN102850783B - A kind of nylon 6/ PP composite material and preparation method thereof - Google Patents
A kind of nylon 6/ PP composite material and preparation method thereof Download PDFInfo
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- CN102850783B CN102850783B CN201110179517.8A CN201110179517A CN102850783B CN 102850783 B CN102850783 B CN 102850783B CN 201110179517 A CN201110179517 A CN 201110179517A CN 102850783 B CN102850783 B CN 102850783B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C2948/92904—Die; Nozzle zone
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Abstract
The invention belongs to technical field of polymer materials, relate to a kind of nylon 6/ PP composite material and preparation method thereof.This composite includes following components and weight portion: 6,50～100 parts of polypropylene of 500～600 parts of nylon, the continuous fiber reinforcing agent of 300～400 parts, 40～50 parts of compatilizers, 10～20 parts of antioxidant and, 2～6 parts of lubricants.Compared with prior art, the product of the present invention ensure that the effective length of glass, thus substantially increases rigidity and the intensity of this material, significantly improves resistant to hydrolysis performance and the heat resistance of material simultaneously, and its fiber is uniformly dispersed, and part weight is stable.It addition, the present invention can directly injection mo(u)lding, production efficiency is high, and product use after can also recycle through pulverization process, free from environmental pollution.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of nylon 6/ PP composite material and preparation method thereof.
Background technology
Nylon 6 (PA6) engineering plastics have good combination property, be widely used in automobile, electronic apparatus, machinery, railway,
Weapons and building field, but because its water suction causes mechanical properties decrease to again limit its wider application.Polypropylene (PP)
Mechanical property is good, and oil resistant and chemicals-resistant processing excellent, easy, water absorption rate are low, cheap, have good complementation with PA6
Property, PA6 Yu PP is blended the water imbibition that can reduce PA6 material, affects smaller on mechanical property and heat resistance, it is also possible to
Reduce cost.
Continuous fiber reinforced thermoplastic resin is a kind of reinforcing fiber unidirectional array and the length enhancing identical with resin granular material length
Thermoplastic composite.It is compared with short fine enhancing thermoplastic composite, owing to fibre length is longer, arrangement is more orderly, from
And make it have more excellent mechanical strength, all it is far above short fiber reinforced materials, especially including stretching, bending, impact strength
It is the heat resistance with excellence, is particularly suitable in automobile or field of household appliances replacing part metals parts.
Using conventional art to prepare fiber reinforcement PA6/PP composite is by PA6, PP resin, the double spiral shells of modified polyolefin resin
Bar extruder melt blending is extruded and is prepared.Although this technology of preparing is capable of lightweight, reduces water absorption rate and cost, but
Due under the shear action of screw rod, this technology of preparing itself continuous fiber or chopped strand can be sheared the shortest (fiber is long
Degree is only 0.05-0.5mm), cause the composite obtained ratio in terms of mechanical strength relatively low.
The most domestic had disclosed in prepare glass fibre reinforced nylon/composite polyolefine material, such as Chinese patent
CN101195707.In that patent, using a kind of nylon 6 and a kind of polypropylene is matrix resin, at the addition of toughener
Under conditions of constant, be can reach by the alloy material of glass fiber reinforcement and be better than without polyacrylic single reinforced nylon 6 material
The mechanical property of material, especially impact property.It is entered twin-screw by after matrix resin, toughener, antioxidant etc. uniformly mixing
Extruder, adds glass fibre at the glass fibre mouth that double screw extruder is special simultaneously, cool down after blending extrusion, air-dry,
Get product after pelletizing.The defect of the method is exactly to use traditional twin-screw modified device, and continuous fiber and resin raw material are double
Melt blending in screw extruder, under the shear action of screw rod, it is the shortest that continuous fiber is also sheared, the Performance comparision of material
Low.
