CN106317867A - Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof - Google Patents
Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106317867A CN106317867A CN201510341795.7A CN201510341795A CN106317867A CN 106317867 A CN106317867 A CN 106317867A CN 201510341795 A CN201510341795 A CN 201510341795A CN 106317867 A CN106317867 A CN 106317867A
- Authority
- CN
- China
- Prior art keywords
- continuous glass
- fiber reinforced
- hydrolysis
- reinforced polyamide
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material. The composite material is prepared from, by weight, 400-560 parts of PA66, 100-140 parts of PA6, 300-500 parts of continuous glass fibers, 6-10 parts of an antioxidant, 2-6 parts of a composite hydrolysis resisting agent, 3-5 parts of a composite light stabilizer, 4-8 parts of a lubricant, 5-15 parts of black master batch, and 5-15 parts of metal oxide. The composite material has excellent weatherability, good hydrolysis resistance, excellent rigidity and excellent impact toughness, surfaces of injection molded products formed by the composite material have no glass fiber exposure, application of glass fiber reinforced polyamide to different fields is met, the material can be directly injection-molded, the production high, and the used products can be recycled after being crushed.
Description
Technical field
The present invention relates to technical field of polymer materials, a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof.
Background technology
Containing highly polar amide groups in nylon66 fiber (PA66) molecular backbone, and the hydrogen bond between amide groups makes intermolecular adhesion stronger, easily make structure generation crystallization, so material has good mechanical property, such as intensity height, good rigidly, shock resistance etc., additionally material also has oil resistant and the advantage, especially thermostability and creep resistance such as chemicals, wearability, self lubricity and processing fluidity be good more preferably.In addition PA66 raw material is easy to get, low cost, thus is widely applied to the fields such as industry, clothing, decoration, engineering plastics.But the impact property that PA66 is under dry state and low temperature is poor, and elastic modelling quantity is low, the most hygroscopic and affect the dimensional stability of goods, it is impossible to meet the requirement of environmental stress resistance and high manufacturing accuracy.
Polyamide is after adding glass fiber reinforcement, it is greatly improved its mechanical performance, heat resistance and dimensional stability, in actual applications can be to mould for steel substituted metal material, meet high-strength structure product in automobile, the application of field of household appliances, for major part appearance member, not only need high mechanical strength, require that product outward appearance is good, it is impossible to have obvious glass emergence on the surface simultaneously.
There is document to be reported in fiber glass reinforced polyamide material interpolation inorganic mineral raw material at present, to the glass emergence on the surface improving product outward appearance, there is certain effect, but after adding inorganic mineral, the mechanical strength of material is decreased obviously, it is impossible to meet the design requirement of high intensity.
Additionally, after fiber glass reinforced polyamide, the water absorption rate of material can be reduced to about 2%, water absorption rate well below polyamide raw materials, but still the performance of material is had a great impact, causes material tensile property to reduce about 50%, the most out of doors under the conditions of use during the reason such as photoaging, material property conservation rate, less than initial state 40%, significantly limit the use field of fiber glass reinforced polyamide material.Therefore higher structure member is required for mechanical property and outdoor use, need the continuous glass-fiber reinforced polyamide composite that development mechanics performance is higher, have more preferable weatherability and resistant to hydrolysis.Use single nylon hydrolysis-resisting agent, it is impossible to ensure the material property of long-term hygrometric state.
Chinese patent CN102010590A proposes a kind of long glass fibre reinforced nylon material and preparation method thereof, and component is: nylon 29-67wt%, long glass fibres 30-60wt%, compatilizer 2-10wt%, antioxidant 0.3-1.0wt%.Preparation method: first nylon, compatilizer, antioxidant are mixed；Adding mixture in double screw extruder, processing temperature is at 235-300 DEG C again；Resin melt is clamp-oned in the impregnation mold being connected with twin-screw extrusion machine head；Then by long glass fibres by impregnation mold, the dipping temperature of impregnation mold is 260-320 DEG C, makes long glass fibres be sufficiently impregnated with by melt, finally cools down, draws, pelletizing, i.e. obtains Long Glass Fiber Reinforced Pa pellet.This invention only proposes material of long glass fiber reinforced nylon and preparation method thereof, but is the failure to further investigate in the resistant to hydrolysis performance and weather resistance of long fiber reinforced nylon material.
Chinese patent CN101921474A provides one to strengthen high-temperature nylon and preparation method thereof.Strengthen high-temperature nylon to be made up of the raw material of following weight part ratio: polyphenyl diamide 55%-80%, glass fibre 20%-45%, Brueggemann antioxidant 0.1%-1.2%.High-temperature nylon is strengthened by polyphenyl diamide to be mixed generation with glass fibre and Brueggemann antioxidant, enhancing high-temperature nylon is made not only to maintain the chemical resistance that other nylon have and the advantage easily processed, and under the effect of glass fibre and Brueggemann antioxidant, improve enhancing high-temperature nylon resistance to elevated temperatures and impact strength, can be more widely used so that strengthening high-temperature nylon.This invention uses Brueggemann copper salt antioxidant to improve the hydrolytic resistance of material to a certain extent, but use the direct blending and modifying of double screw extruder, owing to the shear action of screw rod causes fibre length the least, the performance for nylon material improves limited, and especially impact strength ratio is relatively low.
