CN104231614B - Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface - Google Patents
Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface Download PDFInfo
- Publication number
- CN104231614B CN104231614B CN201410439650.6A CN201410439650A CN104231614B CN 104231614 B CN104231614 B CN 104231614B CN 201410439650 A CN201410439650 A CN 201410439650A CN 104231614 B CN104231614 B CN 104231614B
- Authority
- CN
- China
- Prior art keywords
- nylon
- glass fiber
- retardant
- composite
- fibre
- 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.)
- Active
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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface: be made up of by weight following component, nylon 6:30 80%, alkali-free roving glass fiber: 10 60%, nano-calcium carbonate: 2 10%, main flame retardant: 1 3%, auxiliary fire retardant: 0.5 1%, low viscosity nylon 6:2 5%, glass modifying agent: 0.5 1%, other auxiliary agents: 0.5 1%.Glass of the present invention and nylon 6 have the good compatibility, and composite material surface does not reveal fibre, smooth surface, attractive in appearance；The present invention uses double fire retardant to be effectively improved product anti-flammability, and product anti-flammability reaches V 0 grade, can be used on the products such as the higher household of product surface fineness or aesthetic measure and security performance, office.
Description
Technical field
The present invention relates to a kind of organic polymer nano composite material, in particular, relate to a kind of surface and do not reveal roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre.
Background technology
Nylon 6 is one of several engineering plastics that application is most at present, his phthalein amine groups has polarity, there is in his structure well-set hydrogen bond, the fusing point making nylon 6 is higher, having good physical and mechanical property and wearability and self lubricity, these Comprehensive Characteristics are not available for other plastics.But the heat distortion temperature of pure nylon 6 is relatively low, water absorption is big, and before water suction, impact strength is on the low side, after water suction, rigidity declines to a great extent again, the shortcomings such as size is unstable simultaneously, thus limit the application of nylon 6, reduce the selection leeway of downstream industry design engineer in turn.Therefore, expand nylon 6 is carried out composite modified research.And improve the most effective most popular method that the comprehensive physical and mechanical property of nylon 6 material is used, it is simply that use glass fiber reinforced nylon 6.
And it is current, glass fiber reinforced nylon 6 is one of several engineering plastics that application is most at present, there is higher mechanical performance and heat distortion temperature, particularly long glass fiber reinforced nylon 6 material, but owing to the wick of glass makes material more easy firing, fire resistance does not reaches the requirement of some industry, limits its wider application, and the halogen-free flame retardants then cost using routine is the most high-leveled and difficult to promote；On the other hand, Nylon-66 reinforced with glass fiber is while being greatly improved nylon66 fiber physical and mechanical property, there is again individual distinct disadvantage, precisely due to glass and nylon66 fiber two-phase interface are difficult to good combination, cause easily producing glass emergence on the surface phenomenon at product surface, make product surface coarse and grow dim, thus limiting the application on the product higher to surface smoothness or aesthetic measure requirement of this raw material.
At present, pass through the research at long glass fiber reinforced fire-retardant nylon composite, wherein a kind of halogen-free flame-retardant long glass fiber reinforced nylon 6 of Chinese invention patent CN102504529A and preparation method, use the composite machinery performance such as phosphate ester, attapulgite and fire resistance, inorganic material adds the interface cohesion effect that have impact on glass with nylon, causes material surface the brightest and the cleanest；A kind of glass fiber reinforced nylon 6 composite of Chinese invention patent CN102690512A and preparation method and application, use the modification of nylon such as glass dispersant, graft polyolefin, grafted elastomeric, glass, good product dispersibility, but complex process, be costly and difficult to fire-retardant；The glass organic reinforced PA66 processing technology not revealing fibre of Chinese invention patent CN102888108A, uses glass inorganic agent, nucleator, heat stabilizer, glass fibre filling nylon, and glass is good with nylon compatibility, but product cost is higher, poor fire；A kind of high fluidity long glass fiber reinforced nylon 6 material of Chinese invention patent CN103013099A and preparation method, use continuous glass-fiber, lubricant, compatilizer, antioxidant modification of nylon 6, good product mobility, and outward appearance is good, but relatively costly, poor fire.
Summary of the invention
The invention aims to the shortcoming overcoming prior art to exist, there is provided a kind of and there is good mechanical property, fire resistance, and roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on the surface that any surface finish, production cost are low, technique is simple and environmentally-friendly.