It addition, prepare the patent of continuous fibre reinforced nylon/composite polyolefine material disclosed in also having, as China is special
Profit CN1131427.In that patent, first prepare continuous fiber reinforcing polyamide master batch, then by this master batch with containing polyamide,
The alloyed resins diluent of crystalline polyolefin resin and unsaturated carboxylic acid-modified olefin crystalline polymer blends and forms.This system
The defect of Preparation Method is: 1) to prepare two kinds of material, process is relatively complicated, adds production cost；2) produce long fibre to increase
During strong nylon resin master batch, owing to nylon resin is easy to change, technology controlling and process is more difficult, it is not easy to ensure the stability of color.
Chinese patent CN1810872 discloses a kind of continuous long fiber reinforced composite nylon/polyolefin material and preparation method thereof.
This composite is to blend the continuous long fiber reinforced polyolefin compound resin master batch of high microsteping content with nylon resin to form.Will
30～the continuous long fiber peacekeeping 20 of 80% (weight portion)～70% (weight portion) polyolefin compound resin use pultrusion method system
Become continuous long fiber reinforced polyolefin compound resin master batch；Continuous long fiber reinforced Nylon/polyolefin it is blended into more multiple with nylon resin
Condensation material.The defect of the method is, the grain length of nylon resin, density aspect and long fibre polyolefin compound resin master batch difference ratio
Relatively big, blend material blanking when injection mo(u)lding is uneven, it is difficult to ensure that the scattered uniformity of fiber and product in Injection moulded part
Weight stability, thus affect the use of client.
Summary of the invention
For the defect overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of nylon 6/ PP composite material and
Its preparation method.This material has higher rigidity and intensity, and the shock resistance of excellence and heat resistance, and this material
Material can be high by injection straight forming, production efficiency, and the product after using can recycle after crushed.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of nylon 6/ PP composite material, this material includes following components and weight portion thereof:
Nylon 6 raw material 500～600 parts,
Pp material 50～100 parts,
Continuous fiber reinforcing agent 300～400 parts,
Compatilizer 40～50 parts,
Antioxidant 10～20 parts,
Lubricant 2～6 parts.
Described nylon 6 raw material (PA6 raw material) 230 DEG C, load be melting means during 2.16Kg be 10～20g/10min.
Described polypropylene is HOPP or COPP, its 230 DEG C, load be that melting means during 2.16Kg is
10～40g/10min；
Described continuous fiber reinforcing agent is selected from continuous glass fibre (alkali-free glass fibre), carbon fiber, metallic fiber or synthesis
Resin fibre.If need high intensity can preferred carbon fiber, as not having particular/special requirement that sexual valence then can be selected higher
Alkali-free glass fibre.
Described continuous fiber reinforcing agent average length in composite prepared by the present invention is 3～60mm, average diameter
It is 3～30 μm, and its length is identical with final material bodies length, and the central principal axis of the composite prepared along the present invention is put down
Row arrangement.
Described compatilizer is selected from maleic anhydride grafts or organo silane coupling agent.
Described maleic anhydride grafts can be maleic anhydride inoculated polypropylene (PP-g), maleic anhydride grafted ethene-1-octene
Copolymer (POE-g) or atactic styrene-maleic anhydride copolymer (SMA resin) etc., maleic anhydride grafting ratio typically exists
0.5～1.5%.
Described organo silane coupling agent is selected from vinyl trimethoxy Ethoxysilane, ethyl trimethoxy silane, vinyl three second
TMOS or γ aminopropyltriethoxy silane, preferably γ aminopropyltriethoxy silane.
The described antioxidant mixture of one or more in Hinered phenols, hindered amines or phosphite ester kind antioxidant,
Preferably antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), antioxidant 1098
(3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine), irgasfos 168 (tricresyl phosphite-(2,4-DTBP ester)
Or one or more in antioxidant PEPQ (four (2,4-di-tert-butylphenols)-4,4 '-xenyl diphosphites) etc..
Described lubricant is ethylene-acrylic acid copolymer or stearate, preferably calcium stearate (CaSt), zinc stearate (ZnSt)
Or one or more in pentaerythrite stearate (PETS).