Summary of the invention
The technical problem to be solved in the present invention is: the shortcoming existed for above prior art and problem, a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof is provided, this material not only has good weather resistance and resistant to hydrolysis performance, and Injection moulded part outward appearance is good, without glass emergence on the surface, owing to using continuous glass-fiber to strengthen, glass is not carried out with being blended of resin in twin screw, also it is provided simultaneously with rigidity and the impact flexibility of excellence, this material can be by injection straight forming, production efficiency is high, product after using can recycle after crushed.
The technical scheme is that
A kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, it is characterized in that, the component of following parts by weight be prepared from: PA66:400-560 part, PA6:100-140 part, continuous glass fibre: 300-500 part, antioxidant: 6-10 part, compounding hydrolysis-resisting agent: 2-6 part, the compounding steady agent of light: 3-5 part, lubricant: 4-8 part, metal-oxide: 5-15 part, black masterbatch: 5-15 part.
Described PA6 resin melt index under test temperature 230 DEG C, test load 2.16Kg is 20g-30g/10min.
Described PA66 resin melt index under test temperature 275 DEG C, test load 0.325Kg is 20-40g/10min.
Described continuous glass fibre is selected from alkali-free glass fibre, and its a diameter of 13-22 μm, line density is 1200-4800g/km.
Described antioxidant includes N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphite ester (anti-168), and the two weight part ratio is 1:2.
Described compounding hydrolysis-resisting agent is polycarbodiimide and diisobutyl phosphordithiic acid copper, and the two weight is 1:1；
The described steady agent of compounding light is hindered amines light stabilizer: N, N '-two formyl-N, N '-two (2,2,6,6-tetramethyl-4-piperidines)-hexamethylene diamine (UV4050) and Octabenzone (UV531), the two weight part ratio is 1:1；
The described lubricant one or more kinds of mixture in ethylene-acrylic acid copolymer wax, calcium stearate (CaSt), silicone and tetramethylolmethane stearate.
Described metal-oxide is the one or two kinds of mixture in zinc oxide or calcium oxide, and the particle diameter of metal-oxide is 4-25 micron.
Described black masterbatch is high melanin blue phase white carbon black, and wherein content of carbon black is more than 90%, and matrix resin is ethylene-vinyl acetate copolymer, and black masterbatch melt index under test temperature 190 DEG C, test load 21.6Kg is 5-10g/10min.Such as black masterbatch T09242, T09294 etc..
The preparation method of a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, comprises the following steps:
(1), PA66, PA6, antioxidant, compounding hydrolysis-resisting agent, the compounding steady agent of light, lubricant, metal-oxide and black masterbatch are added sequentially in high mixer 40-60 DEG C of batch mixing 3-5 minute.Then being added in the hopper of extruder standby by mixed uniform mixed material, the baking temperature of extruder hopper is set as 80-90 DEG C；
(2) impregnating equipment of continuous fiber reinforced thermoplastic material, is used, by double screw extruder, the plasticizing of above-mentioned material melts is injected in impregnating equipment, continuous glass fibre is incorporated in impregnation mold by the access road of impregnation mold simultaneously, alternately walk around groups of jockey pulley tailing edge broken line to advance, glass by jockey pulley disperse uniformly dipping and dispersed with molten resin after by sizing mouth die, cooled, traction, pelletizing become the low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of a length of 6-25mm.
In described low floating fine hydrolysis continuous glass-fiber reinforced polyamide pellet, roving glass fiber is arranged in parallel with each other along pellet length direction, and fibre length is identical with pellet length；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40:1, mixed melting temperature is set as: first paragraph 140-160 DEG C, second segment 230-240 DEG C, the 3rd section 250-260 DEG C, 4th section 260-270 DEG C, 5th section 270-280 DEG C, melt temperature 250-270 DEG C, head temperature 265-275 DEG C
Size 2.5-3.5mm of described sizing mouth die；
Described impregnating equipment temperature is 280-300 DEG C；
Described PA66, PA6 is dried 6-8h before combination in the environment of temperature 90-100 DEG C.
Due to the fact that and have employed above technical scheme, the steady agent of light and the hydrolysis-resisting agent that are i.e. compounded by interpolation prepare continuous glass-fiber reinforced polyamide composite, owing to glass carries out dispersion mixing with molten resin in impregnating equipment, glass fibre is orientated at same direction within this material, and a length of 6-25mm of glass fibre in pellet, long fibre length can form stable three-dimensional net structure in material or product, thus the rigidity of material and impact flexibility and weather-proof and resistant to hydrolysis performance are greatly improved.Owing to using PA6 as processing adjuvant, reduce the viscosity of system, improve the processability of material, and solve the floating fine problem of article surface, improve article surface quality.
The present invention compared with the existing technology, has the advantage that and beneficial effect:
1, compared with prior art, the present invention uses continuous glass fibre reinforced plastic PA66, by impregnating equipment, continuous glass fibre is carried out dispersed, thorough impregnation, improve the interface interaction of glass fibre and PA66, ensure that the effective length of glass fibre, glass fibre length is identical with gained composite pellet length all at 6-25mm, thus substantially increases the rigidity of this material and intensity and the shock resistance of material.