The technical scheme of roving glass fiber flame-retardant reinforced nylon 6 composite that fibre is not revealed on surface of the present invention is: it is characterized in that: be made up of by weight following component, nylon 6:30% 80%, alkali-free roving glass fiber: 10% 60%, nano-calcium carbonate: 2% 10%, main flame retardant: 1% 3%, auxiliary fire retardant: 0.5% 1%, low viscosity nylon 6:2% 5%, glass modifying agent: 0.5% 1%, other auxiliary agents: 0.5% 1%.
Further, the relative viscosity of described nylon 6 resin is 2.4 3.6, and melt index is 4 8g/10min.
Further, the draw ratio of described alkali-free roving glass fiber is 100 300.
Further, described nano-calcium carbonate is particle diameter at the super fine calcium carbonate of 0.1 10 microns.
Further, described main flame retardant is made up of one or more in tripolycyanamide, APP, poly-ammonium polyphosphate, Firebrake ZB, phosphate ester.
Further, described auxiliary fire retardant is combined by one or more in antimony oxide, magnesium hydroxide, aluminium hydroxide.
Further, described low viscosity nylon 6 viscosity is 0.8 1.6, and melt index is 15 25 g/10min.
Further, described glass modifying agent is that one or more in γ aminopropyl triethoxysilane, γ glycidyl ether oxygen propyl trimethoxy silicane, γ methacryloxypropyl trimethoxy silane, γ mercaptopropyl trimethoxysilane combine.
Further, other described auxiliary agents include little molecule lubricant and antioxidant, and described little molecule lubricant 0.25% 0.5%, is that one or more in 13 generation spherical dendritic macromole PAMAM combine；Antioxidant 0.25% 0.5%, is 2,6 three grades of butyl 4 methylphenols.
The technical scheme of the preparation method that roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface of the present invention is: comprise the following steps:
A, by glass modifying agent and alkali-free roving glass fiber blending and modifying in proportion, add in low viscosity nylon 6 the most by a certain percentage, obtain glass master batch；
B, glass master batch, nylon 6, nano-calcium carbonate are dried process, put into main flame retardant, auxiliary fire retardant, other auxiliary agents mix and blend 5 15 minutes in homogenizer the most in proportion, obtain mixture；
C, mixture is placed 14 hours in 70 100 DEG C of vacuum drying ovens after, extrude through double screw extruder blended melting, cooling, through pelletizer, be cut into the particle of fixing requirement.
Further, extruder screw heats seven district's temperature and is respectively a district: 230 DEG C 260 DEG C, 2nd district: 235 DEG C 265 DEG C, 3rd district: 250 DEG C 280 DEG C, 4th district: 260 DEG C 280 DEG C, 5th district: 255 DEG C 270 DEG C, 6th district: 240 DEG C 260 DEG C, 7th district: 220 DEG C 235 DEG C.
The present invention prepares glass master batch by carrying out being blended with modified glass by low viscosity nylon, for filling-modified nylon 6, good compared with same series lubricant agent or polymeric lubricant effect；Using cheap nano-calcium carbonate is nucleator and auxiliary reinforcing agent, compounds with glass and plays nano double reinforced effects, and more single reinforcing agent is effective；Meanwhile, product uses organic fire-retardant and inorganic combustion inhibitor to compound, and solution organic fire-retardant is expensive, inorganic combustion inhibitor weak effect easily makes the problems such as composite becomes fragile, and effectively reduces fire-retardant cost, improves the fire-retardant property of composite；The present invention also utilizes dendritic macromole to be little molecule lubricant, is effectively improved the compatibility of each component of material.Present invention process is simple, cheaper starting materials, low cost, the nanocomposite constituents compatibility is good, there is good mechanical property, anti-flammability reaches V 0 grade, smooth surface, do not reveal fibre, can be used for, on the products such as the higher household of product surface fineness or aesthetic measure and security performance, office, there is good social value and experience is worth.
Accompanying drawing explanation
Fig. 1 is test Data Comparison in each embodiment.