A kind of preparation method of above-mentioned nylon 6/ PP composite material, the method comprises the following steps:
(1) each raw material is weighed according to the above ratio, by PA6 raw material, pp material, compatilizer, antioxidant, lubricant,
It is added sequentially to high-speed mixer and mixing uniform, then mixed material is added to drying for standby in the hopper of extruder；
(2) mixed material in step (1) is put into double screw extruder adds heat fusing, more defeated through double screw extruder
In the dipping tank of the impregnating equipment delivering to continuous fiber reinforced thermoplastic material；
(3) preparation of continuous lod polyester elastomer materials: then in dipping tank, continuous fiber reinforcing agent is disperseed,
It is impregnated in step (2) in the fused materials prepared, is then drawn off from the sizing mouth die of impregnating equipment, cooling, pelletizing.
In described step (1), mixture temperature is 40～60 DEG C, and mixing time is 3-5 minute；
In described step (1), the baking temperature of extruder hopper is 80～90 DEG C.
In described step (2), the engine speed of extruder is 16～20Hz, and rate of feeding is 12～16Hz；Described step
(2) the screw diameter 65mm of double screw extruder in, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as: the
One section 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section 230～240 DEG C,
Melt temperature 220～225 DEG C, head temperature 225～235 DEG C.
The described dispersion in step (3), impregnating equipment are the special impregnating equipment of continuous fiber reinforced thermoplastic material.It is special
Profit number is CN1488674.The size of the sizing mouth die of described impregnating equipment is 2.0～4.0mm.
Described dipping tank temperature is 220～240 DEG C；
Described pelletizing speed is 170～240r/min.
The a length of 9-13mm of described pellet, particle diameter is 2.0～4.0mm.
Due to the fact that and have employed above technical scheme, i.e. use Long Glass Fiber Reinforced Pa 6/ PP composite material, at this
In material, glass fibre is orientated at same direction, and the length of fiber is more than 4mm, thus the rigidity of material is greatly improved
And intensity, and hydrolytic resistance and heat resistance.
The present invention compared with the existing technology, has the advantage that and beneficial effect:
1, the present invention uses Long Glass Fiber Reinforced Pa 6/ PP composite material, is carried out continuous glass-fiber all by impregnating equipment
Even dispersion, thorough impregnation, improve the interface interaction of glass and compound resin, it is ensured that the effective length of glass, thus significantly
Improve rigidity and the intensity of this material, significantly improve resistant to hydrolysis performance and the heat resistance of material simultaneously.
2, using continuous lod PA6/PP composite prepared by the present invention, fiber is uniformly dispersed, and part weight is stable.
3, the present invention is reasonable in design, simple in construction, practical, product be have certain length pellet (grain length: 9～13mm,
Diameter: 2.0～4.0mm), be dried after processing can directly injection mo(u)lding, production efficiency is high, and after product use at pulverizing
Reason can also recycle, free from environmental pollution.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
(1) each raw material is weighed according to following ratio,
PA6 raw material 500 parts,
PP raw material 100 parts,
Continuous fiber reinforcing agent 350 parts,
Compatilizer 50 parts,
12 parts of antioxidant,
Lubricant 5 parts.
PA6 raw material, its melting means is 10～20g/10min (230 DEG C, 2.16Kg)；
PP is HOPP, and its melting means is 10～40g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Compatilizer is PP-g (maleic anhydride inoculated polypropylene resin), and wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By PA6, PP, compatilizer, antioxidant, lubricant, it is added sequentially in high mixer, mixture temperature
Controlling at 40～60 DEG C, mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material, squeezed
The baking temperature going out machine hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (3.5mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (16～20Hz) and main frame feeding (12-16Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 35 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of double screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as:
First paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section
230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C.Dipping tank temperature controls at 220～240 DEG C；Grain
Expecting a length of 9-13mm, particle diameter is 2.0～4.0mm.
Injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above 90～100 DEG C in an oven
Being molded after being dried 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
Embodiment 2
(1) each raw material is weighed according to following ratio；
PA6 raw material 530 parts,
PP raw material 70 parts,
Continuous fiber reinforcing agent 350 parts,
Compatilizer 50 parts,
12 parts of antioxidant,
Lubricant 5 parts.
Wherein, the melting means of PA6 is 10～20g/10min (230 DEG C, 2.16Kg)；
PP is HOPP, and its melting means is 10～40g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Compatilizer is PP-g (maleic anhydride inoculated polypropylene resin), and wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By PA6, PP, compatilizer, antioxidant, lubricant, it is added sequentially in high mixer, mixture temperature
Controlling at 40～60 DEG C, mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material, squeezed
The baking temperature going out machine hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (3.5mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (16～20Hz) and main frame feeding (12-16Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 35 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of double screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as:
First paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section
230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C.
Dipping tank temperature controls at 220～240 DEG C；
The a length of 9-13mm of pellet, particle diameter is 2.0～4.0mm
Injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above 90～100 DEG C in an oven
Being molded after being dried 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
Embodiment 3
(1) each raw material is weighed according to following ratio；
PA6 raw material 550 parts,
PP raw material 50 parts,
Continuous fiber reinforcing agent 350 parts,
Compatilizer 50 parts,
12 parts of antioxidant,
Lubricant 5 parts.
PA6 raw material, its melting means is 10～20g/10min (230 DEG C, 2.16Kg)；
PP is HOPP, and its melting means is 10～40g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Compatilizer is PP-g (maleic anhydride inoculated polypropylene resin), and wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By PA6, PP, compatilizer, antioxidant, lubricant, it is added sequentially in high mixer, mixture temperature
Controlling at 40～60 DEG C, mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material, squeezed
The baking temperature going out machine hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (3.5mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (16～20Hz) and main frame feeding (12-16Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 35 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of double screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as:
First paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section
230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C.
Dipping tank temperature controls at 220～240 DEG C；
The a length of 9-13mm of pellet, particle diameter is 2.0～4.0mm
(4) injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above in an oven
Being molded after 90～100 DEG C dry 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
Embodiment 4
(1) each raw material is weighed according to following ratio；
PA6 raw material 600 parts,
PP raw material 50 parts,
Continuous fiber reinforcing agent 300 parts,
Compatilizer 50 parts,
12 parts of antioxidant,
Lubricant 5 parts.
PA6 raw material, its melting means is 10～20g/10min (230 DEG C, 2.16Kg)；
PP is HOPP, and its melting means is 10～40g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Compatilizer is PP-g (maleic anhydride inoculated polypropylene resin), and wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By PA6, PP, compatilizer, antioxidant, lubricant, it is added sequentially in high mixer, mixture temperature
Controlling at 40～60 DEG C, mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material, squeezed
The baking temperature going out machine hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (4.0mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (16～20Hz) and main frame feeding (14-18Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 30 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of double screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as:
First paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section
230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C.Dipping tank temperature controls at 220～240 DEG C；Grain
Expecting a length of 9-13mm, particle diameter is 2.0～4.0mm；
(4) injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above in an oven
Being molded after 90～100 DEG C dry 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
Embodiment 5
(1) each raw material is weighed according to following ratio；
PA6 raw material 500 parts,
PP raw material 50 parts,
Continuous fiber reinforcing agent 400 parts,
Compatilizer 50 parts,
12 parts of antioxidant,
Lubricant 5 parts.
PA6 raw material, its melting means is 10～20g/10min (230 DEG C, 2.16Kg)；
PP is HOPP, and its melting means is 10～40g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Compatilizer is PP-g (maleic anhydride inoculated polypropylene resin), and wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By PA6, PP, compatilizer, antioxidant, lubricant, it is added sequentially in high mixer, mixture temperature
Controlling at 40～60 DEG C, mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material, squeezed
The baking temperature going out machine hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (3.0mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (14～20Hz) and main frame feeding (11-16Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 40 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as: the
One section 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section 230～240 DEG C,
Melt temperature 220～225 DEG C, head temperature 225～235 DEG C.
Dipping tank temperature controls at 220～240 DEG C；
The a length of 9-13mm of pellet, particle diameter is 2.0～4.0mm
(4) injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above in an oven
Being molded after 90～100 DEG C dry 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
Comparative example 1
It is not added with long fiber reinforced Nylon 6 composite during polypropylene.
(1) each raw material is weighed according to following ratio,
PA6 raw material 650 parts,
Continuous fiber reinforcing agent 350 parts,
12 parts of antioxidant,
Lubricant 5 parts.
PA6 raw material, its melting means is 10～20g/10min (230 DEG C, 2.16Kg)；
Continuous fiber reinforcing agent is continuous alkali-free glass fibre, and fibre diameter is 27 μm；
Antioxidant is antioxidant 1098 (3,5-di-t-butyl-4 hydroxy benzenes propionyl-hexamethylene diamine) and irgasfos 168 (tricresyl phosphite
-(2,4-DTBP ester)) mixture, the two weight ratio is 1: 2；
Lubricant is ethylene-acrylic acid copolymer；
PA6 is dried preparation: baking temperature: 90～100 DEG C；Drying time: 6～8h；
(2) batch mixing prepares；By 650 parts of PA6,12 parts of antioxidant, 5 parts of lubricants, it is added sequentially in high mixer, batch mixing temperature
Degree controls at 40～60 DEG C, and mixing time stopped after 3-5 minute, was then added in the hopper of extruder standby by mixed material,
The baking temperature of extruder hopper is set as 80～90 DEG C；
(3) above-mentioned mixed material adds heat fusing in double screw extruder (parameter adding heat fusing is the temperature of double screw extruder
Degree parameter), then be transported in dipping tank, glass enters into dipping tank from glass entrance under the traction of hauling machine, at dipping
The effect of groove jockey pulley is lower to be realized and the dispersion of molten resin, dipping, by selecting the size (3.5mm) of sizing mouth die, simultaneously
Adjust extruder rotating speed (16～20Hz) and main frame feeding (12-16Hz), adjust continuous fiber reinforced thermoplastic polyester bullet
In elastomer material, the content of continuous fiber reinforcing agent is 35 ± 2%, adjusts the cutter rotating velocity (170～240r/min) of pelleter,
The pelletizing length making the continuous fiber reinforced thermoplastic polyester elastomer materials prepared controls 9～13mm, particle diameter
2.0～4.0mm.
Wherein, the screw diameter 65mm of double screw extruder, the draw ratio of screw rod is 40: 1, and mixed melting temperature is set as:
First paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the 5th section
230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C.
Dipping tank temperature controls at 220～240 DEG C；
The a length of 9-13mm of pellet, particle diameter is 2.0～4.0mm
Injection and batten are tested: by continuous glass-fiber strengthened thermoplastic polyester elastomeric material obtained above 90～100 DEG C in an oven
Being molded after being dried 6～8h, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 210～220 DEG C；Second segment: 220～230 DEG C；3rd section: 230～240 DEG C；Nozzle: 225～235 DEG C.
The each embodiment of table 1 is tested Data Comparison
| ASTM | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Remarks |
| Hot strength (MPa) | 162 | 167 | 170 | 150 | 180 | 174 | |
| Bending strength (MPa) | 254 | 259 | 264 | 220 | 275 | 268 | |
| Bending modulus (MPa) | 7200 | 7219 | 7320 | 6300 | 8100 | 7325 | |
| Izod notch shock (kJ/m2) | 36 | 36 | 38 | 35 | 36 | 35 | 23℃ |
| Izod non-notch impact (kJ/m2) | 76 | 75 | 78 | 73 | 79 | 80 | |
| Glass fiber content (%) | 34 | 34 | 34 | 30 | 40 | 35 | |
| Density (g/cm3) | 1.32 | 1.32 | 1.33 | 1.30 | 1.45 | 1.36 |
From above-mentioned table, data are not difficult to find out, the composite formed after polyacrylic addition, and density is significantly lower than continuous fiber
Reinforced nylon 6 composite, material cost also decreases, but the mechanical strength of material but differs little, it may be assumed that fine continuously
Dimension reinforced nylon 6/PP composite material is while keeping properties of nylons, and the density of material and cost have substantially reduction.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.It is familiar with
These embodiments obviously easily can be made various amendment by the personnel of art technology, and should General Principle described herein
Use in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, this area skill
Art personnel should be at the protection model of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment
Within enclosing.