2, compared with prior art, the present invention uses compound nylon hydrolysis-resisting agent and the steady agent of complex light, makes the composite of system have the hydrolytic resistance of excellence and good weatherability；
3, with prior art ratio, due to the use of metal-oxide, adding the compatibility of nylon resin and glass, the product appearance surfaces of material injection prepared by the use present invention is good, without glass emergence on the surface and floating fibre；
4, the present invention is reasonable in design, simple to operate, practical, product has pellet (grain length: the 6-25mm of certain length, diameter: 2.5-3.5mm), can directly injection mo(u)lding after dried, production efficiency is high, and can also recycle through pulverization process after product use, free from environmental pollution.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Wherein, PA66 resin, melt index is 20-30g/10min, and test condition is 275 DEG C, 0.325Kg；PA6 resin, melt index is 20g-40g/10min, and test condition is 230 DEG C, 2.16Kg；Continuous glass fibre is alkali-free continuous glass fibre, and fibre diameter is 17 μm, and line density is 1200-4800g/km；Antioxidant includes N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (anti-1098) and three ［ 2.4-di-tert-butyl-phenyl ］ phosphite ester (anti-168), and the weight part ratio of the two is 1:2；Compound hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphordithiic acid copper of Rhein chemistry, and the two weight is 1:1；The compounding steady agent of light is UV531 and UV4050 of BASF, and the weight part ratio of the two is 1:1；Lubricant includes ethylene-acrylic acid copolymer wax (AC540A), calcium stearate (CaSt), silicone (GM100) and tetramethylolmethane stearate (PETS)；Metal-oxide is zinc oxide or calcium oxide, and particle diameter is 20 microns, and the black masterbatch trade mark is the commercially available trade mark T09242, T09294；
Embodiment 1
(1), a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, this material pelletizing length 6-25mm, particle diameter 3.5mm, it includes the component of following weight part ratio: PA6:140 part, PA66:560 part, continuous glass fibre: 300 parts, antioxidant: 8 parts, compounding hydrolysis-resisting agent: 4 parts, the compounding steady agent of light: 4 parts, lubricant: 6 parts, zinc oxide: 15 parts, black masterbatch: 10 parts；Wherein, PA66 resin, melt index is 26g/10min, and test condition is 275 DEG C, 0.325Kg；PA6 resin, melt index is 32g/10min, and test condition is 230 DEG C, 2.16Kg；Continuous glass fibre is alkali-free continuous glass fibre, and fibre diameter is 17 μm, and line density is 2400g/km；Lubricant includes ethylene-acrylic acid copolymer wax (AC540A) and calcium stearate (CaSt), and the weight part ratio of the two is 1:1；Metal-oxide used be zinc oxide particle diameter be 20 microns, the black masterbatch trade mark is commercially available T09242；
(2), the preparation method of a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, comprise the following steps:
A, dry preparation: PA66/PA6 raw material is placed in exsiccator, baking temperature: 95 DEG C, drying time: 6h；
B, batch mixing prepare: 560 parts of PA66,140 parts of PA6,8 parts of antioxidant, 4 parts of compounding hydrolysis-resisting agents, 4 parts of steady agent of compounding light, 6 parts of lubricants, 15 parts of zinc oxide, 10 parts of black masterbatchs are added sequentially in high mixer, mixture temperature controls at 50 DEG C, mixing time stopped after 4 minutes, then being added in the hopper of extruder standby by mixed material, the baking temperature of extruder hopper is set as 85 DEG C；
C, the preparation of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite: use patent (CN1488674, publication date: 2004.04.14) in the special impregnating equipment of continuous fiber reinforced thermoplastic material that proposes, above-mentioned material melts is injected in impregnating equipment by extruder, continuous glass fibre is joined in impregnating equipment dispersed with molten resin simultaneously, by selecting size 3.5mm of sizing mouth die, , adjust the engine speed of extruder at 16-22Hz simultaneously, rate of feeding is at 15.0-17.0Hz, glass fiber content controls at 300 parts, adjust the cutter rotating velocity of pelleter, the low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite pelletizing length prepared is made to control at 11-13mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40:1, and mixed melting temperature is set as: first paragraph 150 DEG C, second segment 240 DEG C, the 3rd section 260 DEG C, the 4th section 270 DEG C, the 5th section 280 DEG C, melt temperature 265 DEG C, head temperature 270 DEG C；
Described impregnating equipment design temperature is 280 DEG C；
Embodiment 2
(1), a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, this material pelletizing length 11-13mm, particle diameter 3.0mm, component including following weight part ratio: PA6:120 part, PA66:480 part, continuous glass fibre: 400 parts, antioxidant: 6 parts, compounding hydrolysis-resisting agent: 2 parts, the compounding steady agent of light: 5 parts, lubricant: 8 parts, calcium oxide: 10 parts, black masterbatch: 5 parts；Wherein, PA66 resin, melt index is 26g/10min, and test condition is 275 DEG C, 0.325Kg；PA6 resin, melt index is 32g/10min, and test condition is 230 DEG C, 2.16Kg；Continuous glass fibre is alkali-free continuous glass fibre, and fibre diameter is 17 μm, and line density is 1200g/km；Lubricant includes ethylene-acrylic acid copolymer wax (AC540A) and silicone (GM100), and the weight part ratio of the two is 1:1；Metal-oxide used is calcium oxide, and particle diameter 25 microns, black masterbatch is commercially available trade mark T09294；