Detailed description of the invention
Embodiment 1
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 2.4, melt index 8g/10min): 80%, draw ratio is the alkali-free roving glass fiber of 100: 10%, particle diameter is the nano-calcium carbonate of 1um: 3%, main flame retardant tripolycyanamide: 2%, auxiliary fire retardant magnesium hydroxide: 1%, low viscosity nylon 6 (relative viscosity 0.8, melt index is 25g/10min): 2%, glass modifying agent γ aminopropyl triethoxysilane: 1%, little molecule lubricant 1 generation PAMAM is 0.5%, antioxidant 2, 6 three grades of butyl 4 methylphenols are 0.5%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ aminopropyl triethoxysilane and alkali-free roving glass fiber are placed in reaction kettle for reaction 1h to alkali-free roving glass fiber modifying surface, are subsequently adding in low viscosity nylon 6, obtain glass master batch；
Secondly B, glass master batch, nylon 6, nano-calcium carbonate are dried process, it is then placed in main flame retardant tripolycyanamide, auxiliary fire retardant magnesium hydroxide, little molecule lubricant 1 generation PAMAM, antioxidant 2,6 three grades of butyl 4 methylphenol mix and blend 5 minutes in homogenizer, obtain mixture；
C, mixture is placed 4 hours in 70 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 230 DEG C of a district; two 235 DEG C of districts; three 250 DEG C of districts, four 260 DEG C of districts, five 255 DEG C of districts; six 240 DEG C of districts; seven 220 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
Embodiment 2:
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 3.0, melt index 6g/10min): 60%, draw ratio is the alkali-free roving glass fiber of 150: 25%, particle diameter is the nano-calcium carbonate of 3um: 8%, main flame retardant APP: 3%, auxiliary fire retardant antimony oxide: 1%, low viscosity nylon 6 (relative viscosity 1.0, melt index is 20g/10min): 2%, glass modifying agent γ glycidyl ether oxygen propyl trimethoxy silicane: 0.5%, little molecule lubricant 2 generation PAMAM is 0.3%, antioxidant 2, 6 three grades of butyl 4 methylphenols are 0.2%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ glycidyl ether oxygen propyl trimethoxy silicane and alkali-free roving glass fiber are placed in reaction kettle for reaction 2h to alkali-free roving glass fiber modifying surface, are subsequently adding in low viscosity nylon 6, obtain glass master batch；
Secondly B, glass master batch, nylon 6, nano-calcium carbonate are dried process, it is then placed in main flame retardant APP, auxiliary fire retardant antimony oxide, little molecule lubricant 2 generation PAMAM, antioxidant 2,6 three grades of butyl 4 methylphenol mix and blend 10 minutes in homogenizer, obtain mixture；
C, mixture is placed 3 hours in 80 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 240 DEG C of a district; two 245 DEG C of districts; three 260 DEG C of districts, four 270 DEG C of districts, five 265 DEG C of districts; six 250 DEG C of districts; seven 230 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
Embodiment 3:
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 3.6, melt index 4g/10min): 30%, draw ratio is the alkali-free roving glass fiber of 300: 50%, particle diameter is the nano-calcium carbonate of 10um: 10%, main flame retardant phosphate ester: 3%, auxiliary fire retardant aluminium hydroxide: 0.5%, low viscosity nylon 6 (relative viscosity 1.6, melt index is 15g/10min): 5%, glass modifying agent γ mercaptopropyl trimethoxysilane: 0.8%, little molecule lubricant 3 generation PAMAM is 0.4%, antioxidant 2, 6 three grades of butyl 4 methylphenols are 0.3%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ mercaptopropyl trimethoxysilane and alkali-free roving glass fiber are placed in reaction kettle for reaction 1.5h to alkali-free roving glass fiber modifying surface, are subsequently adding in low viscosity nylon 6, obtain glass master batch；
Secondly B, glass master batch, nylon 6, nano-calcium carbonate are dried process, it is then placed in main flame retardant phosphate ester, auxiliary fire retardant aluminium hydroxide, little molecule lubricant 3 generation PAMAM, antioxidant 2,6 three grades of butyl 4 methylphenol mix and blend 15 minutes in homogenizer, obtain mixture；
C, mixture is placed 1 hour in 100 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 250 DEG C of a district; two 255 DEG C of districts; three 260 DEG C of districts, four 270 DEG C of districts, five 255 DEG C of districts; six 255 DEG C of districts; seven 235 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