Claims (8)
1. nylon 6/ PP composite material, it is characterised in that: this material includes following components and weight portion thereof:
Described nylon 6 raw material 230 DEG C, load be melting means during 2.16Kg be 10～20g/10min；
Described polypropylene is HOPP or COPP, its 230 DEG C, load be that melting means during 2.16Kg is
10～40g/10min；
The preparation method of described nylon 6/ PP composite material comprises the following steps:
(1) each raw material is weighed in proportion, by nylon 6 raw material, pp material, compatilizer, antioxidant, lubricant, successively
Join high-speed mixer and mixing uniform, then mixed material is added to drying for standby in the hopper of extruder；
(2) mixed material in step (1) is put into double screw extruder adds heat fusing, then carry through double screw extruder
In the dipping tank of the impregnating equipment of continuous fiber reinforced thermoplastic material；
(3) then in dipping tank, continuous fiber reinforcing agent disperseed, be impregnated in step (2) in the fused materials of preparation,
Then it is drawn off from the sizing mouth die of impregnating equipment, cooling, pelletizing；
In described step (1), mixture temperature is 40～60 DEG C, and mixing time is 3-5 minute；
In described step (1), the baking temperature of extruder hopper is 80～90 DEG C；
In described step (2), the engine speed of extruder is 16～20Hz, and rate of feeding is 12～16Hz；
The screw diameter 65mm of double screw extruder in described step (2), the draw ratio of screw rod is 40:1, mixed melting temperature
Degree is set as: first paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C, the
Five sections 230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C；
Described continuous fiber reinforcing agent is continuous alkali-free glass fibre, and described compatilizer is selected from maleic anhydride grafts or has
Machine silane coupling agent；
Described maleic anhydride grafts is randomly total to selected from maleic anhydride grafted ethene-1-octene copolymer or phenylethylene-maleic anhydride
Polymers, wherein the percent grafting of maleic anhydride is 0.5～1.5%；
Described organo silane coupling agent is selected from vinyl trimethoxy Ethoxysilane, ethyl trimethoxy silane, vinyl three ethoxy
Base silane or γ aminopropyltriethoxy silane；
The size of the sizing mouth die of described impregnating equipment is 2.0～4.0mm；
Described continuous fiber reinforcing agent average length in final nylon 6/ PP composite material is 4～60mm, flat
The most a diameter of 3～30 μm, and its length is identical with final nylon 6/ PP composite material body length, and along final nylon
The central principal axis of 6/ PP composite material is arranged in parallel.
Nylon 6/ PP composite material the most according to claim 1, it is characterised in that: described organo silane coupling agent choosing
From γ aminopropyltriethoxy silane.
Nylon 6/ PP composite material the most according to claim 1, it is characterised in that: described antioxidant is selected from hindered phenol
The mixture of one or more in class, hindered amines or phosphite ester kind antioxidant.
Nylon 6/ PP composite material the most according to claim 3, it is characterised in that: described antioxidant selected from four (β-
(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester, antioxidant 1098, irgasfos 168 or four (2,4-bis-tertiary fourths
Base phenol)-4,4 ' one or more in-xenyl diphosphites.
Nylon 6/ PP composite material the most according to claim 1, it is characterised in that: described lubricant selected from ethene-
Acrylic copolymer or stearate.