(2), the preparation method of a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, comprise the following steps:
A, dry preparation: PA66/PA6 raw material is placed in exsiccator, baking temperature: 100 DEG C, drying time: 6h；
B, batch mixing prepare: 480 parts of PA66,120 parts of PA6,6 parts of antioxidant, 2 parts of compound hydrolysis-resisting agents, 5 parts of steady agent of complex light, 8 parts of lubricants, 10 parts of calcium oxide, 5 parts of black masterbatch are added sequentially in high mixer, mixture temperature controls at 60 DEG C, mixing time stopped after 3 minutes, then being added in the hopper of extruder standby by mixed material, the baking temperature of extruder hopper is set as 80 DEG C；
C, the preparation of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite: use patent (CN1488674, publication date: 2004.04.14) in the special impregnating equipment of continuous fiber reinforced thermoplastic material that proposes, above-mentioned material melts is injected in impregnating equipment by extruder, continuous glass fibre is joined in impregnating equipment dispersed with molten resin simultaneously, by selecting size 3.0mm of sizing mouth die, , adjust the engine speed of extruder at 16-22Hz simultaneously, rate of feeding is at 15.0-17.0Hz, glass fiber content controls at 400 parts, adjust the cutter rotating velocity of pelleter, the low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite pelletizing length prepared is made to control at 6-25mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40:1, and mixed melting temperature is set as: first paragraph 160 DEG C, second segment 240 DEG C, the 3rd section 260 DEG C, the 4th section 270 DEG C, the 5th section 280 DEG C, melt temperature 250 DEG C, head temperature 265 DEG C；
Described impregnating equipment temperature is 300 DEG C；
Embodiment 3
(1), a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, this material pelletizing length 11-13mm, particle diameter 3.5mm, component including following weight part ratio: PA6:100 part, PA66:400 part, continuous glass fibre: 500 parts, antioxidant: 10 parts, compounding hydrolysis-resisting agent: 6 parts, the compounding steady agent of light: 3 parts, lubricant: 4 parts, zinc oxide 5 parts, black masterbatch: 15 parts；Wherein, PA66 resin, melt index is 24g/10min, and test condition is 275 DEG C, 0.325Kg；PA6 resin, melt index is 20g/10min, and test condition is 230 DEG C, 2.16Kg；Continuous glass fibre is alkali-free continuous glass fibre, and fibre diameter is 17 μm, and line density is 4800g/km；Lubricant includes silicone (GM100) and tetramethylolmethane stearate (PETS), and the weight part ratio of the two is 1:1；Burning is the zinc oxide of particle diameter 4 microns, and black masterbatch is commercially available trade mark T09294；
(2), the preparation method of a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, comprise the following steps:
A, dry preparation: PA66/PA6 raw material is placed in exsiccator, baking temperature: 95 DEG C, drying time: 6h；
B, batch mixing prepare: 400 parts of PA66,100 parts of PA6,10 parts of antioxidant, 6 parts of compounding hydrolysis-resisting agents, 2 parts of steady agent of compounding light, 4 parts of lubricants, 5 parts of zinc oxide, 15 parts of black masterbatch are added sequentially in high mixer, mixture temperature controls at 40 DEG C, mixing time stopped after 5 minutes, then being added in the hopper of extruder standby by mixed material, the baking temperature of extruder hopper is set as 90 DEG C；
C, the preparation of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite: use patent (CN1488674, publication date: 2004.04.14) in the special impregnating equipment of continuous fiber reinforced thermoplastic material that proposes, above-mentioned material melts is injected in impregnating equipment by extruder, continuous glass fibre is joined in impregnating equipment dispersed with molten resin simultaneously, by selecting size 2.5mm of sizing mouth die, , adjust the engine speed of extruder at 16-22Hz simultaneously, rate of feeding is at 15.0-17.0Hz, glass fiber content controls at 500 parts, adjust the cutter rotating velocity of pelleter, the low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite pelletizing length prepared is made to control at 6-25mm；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40:1, and mixed melting temperature is set as: first paragraph 140 DEG C, second segment 230 DEG C, the 3rd section 250 DEG C, the 4th section 260 DEG C, the 5th section 270 DEG C, melt temperature 270 DEG C, head temperature 275 DEG C；
Described impregnating equipment temperature is 290 DEG C；
Comparative example 1
In order to compare with prior art, this comparative example use continuous glass fibre disperse in the direct melting mixing of double screw extruder with PA66/PA6 resin, i.e. in step (2), continuous glass fibre is directly added to double screw extruder from fiber entry, by adjusting screw speed and feeding rotating speed, control content of glass fiber, at 300 parts, pulls out material strip from double screw extruder, and material strip crosses water cooling, blower fan dries up the water on material strip surface, then carries out pelletizing；Other components, formula proportion are identical with embodiment 1 with preparation method, and its performance test results is shown in Table 4.
Comparative example 2
In order to compare with technical scheme, in this comparative example, hydrolysis-resisting agent is selected from the polycarbodiimide (Stabaxol of Rhein chemistry
P), addition is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 4.
Comparative example 3
In order to compare with technical scheme, in this comparative example, hydrolysis-resisting agent is selected from diisobutyl phosphordithiic acid, and addition is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 4.
Comparative example 4
In order to compare with technical scheme, in this comparative example, the steady agent of light is the UV531 of BASF, and addition is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 3.
Comparative example 5
In order to compare with technical scheme, in this comparative example, the steady agent of light is the UV4050 of BASF, and addition is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 3.
Comparative example 6
In order to compare with technical scheme, in this comparative example, the steady agent of complex light is UV531 and UV4050 of BASF, and addition is 2 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 3.
Comparative example 7
In order to compare with technical scheme, in this comparative example, hydrolysis-resisting agent is selected from polycarbodiimide (Stabaxol P) and the diisobutyl phosphordithiic acid copper of Rhein chemistry, the two weight is 1:1, addition is 2 parts, other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 4.
Comparative example 8
In order to compare with technical scheme, in this comparative example, the addition of metal oxide zinc is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 9
In order to compare with technical scheme, in this comparative example, the addition of metal oxide calcium is 4 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 10
In order to compare with technical scheme, in this comparative example, the addition of metal oxide zinc is 16 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Comparative example 11
In order to compare with technical scheme, in this comparative example, the addition of metal oxide calcium is 16 parts, and other components and formula proportion, preparation method are identical with embodiment 1, and its performance test results is shown in Table 5；
Injection and batten are tested:
Being molded after being dried 6-8h under low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite 80-100 DEG C of environment in an oven obtained above, injection batten is ASTM batten, and injection temperature is as follows:
Blanking section: 260 DEG C；Second segment: 280 DEG C；3rd section: 290 DEG C；Nozzle: 270 DEG C；
Finally injection batten is put in exsiccator and carries out status adjustment: regulation temperature: 23 DEG C, regulating time: 16h；Batten performance test is carried out according to following standard scale 1, and test result is shown in Table 2.
Table 1 Mechanics Performance Testing standard
| Test event | Measuring unit | Testing standard | Remarks |
| Hot strength | MPa | ASTM D638 | |
| Bending strength | MPa | ASTM D790 | |
| Bending modulus | MPa | ASTM D790 | |
| Izod notched impact strength | KJ/m2 | ASTM D256 | 23℃ |
| Ash | % | ASTM D2584 | |
| Density | g/cm3 | ASTM D792 | |
| Heat distortion temperature | ℃ | ASTM D648 | 1.82MPa |
Weather-proof test:
Testing standard: SAE J1960-2004. is with controlling the water-cooled xenon arc lamp acceleration irradiation to automotive exterior materials；Performance comparison before and after using injection batten to test aging 1000h, test result is shown in Table 3；
Hydrolysis is tested:
95 DEG C of heating in water bath 100h of distilled water, are placed in 100 DEG C of oven drying 6h, and after status adjustment 16h, the batten performance before and after test water-bath, test result is shown in Table 4；
The each embodiment of table 2 is tested Data Comparison
| ASTM | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Remarks |
| Hot strength (MPa) | 182 | 229 | 246 | 165 | |
| Bending strength (MPa) | 280 | 305 | 355 | 245 | |
| Bending modulus (MPa) | 7500 | 12500 | 16000 | 6800 | |
| Izod notched impact strength (KJ/m2) | 35 | 43 | 48 | 11 | 23℃ |
| Ash (%) | 31 | 40 | 51 | 30 | |
| Density (g/cm3) | 1.36 | 1.46 | 1.58 | 1.36 | |
| Heat distortion temperature (DEG C) | 220 | 220 | 221 | 190 | 1.82MPa |
Table 3 each embodiment xenon lamp aging 1000h tests Data Comparison
| ASTM | Embodiment 1 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Remarks |
| Hot strength (MPa) | 110 | 82 | 78 | 95 | |
| Bending strength (MPa) | 190 | 132 | 145 | 166 | |
| Bending modulus (MPa) | 6300 | 3600 | 3800 | 4200 | |
| Izod notched impact strength (KJ/m2) | 32 | 26 | 24 | 27 | 23℃ |
| Ash (%) | 31 | 30 | 31 | 30 | |
| The floating fine situation of outward appearance | Slight floating fibre | The most floating fibre | The most floating fibre | The most floating fibre |
Table 4 each embodiment heating in water bath 100h tests Data Comparison
| ASTM | Embodiment 1 | Comparative example 2 | Comparative example 3 | Comparative example 7 | Remarks |
| Hot strength (MPa) | 115 | 79 | 81 | 86 | |
| Bending strength (MPa) | 185 | 130 | 127 | 142 | |
| Bending modulus (MPa) | 5900 | 3550 | 3801 | 4655 | |
| Izod notched impact strength (KJ/m2) | 38 | 24 | 26 | 29 | 23℃ |
| Ash (%) | 31 | 30 | 31 | 30 |
Table 5 each embodiment product outward appearance and Mechanics Performance Testing contrast
| ASTM | Embodiment 1 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Remarks |
| Hot strength (MPa) | 115 | 114 | 117 | 105 | 102 | |
| Bending strength (MPa) | 185 | 180 | 190 | 169 | 165 | |
| Bending modulus (MPa) | 5900 | 5860 | 6100 | 5650 | 5560 | |
| Izod notched impact strength (KJ/m2) | 38 | 36 | 38 | 26 | 25 | 23℃ |
| Ash (%) | 31 | 30 | 31 | 35 | 35 | |
| The floating fine situation of outward appearance | Without floating fibre | The most floating fibre | The most floating fibre | Without floating fibre | Without floating fibre |
Finding out according to the data in table 2, in embodiment 1,2,3, along with the increase of continuous glass fibre content, the mechanical strength of material presents the trend being gradually increased.The test result that comparative example 1 and embodiment 1 prepare material is compared, can be seen that, the embodiment of the present invention 1 uses roving glass fiber to impregnate reinforced polyamide composite, make gained composite pellet length identical with glass fibre length all at 6-25mm, owing to fibre length to exceed much compared with the material property of common double screw rod pelletize, thus especially particularly evident in terms of notch impact strength in mechanical property.