Comparative example 1:
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 2.2, melt index 7g/10min): 55%, draw ratio is the alkali-free roving glass fiber of 210: 40%, main flame retardant Firebrake ZB: 4%, glass modifying agent γ methacryloxypropyl trimethoxy silane: 0.5%, antioxidant 2,6 three grades of butyl 4 methylphenols are 0.5%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ methacryloxypropyl trimethoxy silane and alkali-free roving glass fiber are placed in reaction kettle for reaction 2.5h to alkali-free roving glass fiber modifying surface, obtain modified glass；
Secondly B, modification glass, nylon 6 are dried process, are then placed in main flame retardant Firebrake ZB, 2,6 three grades of butyl 4 methylphenol mix and blend 12 minutes in homogenizer of antioxidant, obtain mixture；
C, mixture is placed 2.5 hours in 95 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 235 DEG C of a district; two 240 DEG C of districts; three 275 DEG C of districts, four 275 DEG C of districts, five 265 DEG C of districts; six 255 DEG C of districts; seven 222 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
Comparative example 2:
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 1.9, melt index 6g/10min): 65%, draw ratio is the alkali-free roving glass fiber of 100: 28%, particle diameter is the nano-calcium carbonate of 6um: 4%, main flame retardant phosphate ester: 1%, auxiliary fire retardant antimony oxide: 0.5%, glass modifying agent γ methacryloxypropyl trimethoxy silane: 0.8%, antioxidant 2,6 three grades of butyl 4 methylphenols are 0.7%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ methacryloxypropyl trimethoxy silane and alkali-free roving glass fiber are placed in reaction kettle for reaction 1.3h to alkali-free roving glass fiber modifying surface, obtain modified glass；
B, modification glass, nylon 6, nano-calcium carbonate are dried process, are then placed in main flame retardant phosphate ester, auxiliary fire retardant antimony oxide, 2,6 three grades of butyl 4 methylphenol mix and blend 8 minutes in homogenizer of antioxidant, obtain mixture；
C, mixture is placed 2.5 hours in 84 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 246 DEG C of a district; two 256 DEG C of districts; three 275 DEG C of districts, four 275 DEG C of districts, five 265 DEG C of districts; six 255 DEG C of districts; seven 234 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
Comparative example 3:
Roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, its formula is by weight composition, nylon 6 (relative viscosity 2.4, melt index 7.5g/10min): 40%, draw ratio is the alkali-free roving glass fiber of 120: 52%, auxiliary fire retardant aluminium hydroxide: 3%, low viscosity nylon 6 (relative viscosity 1.5, melt index is 23g/10min): 3.6%, glass modifying agent γ glycidyl ether oxygen propyl trimethoxy silicane: 0.6%, 2 generation dendritic macromoles: 0.4%, antioxidant 2,6 three grades of butyl 4 methylphenols are 0.4%.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface, comprises the following steps:
A, glass modifying agent γ glycidyl ether oxygen propyl trimethoxy silicane and alkali-free roving glass fiber are placed in reaction kettle for reaction 1.9h to alkali-free roving glass fiber modifying surface, are subsequently adding in low viscosity nylon 6, obtain glass master batch；
Secondly B, glass master batch, nylon 6 are dried process, are then placed in auxiliary fire retardant aluminium hydroxide, 2 generation dendritic macromoles, 2,6 three grades of butyl 4 methylphenol mix and blend 13 minutes in homogenizer of antioxidant, obtain mixture；
C, mixture is placed 2.7 hours in 88 DEG C of vacuum drying ovens after; through double screw extruder, (screw rod heats seven district's temperature and is respectively 257 DEG C of a district; two 265 DEG C of districts; three 270 DEG C of districts, four 270 DEG C of districts, five 265 DEG C of districts; six 260 DEG C of districts; seven 220 DEG C of districts) blended melting extrusion, cooling, through pelletizer, it is cut into the particle of fixing requirement.
The surface of above-described embodiment formula is not revealed roving glass fiber flame-retardant reinforced nylon 6 composite of fibre and is used injection machine to be molded into standard batten through the most dried, carries out the performance tests such as mechanical property, thermostability, anti-flammability and outward appearance compare, and detailed performance is shown in Fig. 1.