Nylon 6/ PP composite material the most according to claim 5, it is characterised in that: described lubricant is selected from stearic acid
One or more in calcium or zinc stearate.
7. the preparation method of arbitrary described nylon 6/ PP composite material of claim 1-6, it is characterised in that: the method
Comprise the following steps:
(1) ratio according to claim 1 weighs each raw material, by nylon 6 raw material, pp material, compatilizer, antioxidant,
Lubricant, is added sequentially to high-speed mixer and mixing uniform, then mixed material is added to drying for standby in the hopper of extruder；
(2) mixed material in step (1) is put into double screw extruder adds heat fusing, then carry through double screw extruder
In the dipping tank of the impregnating equipment of continuous fiber reinforced thermoplastic material；
(3) then in dipping tank, continuous fiber reinforcing agent disperseed, be impregnated in step (2) in the fused materials of preparation,
Then it is drawn off from the sizing mouth die of impregnating equipment, cooling, pelletizing；
In described step (1), mixture temperature is 40～60 DEG C, and mixing time is 3-5 minute；Or in described step (1)
The baking temperature of extruder hopper is 80～90 DEG C；
In described step (2), the engine speed of extruder is 16～20Hz, and rate of feeding is 12～16Hz；
The screw diameter 65mm of double screw extruder in described step (2), the draw ratio of screw rod is 40:1, mixed melting temperature
Degree is set as: first paragraph 160～180 DEG C, second segment 200～210 DEG C, the 3rd section 210～220 DEG C, the 4th section 220～230 DEG C,
5th section 230～240 DEG C, melt temperature 220～225 DEG C, head temperature 225～235 DEG C；
The size of the sizing mouth die of described impregnating equipment is 2.0～4.0mm.
Preparation method the most according to claim 7, it is characterised in that: described dipping tank temperature is 220～240 DEG C；Or institute
The pelletizing speed stated is 170～240r/min.
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| CN103194023B (en) * | 2013-03-19 | 2015-12-23 | 深圳市亚塑科技有限公司 | A kind of fiberglass reinforced PP/PA6 matrix material and preparation method thereof and application |
| CN103289375A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Continuous glass fiber reinforced polypropylene-nylon composite material and preparation method thereof |
| CN103289205A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | PP/PA6/HDPE composite material |
| CN103788627A (en) * | 2014-01-27 | 2014-05-14 | 上海日之升新技术发展有限公司 | Reaction type continuous long glass fiber reinforced nylon composite and preparation method thereof |
| CN103937231B (en) * | 2014-03-12 | 2016-11-02 | 金发科技股份有限公司 | A kind of glass fiber enhanced nylon complex for extrusion molding and its preparation method and application |
| EP3127958B1 (en) * | 2015-08-04 | 2021-09-01 | FUJIFILM Business Innovation Corp. | Resin composition, resin molded article, and method of preparing resin composition |
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| CN113462150B (en) * | 2021-06-28 | 2023-05-09 | 中广核瑞胜发（厦门）新材料有限公司 | Flame-retardant nylon composite material and preparation method thereof |
| CN113527873A (en) * | 2021-07-29 | 2021-10-22 | 宁波华腾首研新材料有限公司 | Glass fiber reinforced PA6 composite material and preparation method and application thereof |
| CN115716959B (en) * | 2022-11-23 | 2024-03-29 | 金旸（厦门）新材料科技有限公司 | Low-odor polypropylene-polyamide alloy material and preparation method thereof |
| CN116355399B (en) * | 2023-05-19 | 2023-08-04 | 山东祥龙新材料股份有限公司 | Flexible extrusion nylon material, preparation method and application thereof |
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| JP2005060547A (en) * | 2003-08-13 | 2005-03-10 | Daicel Chem Ind Ltd | Resin structure of long fiber-reinforced polymer alloy and molded article |
| CN101760009A (en) * | 2008-12-23 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Reinforced nylon alloy material capable of being directly bonded with TPE in injection molding way and preparation method thereof |
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