Xenon lamp aging data from table 3 are it can be seen that comparative example 1 and comparative example 4,5,6, after reducing the content of the steady agent of light or use single light steady agent system, all do not reach the material property of the present invention.
Data Comparison is tested after hot bath heating from table 4, can be seen that from the test data of embodiment 1 and comparative example 2,3,7, after reducing the addition of hydrolysis-resisting agent or using single resistant to hydrolysis system, the obvious step-down of material property, illustrates that the compound hydrolysis-resisting agent in the present invention has obvious action in terms of the resistant to hydrolysis of polyamide.
From table 5 in terms of the different adding proportions of metal-oxide, after the adding proportion of zinc oxide or calcium oxide is less than 5 parts, floating fine problem can substantially occur, after the adding proportion of zinc oxide or calcium oxide is more than 15 parts, although not havinging floating fine problem, but the mechanical properties decrease of material is obvious, therefore from improving the mechanical property of floating fine and stabilizing material comprehensively, the adding proportion of metal-oxide should be optimum addition 5-15 part.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.These embodiments obviously easily can be made various amendment by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art should be within protection scope of the present invention according to the announcement of the present invention, the improvement made without departing from scope and amendment.
Claims (10)
1. one kind low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite, it is characterized in that, the component of following parts by weight be prepared from: PA66:400-560 part, PA6:100-140 part, continuous glass fibre: 300-500 part, antioxidant: 6-10 part, compounding hydrolysis-resisting agent: 2-6 parts, the compounding steady agent of light: 3-5 part, lubricant: 4-8 part, metal-oxide: 5-15 part, black masterbatch: 5-15 part.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterised in that: described PA6 resin melt index under test temperature 230 DEG C, test load 2.16Kg is 20g-40g/10min；Described PA66 resin melt index under test temperature 275 DEG C, test load 0.325Kg is 20-30g/10min.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterised in that: described continuous glass fibre is selected from alkali-free glass fibre, and its a diameter of 13-22 μm, line density is 1200-4800g/km.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1; it is characterized in that: described antioxidant includes N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and three ［ 2.4-di-tert-butyl-phenyl ］ phosphite ester, the two weight part ratio is 1:2；Described compounding hydrolysis-resisting agent is selected from polycarbodiimide and diisobutyl phosphordithiic acid copper, and the two weight is 1:1.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterized in that: the described steady agent of compounding light is selected from hindered amines light stabilizer N, N '-two formyl-N, N '-two (2,2,6,6-tetramethyl-4-piperidines)-hexamethylene diamine and Octabenzone, the two weight part ratio is 1:1.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterised in that: the described lubricant one or more kinds of mixture in ethylene-acrylic acid copolymer wax, calcium stearate, silicone and tetramethylolmethane stearate.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterised in that: described metal-oxide is the one or two kinds of mixture in zinc oxide or calcium oxide, and the particle diameter of metal-oxide is 4-25 micron.
The low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite of one the most according to claim 1, it is characterised in that: described black masterbatch is high melanin blue phase white carbon black, and wherein content of carbon black is more than 90%.
9. the preparation method of the low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite described in any one of claim 1-8, it is characterised in that comprise the following steps:
(1), PA66, PA6, antioxidant, compounding hydrolysis-resisting agent, the compounding steady agent of light, lubricant, metal-oxide, black masterbatch are added sequentially in high mixer 40-60 DEG C of batch mixing 3-5 minute；Then being added in the hopper of extruder standby by the mixed material of mix homogeneously, the baking temperature of extruder hopper is set as 80-90 DEG C；
(2) impregnating equipment of continuous fiber reinforced thermoplastic material, is used, by double screw extruder, the plasticizing of above-mentioned material melts is injected in impregnating equipment, continuous glass fibre is incorporated in impregnating equipment by the access road of impregnation mold simultaneously, alternately walk around groups of jockey pulley tailing edge broken line to advance, glass by jockey pulley disperse uniformly dipping and dispersed with molten resin after by sizing mouth die, cooled, traction, pelletizing become the low floating fine hydrolysis continuous glass-fiber reinforced polyamide pellet of a length of 6-25mm；
In described low floating fine hydrolysis continuous glass-fiber reinforced polyamide pellet, roving glass fiber is arranged in parallel with each other along pellet length direction, and fibre length is identical with pellet length；
Double screw extruder used, screw diameter 65mm, the draw ratio of screw rod is 40:1, mixed melting temperature is set as: first paragraph 140-160 DEG C, second segment 230-240 DEG C, the 3rd section 250-260 DEG C, 4th section 260-270 DEG C, 5th section 270-280 DEG C, melt temperature 250-270 DEG C, head temperature 265-275 DEG C.
The preparation method of a kind of low floating fine hydrolysis continuous glass-fiber reinforced polyamide composite the most according to claim 11, it is characterised in that: described impregnating equipment temperature is 280-300 DEG C；Described PA66, PA6 is dried 6-8h before combination in the environment of temperature 90-100 DEG C；Size 2.5-3.5mm of described sizing mouth die.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341795.7A CN106317867A (en) | 2015-06-18 | 2015-06-18 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341795.7A CN106317867A (en) | 2015-06-18 | 2015-06-18 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106317867A true CN106317867A (en) | 2017-01-11 |
Family
ID=57733035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510341795.7A Pending CN106317867A (en) | 2015-06-18 | 2015-06-18 | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317867A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698970A (en) * | 2017-10-25 | 2018-02-16 | 惠州市纳米金塑胶科技有限公司 | A kind of nylon resin alloy for having high rigidity high intensity and hydrolysis |
| 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 |
| CN107778857A (en) * | 2017-11-17 | 2018-03-09 | 江门市荣龙新材料科技有限公司 | Anti- nylon 66 composite material of UV hydrolysis nylon 6/ of warp resistance and preparation method thereof |
| CN109486179A (en) * | 2018-09-30 | 2019-03-19 | 张家港绿洲新材料科技有限公司 | A kind of nylon 6 composition and its application in the long runner product of thin-walled |
| CN110776734A (en) * | 2019-09-26 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
| CN110903641A (en) * | 2018-09-17 | 2020-03-24 | 汉达精密电子(昆山)有限公司 | Hydrolysis-resistant glass fiber reinforced polyamide composite material and product thereof |
| CN110922749A (en) * | 2019-10-26 | 2020-03-27 | 张家港大塚化学有限公司 | Preparation method of high-weather-resistance and high-reflectivity polyamide composite material for LED |
| CN111100449A (en) * | 2019-12-03 | 2020-05-05 | 天津金发新材料有限公司 | Polyamide composition and preparation method thereof |
| CN111205638A (en) * | 2020-02-25 | 2020-05-29 | 合复新材料科技(无锡)有限公司 | Injection-moldable ceramic-like material, preparation method thereof and application thereof in rear cover of mobile communication equipment |
| CN112552674A (en) * | 2020-12-11 | 2021-03-26 | 天津金发新材料有限公司 | Polyamide composite material with low floating fiber and high impact strength |
| CN113185832A (en) * | 2021-04-29 | 2021-07-30 | 青岛东一岳新材料有限公司 | Special glass fiber reinforced PA6 material for automobile handles and processing technology |
| CN115260757A (en) * | 2022-08-15 | 2022-11-01 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant glass fiber reinforced PPA material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102684A (en) * | 2013-02-20 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and its preparation method |
| CN103756014A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Application of zinc oxide as anti-floating fiber agent of glass fiber enhanced thermoplastic plastic and anti-floating fiber master batch with zinc oxide |
| CN103772813A (en) * | 2014-01-06 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Low-floating fiber glass fiber reinforced polypropylene composite material and preparation method thereof |
-
2015
- 2015-06-18 CN CN201510341795.7A patent/CN106317867A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102684A (en) * | 2013-02-20 | 2013-05-15 | 合肥杰事杰新材料股份有限公司 | Weather-proof and hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and its preparation method |
| CN103772813A (en) * | 2014-01-06 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Low-floating fiber glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN103756014A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Application of zinc oxide as anti-floating fiber agent of glass fiber enhanced thermoplastic plastic and anti-floating fiber master batch with zinc oxide |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698970A (en) * | 2017-10-25 | 2018-02-16 | 惠州市纳米金塑胶科技有限公司 | A kind of nylon resin alloy for having high rigidity high intensity and hydrolysis |
| 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 |
| CN107778857A (en) * | 2017-11-17 | 2018-03-09 | 江门市荣龙新材料科技有限公司 | Anti- nylon 66 composite material of UV hydrolysis nylon 6/ of warp resistance and preparation method thereof |
| CN110903641A (en) * | 2018-09-17 | 2020-03-24 | 汉达精密电子(昆山)有限公司 | Hydrolysis-resistant glass fiber reinforced polyamide composite material and product thereof |
| CN109486179B (en) * | 2018-09-30 | 2021-03-30 | 张家港绿洲新材料科技有限公司 | Nylon 6 composition and application thereof in thin-wall long flow channel product |
| CN109486179A (en) * | 2018-09-30 | 2019-03-19 | 张家港绿洲新材料科技有限公司 | A kind of nylon 6 composition and its application in the long runner product of thin-walled |
| CN110776734B (en) * | 2019-09-26 | 2022-04-01 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
| CN110776734A (en) * | 2019-09-26 | 2020-02-11 | 中广核俊尔(浙江)新材料有限公司 | Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof |
| CN110922749A (en) * | 2019-10-26 | 2020-03-27 | 张家港大塚化学有限公司 | Preparation method of high-weather-resistance and high-reflectivity polyamide composite material for LED |
| CN111100449A (en) * | 2019-12-03 | 2020-05-05 | 天津金发新材料有限公司 | Polyamide composition and preparation method thereof |
| CN111205638A (en) * | 2020-02-25 | 2020-05-29 | 合复新材料科技(无锡)有限公司 | Injection-moldable ceramic-like material, preparation method thereof and application thereof in rear cover of mobile communication equipment |
| CN112552674A (en) * | 2020-12-11 | 2021-03-26 | 天津金发新材料有限公司 | Polyamide composite material with low floating fiber and high impact strength |
| CN112552674B (en) * | 2020-12-11 | 2022-06-07 | 天津金发新材料有限公司 | Polyamide composite material with low floating fiber and high impact strength |
| CN113185832A (en) * | 2021-04-29 | 2021-07-30 | 青岛东一岳新材料有限公司 | Special glass fiber reinforced PA6 material for automobile handles and processing technology |
| CN115260757A (en) * | 2022-08-15 | 2022-11-01 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant glass fiber reinforced PPA material and preparation method thereof |
| CN115260757B (en) * | 2022-08-15 | 2023-04-21 | 金旸（厦门）新材料科技有限公司 | Alcoholysis-resistant glass fiber reinforced PPA material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102684B (en) | A kind of weather-proof resistant to hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof | |
| CN106317867A (en) | Low-fiber exposure hydrolysis-resistant continuous glass fiber reinforced polyamide composite material and preparation method thereof | |
| CN106995606A (en) | A kind of dissaving polymer modified polyamide composite and preparation method thereof | |
| CN107501924A (en) | A kind of graphene, continuous glass-fiber collaboration reinforced polyamide composite and preparation method thereof | |
| CN107778853A (en) | A kind of heat oxygen aging resistance hydrolysis continuous glass-fiber reinforced polyamide composite and preparation method thereof | |
| CN103059562B (en) | High-glossiness anti-warping high-strength PA6 (polyamide 6) composite material, and preparation and application thereof | |
| CN103525088A (en) | Polyphenylene sulfide composite material and preparation method thereof | |
| CN110982258A (en) | Floating-fiber-free high-glass-fiber-reinforced nylon material and preparation method thereof | |
| CN108624006B (en) | High-fluidity glass fiber reinforced flame-retardant PC/PBT alloy material and preparation method thereof | |
| CN104530563A (en) | Injection-molding carbon fiber composite material and preparation method thereof, application of injection-molding carbon fiber composite material in automobile parts | |
| CN102558847B (en) | Hydrolysis resistant continuous carbon fiber reinforced nylon 6 material and preparation method thereof | |
| CN103030972A (en) | High heat resistance and low warping nylon 66 composite and preparation method thereof | |
| CN108070253B (en) | High-temperature-resistant thermo-oxidative-aging-resistant polyamide composition and preparation method thereof | |
| CN109401302A (en) | Good surface high impact nylon/POK alloy and preparation method thereof | |
| CN107501925A (en) | Fine collaboration reinforced polyamide composite of a kind of graphene, continuous carbon and preparation method thereof | |
| CN108264749A (en) | A kind of high good surface carbon fiber reinforced polycarbonate composite material of flowing and preparation method thereof | |
| CN103740027A (en) | Glass fiber reinforced AES composite material and preparation method thereof | |
| CN102702735A (en) | Highly-filled enhanced PA 66 composite material and preparation method thereof | |
| CN104419058A (en) | Polypropylene composition and preparation method thereof | |
| CN105924955A (en) | Low-moisture-absorption wear-resistant carbon-fiber-reinforced high-temperature-resistant nylon composite material and preparation method thereof | |
| CN107541049B (en) | Graphene-continuous glass fiber reinforced halogen-free flame-retardant weather-resistant PPO/HIPS alloy material and preparation method thereof | |
| CN103740025A (en) | Glass fiber reinforced inflaming retarding AES (Acrylonitrile-Ethylene propylene diene monomer-Styrene) composite material and preparation method thereof | |
| CN111073273A (en) | Glass fiber reinforced PA6 composite material for improving floating fiber and high surface smoothness and preparation method thereof | |
| CN109486013B (en) | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of polypropylene and preparation method thereof | |
| CN113429781A (en) | Long glass fiber reinforced bio-based polyamide 56, alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170111 |