Claims (9)
1. the preparation method of fine roving glass fiber flame-retardant reinforced nylon 6 composite is not revealed on surface, it is made up of by weight following component, nylon 6:30% 80%, alkali-free roving glass fiber: 10% 60%, nano-calcium carbonate: 2% 10%, main flame retardant: 1% 3%, auxiliary fire retardant: 0.5% 1%, low viscosity nylon 6:2% 5%, glass modifying agent: 0.5% 1%, other auxiliary agents: 0.5% 1%, other auxiliary agents include little molecule lubricant and antioxidant, described little molecule lubricant 0.25% 0.5%, is that one or more in 13 generation spherical dendritic macromole PAMAM combine；Described antioxidant 0.25% 0.5%, is 2,6 three grades of butyl 4 methylphenols；It is characterized in that, comprise the following steps:
A, by glass modifying agent and alkali-free roving glass fiber blending and modifying in proportion, add in low viscosity nylon 6 the most by a certain percentage, obtain glass master batch；
B, glass master batch, nylon 6, nano-calcium carbonate are dried process, put into main flame retardant, auxiliary fire retardant, other auxiliary agents mix and blend 5 15 minutes in homogenizer the most in proportion, obtain mixture；
C, mixture is placed 14 hours in 70 100 DEG C of vacuum drying ovens after, extrude through double screw extruder blended melting, cooling, through pelletizer, be cut into the particle of fixing requirement.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: the relative viscosity of nylon 6 is 2.4 3.6, and melt index is 4 8g/10min.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: the draw ratio of alkali-free roving glass fiber is 100 300.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: nano-calcium carbonate is the particle diameter super fine calcium carbonate at 0.1 10um.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: main flame retardant is made up of one or more in tripolycyanamide, APP, poly-ammonium polyphosphate, Firebrake ZB, phosphate ester.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: auxiliary fire retardant is combined by one or more in antimony oxide, magnesium hydroxide, aluminium hydroxide.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: low viscosity nylon 6 viscosity is 0.8 1.6, and melt index is 15 25 g/10min.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterised in that: glass modifying agent is that one or more in γ aminopropyl triethoxysilane, γ glycidyl ether oxygen propyl trimethoxy silicane, γ methacryloxypropyl trimethoxy silane, γ mercaptopropyl trimethoxysilane combine.
The preparation method of roving glass fiber flame-retardant reinforced nylon 6 composite of fibre is not revealed on surface the most according to claim 1, it is characterized in that: extruder screw heats seven district's temperature and is respectively a district: 230 DEG C 260 DEG C, 2nd district: 235 DEG C 265 DEG C, 3rd district: 250 DEG C 280 DEG C, 4th district: 260 DEG C 280 DEG C, 5th district: 255 DEG C 270 DEG C, 6th district: 240 DEG C 260 DEG C, 7th district: 220 DEG C 235 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410439650.6A CN104231614B (en) | 2014-09-01 | 2014-09-01 | Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410439650.6A CN104231614B (en) | 2014-09-01 | 2014-09-01 | Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104231614A CN104231614A (en) | 2014-12-24 |
| CN104231614B true CN104231614B (en) | 2016-08-17 |
Family
ID=52220569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410439650.6A Active CN104231614B (en) | 2014-09-01 | 2014-09-01 | Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104231614B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385137A (en) * | 2015-12-02 | 2016-03-09 | 威海晨源分子新材料有限公司 | Application of hyperbranched poly(amide amine)s in plastic processing |
| CN105419316B (en) * | 2015-12-08 | 2018-03-02 | 广州市合诚化学有限公司 | A kind of polyamide material of high weld mark strength enhancing and preparation method and application |
| CN108485257A (en) * | 2018-05-10 | 2018-09-04 | 句容市百事特复合材料有限公司 | A kind of long glass fiber reinforced polyamide compoiste material |
| CN109749436A (en) * | 2018-12-05 | 2019-05-14 | 上海普利特伴泰材料科技有限公司 | It is a kind of for making the high-temperature nylon plastic and preparation method thereof of alloy chopsticks |
| CN110256845A (en) * | 2019-06-27 | 2019-09-20 | 上海海事大学 | A kind of chopped strand enhancing nylon resin composite material and preparation method |
| CN113354943B (en) * | 2021-05-14 | 2023-05-12 | 金旸（厦门）新材料科技有限公司 | Wear-resistant high-temperature nylon material for electronic connector |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921472A (en) * | 2010-08-18 | 2010-12-22 | 苏州奔腾塑业有限公司 | High impact-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof |
| CN102391643B (en) * | 2011-09-07 | 2014-04-09 | 上海日之升新技术发展有限公司 | High temperate-resistant nanometer fire resistance-enhanced PA6 composite material and preparation method thereof |
| CN103113737B (en) * | 2012-10-08 | 2016-01-20 | 天津万塑新材料科技有限公司 | Glass fiber reinforcement resistant to hydrolysis nylon PA6/PA66 matrix material and preparation method thereof |
| CN103467978B (en) * | 2013-09-23 | 2016-06-29 | 湖南工业大学 | A kind of carrying roller multiple elements design modified nylon 6 composites and preparation method thereof |
-
2014
- 2014-09-01 CN CN201410439650.6A patent/CN104231614B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104231614A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104231614B (en) | Roving glass fiber flame-retardant reinforced nylon 6 composite and the preparation method of fibre is not revealed on surface | |
| CN103467851B (en) | The halogen-free flameproof PP of a kind of alternative flame-proof ABS adds fiber material and preparation method thereof | |
| CN103421293B (en) | Polycarbonate composite material and preparation method thereof | |
| CN103013109B (en) | Glass-fiber-reinforced PA66/PBT (polyamide 66/polybutylene terephthalate) resin alloy material and preparation method thereof | |
| CN102850650A (en) | Basalt fiber reinforced polypropylene composite material and preparation method thereof | |
| CN105504489A (en) | Alkali-free glass fiber reinforcing modified polypropylene composite material and preparing method thereof | |
| CN103304911A (en) | Flame-retardant reinforced ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof | |
| CN103289164A (en) | Flame-retardant polymer antistatic plastic | |
| CN103087481B (en) | High-strength halogen-free flame retardant PBT (Polybutylece Terephthalate) nano composite material and preparation method thereof | |
| CN106084769A (en) | A kind of fiberglass reinforced environmental protection nylon composite materials and preparation method thereof | |
| CN103351596A (en) | Improved glass fiber reinforced PC/ASA composition | |
| CN104693596A (en) | Scraping-resistant polypropylene resin and preparation method thereof | |
| CN105482255A (en) | Environment-friendly flame-retardant long-glass-fiber-reinforced polypropylene composite material and preparation method thereof | |
| CN108948737A (en) | A kind of enhancement engineering plastics and preparation method | |
| CN103044891A (en) | Halogen-free flame-retardant PC (polycarbonate) material and preparation method thereof | |
| CN101717578B (en) | Enhanced PA66 composite material and preparation method thereof | |
| CN103289368B (en) | A kind of continuous carbon fibre strengthens halogen-free reinforced nylon composite and preparation method thereof | |
| CN103540107B (en) | High-impact strengthens flame-retardant PBT material and preparation method thereof | |
| CN104086912B (en) | A kind of halogen-free flame-retardant glass fiber strengthens polyphenyl ether/styrene compositions and preparation method thereof | |
| CN108084623A (en) | A kind of low floating fine fiberglass reinforced AS compositions and its preparation method and application | |
| CN103289390A (en) | Reinforced PA66 composition | |
| CN104744772A (en) | Glass fiber reinforced polyethylene powder | |
| CN102604212A (en) | Aramid fiber pulp-enhanced expansion flame retardant polypropylene composite material and preparation method thereof | |
| CN110698768A (en) | Flexible touch polypropylene material with flame retardant and antibacterial properties as well as preparation method and application thereof | |
| CN109385092A (en) | PPS composite material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Long glass fiber flame-retardant reinforced nylon 6 composite material without fibers exposed to surface and preparation method of material Effective date of registration: 20180806 Granted publication date: 20160817 Pledgee: Industrial Commercial Bank of China Ltd Taizhou Huangyan branch Pledgor: Starway International Home-Living Co., Ltd. Registration number: 2018330000214 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 318020 No. 97 Shiyuan Road, Nancheng, Huangyan District, Taizhou City, Zhejiang Province Patentee after: Starway International Home Co., Ltd. Address before: 318020 No. 97 Shiyuan Road, Nancheng, Huangyan District, Taizhou City, Zhejiang Province Patentee before: Starway International Home-Living Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |