CN108948345A - Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application - Google Patents
Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application Download PDFInfo
- Publication number
- CN108948345A CN108948345A CN201810662591.7A CN201810662591A CN108948345A CN 108948345 A CN108948345 A CN 108948345A CN 201810662591 A CN201810662591 A CN 201810662591A CN 108948345 A CN108948345 A CN 108948345A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- carbon fiber
- caprolactam
- molding
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of preparation methods of fibre reinforced successive reaction molding nylon composite materials, include the following steps: the dehydration of S1, caprolactam；The preparation of S2, caprolactam activated monomer: being separately added into dewatered caprolactam into A, B activation kettle, and catalyst be added into the A activation kettle, co-catalyst is added into the B activation kettle, obtains A material and B material；The preparation of S3, PA6/ carbon fiber composite sheet: A material and B are expected that 1:1 is after mixing by volume, it is continuously conveyed with carbon fibre fabric to reacting in die head and is solidified respectively, PA6/ carbon fiber composite sheet is obtained through traction, cooling, winding, then is laid with molding through continuous lamination and obtains PA6/ carbon fiber composite board；Have the advantages that high intensity, high-modulus, light specific gravity, can secondary operation molding, can be used for manufacturing automobile, rail traffic vehicle body component, laptop, desktop computer, phone housing, suitcase, briefcase and bag.
Description
Technical field
The present invention relates to thermoplastic composite fields, compound more particularly to fibre reinforced successive reaction molding nylon
Material and its preparation method and application.
Background technique
With the process of global industry, the especially development of intermodal transport industry, the destruction of human living environmental protection environment
Also constantly aggravation, is continuously increased the consumption of petroleum limited resources, develops clean energy resource and energy conservation and environmental protection technology has become entirely
The important directions of ball transportation equipment industry development.The whole world is Japanese, German, U.S.A is that three big automotive giants lead vehicle energy saving to subtract
Row, safe and environment-friendly, comfortableization technology development.In last century Mo, vehicle structure largely is manufactured using polymer composite
Component, automobile lightweight significantly reduce oil consumption.Especially Japanese automobile fuel consumption is minimum, 5l/km or less；In recent years, vapour
The development of vehicle lightweight especially new-energy automobile is quick, and German Bayerische Motorne Werke Aktiengeellschaft produces full carbon fiber composite for the first time within 2016
Expect bodied vehicle.France, Germany, Italy, Japan, India etc. formulate fuel vehicle one after another and prohibit pin timetable, until the year two thousand thirty is basic
Cancel the sale of fuel vehicle.
2017, sale of automobile amount in China's was up to 28,870,000.Occupy Global Auto production and marketing first within continuous 8 years.Automobile enters house
Front yard consumption, becomes the indispensable tool of the lives of the people.Meanwhile also bringing a large amount of consumption and the exhaust emissions environmental pollution of petroleum
Social concern.Energy-saving and emission-reduction become the key subjects that China's development of automobile industry must solve.Therefore, automotive light weight technology and electricity
The development of the new-energy automobiles such as motor-car will become the only way of China's development of automobile industry.Especially, the development of electric car
It also will be the main path for catching up with and surpassing world car manufacture.
Either existing fuel vehicle or electric vehicle require to solve the problems, such as light-weighted.Except automobile chassis metal material knot
Outside structure lightweight, the application of composite material is the only way of automotive light weight technology.Polymer composite intensity with higher,
Specific gravity is the 1/4 of metal, and vehicle weight can be greatly reduced, and for fuel vehicle, oil consumption can be greatly decreased；It, can for electric vehicle
Greatly improve course continuation mileage.
Currently, extensive exploitation promotes carbon fiber-reinforced thermosetting composite material in the industry, but due to carbon fiber-reinforced thermosetting
Composite material is difficult to realize serialization, large-scale production, and production efficiency is low, is difficult to meet automobile serialization, scale requirement, together
When, same with thermosetting compound material can not post forming, recoverable, will not cause the pollution to environment.Fibre reinforced thermoplastic
Property composite material have high strength and modulus, can serialization large-scale production, can secondary operation, recoverable is automobile, rail
The composite material of road traffic equipment lightweight most application prospect.
Patent CN104890259A, CN103978693A, CN103289381A, CN201610688079 be all made of glass with
It activates caprolactam mixed liquor and is added in casting mold and react molding, belong to batch process route.There are techniques for this technique
The disadvantages such as control is inaccurate, batch products performance is uneven, yield rate is low, production efficiency is low.Patent CN103847053A is using activation
Caprolactam mixed liquor prepolymer coat roving glass fiber yarn on, then by the continuous fiber after coating processing successively by compacting,
Drying, cooling, slice obtain the sheet material monolithic of continuously unidirectional long fiber reinforcement MC nylon sheet material, and sheet material laying molding obtains continuous
Glass fiber reinforced nylon 6 composite board.There are two big defects for this technique: first is that Unidirectional Glass Fiber yarn be difficult to ensure it is evenly dispersed；Two
Be caprolactam activation performed polymer can quickly absorb water during coat glass fibre yarn so that caprolactam active matter occur hydrolyze and
Reaction is terminated, leads to not to form macromolecular chain.Therefore, the material mechanical performance of preparation is poor.Patent CN1292394A is used
Short carbon fiber is mixed with caprolactam activator, is injected reaction molding in die head and is obtained carbon fiber reinforced nylon composite board.This
Owned by France to form in intermittent intensified response, compared with the molding of continuous fiber continuous reaction, it is uneven that there are products, production efficiency
Low problem.
Summary of the invention
It is asked to solve the technology that carbon fibre reinforced composite in the prior art is uneven, is difficult to realize continuous production
Topic, the present invention propose that a kind of fibre reinforced successive reaction forms nylon composite materials and its preparation method and application.
Technical problem of the invention is resolved by technical solution below:
A kind of preparation method of fibre reinforced successive reaction molding nylon composite materials, includes the following steps:
The dehydration of S1, caprolactam；
The preparation of S2, caprolactam activated monomer: being separately added into dewatered caprolactam into A, B activation kettle, and to
Catalyst is added in the A activation kettle, co-catalyst is added into the B activation kettle, obtains A material and B material；
The preparation of S3, PA6/ carbon fiber composite sheet: by A material and B material, 1:1 is obtained after mixing by volume
It to mixed liquor, and is continuously conveyed respectively with carbon fibre fabric to reacting and carries out curing reaction in die head, through traction, cooling, winding
Obtain PA6/ carbon fiber composite sheet.
Preferably, the catalyst is NaOH, KOH, Na2CO3Or NaHCO3, additional amount is 0.5~2.0%.
Preferably, the additional amount of the NaOH is 0.9~1.5%.
Preferably, the co-catalyst is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), six
Methylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or triphenylmethane triisocyanate (TTI), add
Entering amount is 1.0~5.0%.
Preferably, the additional amount of the co-catalyst is 1.5~3.0%.
Preferably, the reaction temperature in the step S2 in A, B activation kettle is respectively 110~160 DEG C, and negative pressure is -0.05
~-0.1MPa, reaction time are 20~40min.
Preferably, the reaction temperature is 120~140 DEG C, and the negative pressure is -0.06~-0.08MPa, when the reaction
Between be 25~35min.
Preferably, in the step S3 mixed liquor conveying capacity be 0.5~5.0kg/min, curing reaction temperature be 140~
200 DEG C, the curing reaction time is 2~10min；The conveying capacity of the carbon fibre fabric is 0.5~12kg/min, and draw-down rate is
1~4m/min, residence time of the material in reaction die head is 2~10min.
Preferably, the conveying capacity of the mixed liquor is 2~4kg/min, and curing reaction temperature is 150~190 DEG C, and solidification is anti-
It is 3~6min between seasonable；The conveying capacity of the carbon fibre fabric is 2~8kg/min, and draw-down rate is 2~3m/min, and material exists
Reacting the residence time in die head is 4~8min.
Preferably, the carbon fibre fabric be plain weave or twills, wide cut be 400~1600mm, grammes per square metre be 200~
2000g/m2；
Preferably, the carbon fibre fabric be plain weave or twills, wide cut be 500~800mm, grammes per square metre be 500~
1500g/m2；
Preferably, the grade of fiber is T300~T1000 in the carbon fibre fabric, and specification is 6~241K.
Preferably, the grade of fiber is T700~T800 in the carbon fibre fabric, and specification is 12~24K.
Preferably, the preparation method further includes forming the PA6/ carbon fiber composite sheet continuous mould pressing, is answered
Plywood material, the continuous mould pressing moulding process include unreel, draw, preheating, being molded, cooling down, trimming, cutting and packaging, wherein
Hauling speed be 1~3m/min, preheating temperature be 140~180 DEG C, molding temperature be 200~250 DEG C, molding pressure be 1~
5MPa, clamp time are 1~10min, and cooling temperature is 60~100 DEG C, and cooling time is 2~10min.
Preferably, the hauling speed is 1.5~2.0m/min, and the preheating temperature is 160~180 DEG C, the molding
Temperature is 210~240 DEG C, the 2.0~4.0MPa of molding pressure, and the clamp time is 2~8min, and the cooling temperature is
60~80 DEG C, the cooling time is 4~6min.
The present invention also proposes a kind of compound using the fibre reinforced successive reaction molding nylon of above-mentioned preparation method preparation
Material.
The present invention also proposes that a kind of above-mentioned fibre reinforced successive reaction forms nylon composite materials in automobile, rail traffic
Application in terms of car body component, laptop computer, desktop computer, suitcase, briefcase or bag.
The beneficial effect of the present invention compared with the prior art includes:
The preparation method of fibre reinforced successive reaction molding nylon composite materials of the invention, include the following steps: S1,
The dehydration of caprolactam；The preparation of S2, caprolactam activated monomer: dewatered acyl in oneself is separately added into A, B activation kettle
Amine, and catalyst is added into the A activation kettle, co-catalyst is added into the B activation kettle, obtains A material and B material；S3,
The preparation of PA6/ carbon fiber composite sheet: by A material and B material, 1:1 obtains mixed liquor after mixing by volume, and
It is continuously conveyed respectively with carbon fibre fabric to reacting and carries out reaction solidification in die head, obtain PA6/ carbon fiber through traction, cooling, winding
Tie up composite sheet；The mixed liquor obtained after A material and B material are mixed according to volume ratio 1:1 carries out it in curing reaction
Before, it is continuously conveyed respectively with the carbon fibre fabric to described and is reacted in die head, since viscosity and the water of caprolactam liquid connect
Closely, and the chief component of mixed liquor is caprolactam liquid, so mixed liquor before curing can carbon described in rapid impregnation
Fabric, and quickly coat the carbon fiber in carbon fibre fabric；Then, mixed liquor is in reaction die head, with the progress of reaction,
Molecular weight rapid growth is simultaneously formed by curing PA6 resin, thus, realize the seamless sticky between PA6 resin and the carbon fibre fabric
Knot fundamentally solves the problems, such as that nylon resin is difficult to thorough impregnation cladding carbon fiber；Meanwhile using carbon fibre fabric conduct
The framework material of composite material, among mold process, due to the effect of carbon fibre fabric intertexture node, in carbon fibre fabric
Carbon fiber, which will not be flowed because heated with PA6 resin melting, generates the dispersion of carbon fiber caused by sliding phenomenon unevenly, into one
Step avoids fibre reinforced successive reaction from forming the non-uniform problem of nylon composite materials, to effectively improve fibre reinforced
The mechanical property of successive reaction molding nylon composite materials；In addition, by the way that the mixed liquor and the carbon fibre fabric is continuous
It is delivered in the reaction die head and carries out curing reaction, then obtain PA6/ carbon fiber composite sheet through traction, cooling, winding, it is real
The continuous production of the fibre reinforced successive reaction molding nylon composite materials is showed.
Other beneficial effects:
1, the catalyst is NaOH, KOH, Na2CO3Or NaHCO3, additional amount is 0.5~2.0%；Due to catalyst
Dosage be affected to the speed of caprolactam monomer polymerization reaction, the dosage of catalyst excessively will lead to reaction speed mistake
Fastly, the curing time of reaction system is too short, and mixed liquor is be easy to cause also to have not enough time to carbon fibre fabric described in thorough impregnation, just by
Liquid becomes solid-like, meanwhile, under solid states, reaction speed can sharply decline reaction system, it is difficult to it is poly- to form macromolecular
Object is closed, the poor mechanical property of fibre reinforced successive reaction molding nylon composite materials is eventually led to；When catalyst amount is very few,
The activation point that reaction system is formed is few, and reaction speed is slow, extended residence time of the material in reaction die head, meanwhile, reaction is just
When the reaction speed of phase is lower, the polymerization reaction in system later period will affect, i.e. polymerization later period molecule chain growth speed is slower, it is difficult to
Form macromolecular chain polymer；By the additional amount of catalyst to be set as 0.5~2.0%, so that the time needed for solidifying is appropriate,
Under the premise of guaranteeing that mixed liquor sufficiently infiltrates carbon fibre fabric, as far as possible the shortening reaction time, carbon fiber is further increased
Enhance the mechanical property of successive reaction molding nylon composite materials.
2, the carbon fibre fabric be plain weave or twills, wide cut be 400~1600mm, grammes per square metre be 200~
2000g/m2；When the wide cut of carbon fibre fabric is too wide, the oversized of die head is reacted, certainly will need to improve the conveying of mixed liquor
Speed just can guarantee its quick infiltration carbon fibre fabric in a short time, and when activated monomer conveying speed is too fast, it may entrainment
Bubble causes product to generate gap；Equally, when carbon fibre fabric grammes per square metre is excessive, the thickness of carbon fibre fabric and density compared with
Greatly, mixed liquor is influenced to the wetting velocity of carbon fibre fabric, and the final fibre reinforced successive reaction that influences forms nylon composite wood
The mechanical property of material；By the way that the wide cut of the carbon fibre fabric is limited to 400~1600mm, grammes per square metre is limited to 200~
2000g/m2, the influence of the generation and mixed liquor of bubble to carbon fibre fabric wetting velocity can be effectively avoided, thus into one
Step improves the mechanical property of fibre reinforced successive reaction molding nylon composite materials.
Specific embodiment
The following further describes the present invention in combination with preferred embodiments.
It should be noted that raw materials caprolactam of the present invention derives from Ba Ling petro-chemical corporation, polymer grade；Carbon fiber
Using toray company, catalyst and co-catalyst are commercially available.
Embodiment 1
The dehydration of step 1, caprolactam.
Solid caprolactam 50kg is weighed, dehydrating kettle is added, is heated to 90 DEG C, after caprolactam melts completely, is opened
Vacuum pump, the negative pressure in dehydrating kettle are -0.02MPa, are dehydrated 10min.
The preparation of step 2, caprolactam activated monomer.
The caprolactam liquid of dehydration is respectively fed to each 20kg of A, B activation kettle through metering pump, 200g is added in A kettle
400g toluene di-isocyanate(TDI) (TDI) is added in NaOH, B kettle, A kettle is heated to 140 DEG C, reacts 30min, observes condenser visor
When anhydrous drippage, reaction terminates, and obtains A material, keeps the temperature spare；B kettle is heated to 160 DEG C, reacts 25min, device visor to be condensed without
Reaction terminates when water drips, and obtains B material, it is spare to be cooled to 140 DEG C of heat preservations.
The preparation of step 3, PA6/ carbon fiber composite sheet.
(1) reaction molding die is heated to 160 DEG C, suitable N is filled in mold2。
(2) material of A obtained in step 2 and B are expected into 1:1 by volume, with 500g/min, is sent into super mixer mixing
Afterwards, it is added from the lower part of reaction die head to reaction die head；
(3) taking carbon fiber twills wide cut is 500mm, grammes per square metre 1kg/m2, after being heat-treated at 350 DEG C, with
The hauling speed of 2m/min enters reaction die head, and the residence time in reaction die head is 3min, i.e. end of reaction；
(4) material is pulled out from reaction die head, through heat rolling light, cooling and shaping, is wound into a roll, obtains PA6/ carbon fiber
Composite sheet A-1.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, the carbon fibre fabric be carbon fiber plain cloth, obtain PA6/ carbon
Fibre composite sheet A-2.
Embodiment 3
The dehydration of step 1, caprolactam.
Solid caprolactam 50kg is weighed, dehydrating kettle is added, is heated to 90 DEG C, after caprolactam melts completely, is opened
Vacuum pump, the negative pressure in dehydrating kettle are -0.02MPa, are dehydrated 10min.
The preparation of step 2, caprolactam activated monomer.
The caprolactam liquid of dehydration is respectively fed to each 20kg of A, B activation kettle through metering pump, 200g is added in A kettle
400g hexamethylene diisocyanate (HDI) is added in NaOH, B kettle, A kettle is heated to 145 DEG C, reacts 30min, observes condenser
When the anhydrous drippage of visor, reaction terminates, and obtains A material, keeps the temperature spare；B kettle is heated to 160 DEG C, reacts 25min, device view to be condensed
Reaction terminates when mirror anhydrous drippage, obtains B material, it is spare to be cooled to 140 DEG C of heat preservations.
The preparation of step 3, PA6/ carbon fiber composite sheet.
(1) reaction molding die is heated to 160 DEG C, suitable N is filled in mold2。
(2) material of A obtained in step 2 and B are expected into 1:1 by volume, with 500g/min, is sent into super mixer mixing
Afterwards, it is added from the lower part of reaction die head to reaction die head；
(3) taking carbon fiber twills wide cut is 500mm, grammes per square metre 1kg/m2, after being heat-treated at 350 DEG C, with
The hauling speed of 2m/min enters reaction die head, and the residence time in reaction die head is 3min, i.e. end of reaction；
(4) material is pulled out from reaction die head, through heat rolling light, cooling and shaping, is wound into a roll, obtains PA6/ carbon fiber
Composite sheet A-3.
Embodiment 4
The present embodiment and the difference of embodiment 3 are that the carbon fibre fabric is carbon fiber plain cloth, obtain PA6/ carbon
Fibre composite sheet A-4.
Embodiment 5
The dehydration of step 1, caprolactam.
Solid caprolactam 50kg is weighed, dehydrating kettle is added, is heated to 90 DEG C, after caprolactam melts completely, is opened
Vacuum pump, the negative pressure in dehydrating kettle are -0.02MPa, are dehydrated 10min.
The preparation of step 2, caprolactam activated monomer.
The caprolactam liquid of dehydration is respectively fed to each 20kg of A, B activation kettle through metering pump, 200g is added in A kettle
400g methyl diphenylene diisocyanate (MDI) is added in NaOH, B kettle, A kettle is heated to 145 DEG C, reacts 30min, observation condensation
When the anhydrous drippage of device visor, reaction terminates, and obtains A material, keeps the temperature spare；B kettle is heated to 170 DEG C, reacts 20min, device to be condensed
Reaction terminates when visor anhydrous drippage, obtains B material, it is spare to be cooled to 140 DEG C of heat preservations.
The preparation of step 3, PA6/ carbon fiber composite sheet.
(1) reaction molding die is heated to 180 DEG C, suitable N is filled in mold2。
(2) material of A obtained in step 2 and B are expected into 1:1 by volume, with 500g/min, is sent into super mixer mixing
Afterwards, it is added from the lower part of reaction die head to reaction die head；
(3) taking carbon fiber twills wide cut is 500mm, grammes per square metre 1kg/m2, after being heat-treated at 350 DEG C, with
The hauling speed of 2m/min enters reaction die head, and the residence time in reaction die head is 3min, i.e. end of reaction；
(4) material is pulled out from reaction die head, through heat rolling light, cooling and shaping, is wound into a roll, obtains PA6/ carbon fiber
Composite sheet A-5.
Embodiment 6
The present embodiment and the difference of embodiment 5 are that the carbon fibre fabric is carbon fiber plain cloth, obtain PA6/ carbon
Fibre composite sheet A-6.
Embodiment 7
The dehydration of step 1, caprolactam.
Solid caprolactam 50kg is weighed, dehydrating kettle is added, is heated to 90 DEG C, after caprolactam melts completely, is opened
Vacuum pump, the negative pressure in dehydrating kettle are -0.02MPa, are dehydrated 10min.
The preparation of step 2, caprolactam activated monomer.
The caprolactam liquid of dehydration is respectively fed to each 20kg of A, B activation kettle through metering pump, 300g is added in A kettle
400g toluene di-isocyanate(TDI) (TDI) is added in NaOH, B kettle, A kettle is heated to 145 DEG C, reacts 30min, observes condenser visor
When anhydrous drippage, reaction terminates, and obtains A material, keeps the temperature spare；B kettle is heated to 160 DEG C, reacts 25min, device visor to be condensed without
Reaction terminates when water drips, and obtains B material, it is spare to be cooled to 140 DEG C of heat preservations.
The preparation of step 3, PA6/ carbon fiber composite sheet.
(1) reaction molding die is heated to 160 DEG C, suitable N is filled in mold2。
(2) material of A obtained in step 2 and B are expected into 1:1 by volume, with 500g/min, is sent into super mixer mixing
Afterwards, it is added from the lower part of reaction die head to reaction die head；
(3) taking carbon fiber twills wide cut is 500mm, grammes per square metre 1kg/m2, after being heat-treated at 350 DEG C, with
The hauling speed of 2m/min enters reaction die head, and the residence time in reaction die head is 3min, i.e. end of reaction；
(4) material is pulled out from reaction die head, through heat rolling light, cooling and shaping, is wound into a roll, obtains PA6/ carbon fiber
Composite sheet A-7.
Embodiment 8
The present embodiment and the difference of embodiment 7 are that the carbon fibre fabric is carbon fiber plain cloth, obtain PA6/ carbon
Fibre composite sheet A-8.
Embodiment 9
The preparation of PA6/ carbon fiber composite board.
A-1, A-2 composite sheet are taken, carries out laser heating by the paving mode of A-1/A-2/A-2/A-1/A-2/A-2/A-1
Molding, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B1；Wherein, mould pressing process are as follows: hauling speed
2m/min, preheating temperature: 180 DEG C, hot pressing temperature: 230 DEG C；Pressure 2.0MPa, hot pressing time: 4min, 80 DEG C of cooling temperature, pressure
Power 3MPa.
Embodiment 10
The present embodiment and the difference of embodiment 9 are, continuously add by the paving mode of A-1/A-2/A-1/A-2/A-1
Hot moulding, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B2.
Embodiment 11
The present embodiment and the difference of embodiment 9 are, by A-1/ (A-1)3The paving mode of/A-1 carries out laser heating mould
Pressure, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B3.
Embodiment 12
The present embodiment and the difference of embodiment 9 are, A-3, A-4 composite sheet are taken, by A-3/A-4/A-4/A-3/A-4A-
The paving mode of 4/A-3 carries out laser heating molding, cooling traction, trimming, cutting packaging, obtains PA6/ carbon fiber composite board
B4。
Embodiment 13
The present embodiment and the difference of embodiment 12 are, carry out by the paving mode of A-3/A-4/A-3/A-4/A-3 continuous
Heating and mould pressing, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B5.
Embodiment 14
The present embodiment and the difference of embodiment 12 are, by A-3/ (A-3)3The paving mode of/A-3 carries out laser heating mould
Pressure, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B6.
Embodiment 15
The present embodiment and the difference of embodiment 9 are, A-5, A-6 composite sheet are taken, by A-5/A-6/A-6/A-5/A-6/
The paving mode of A-6/A-5 carries out laser heating molding, cooling traction, trimming, cutting packaging, obtains PA6/ carbon fiber composite board
Material B7.
Embodiment 16
The present embodiment and the difference of embodiment 15 are, carry out by the paving mode of A-6/A-5/A-6/A-5/A-6 continuous
Heating and mould pressing, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B8.
Embodiment 17
The present embodiment and the difference of embodiment 15 are, by A-6/ (A-6)3The paving mode of/A-6 carries out laser heating mould
Pressure, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B9.
Embodiment 18
The present embodiment and the difference of embodiment 9 are, A-7, A-8 composite sheet are taken, by A-8/A-7/A-7/A-8/A-7/
The paving mode of A-7/A-8 carries out laser heating molding, cooling traction, trimming, cutting packaging, obtains PA6/ carbon fiber composite board
Material B10.
Embodiment 19
The present embodiment and the difference of embodiment 18 are, carry out by the paving mode of A-8/A-7/A-8/A-7/A-8 continuous
Heating and mould pressing, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B11.
Embodiment 20
The present embodiment and the difference of embodiment 18 are, by A-8/ (A-8)3The paving mode of/A-8 carries out laser heating mould
Pressure, cooling traction, trimming, cutting packaging, obtain PA6/ carbon fiber composite board B12.
The PA6/ carbon fiber composite board B1-B12 that embodiment 9-20 is obtained is tested, test result is shown in Table 1.
The detection project and standard of PA6/ carbon fiber composite board of the present invention are as follows:
Tensile strength (MPa): ASTM D638-2014；
Bending strength (MPa): ASTM D790-2007；
Bending modulus (MPa): ASTM D790-2007；
Impact strength (kJ/m2): ASTM D756-1993；
Heat distortion temperature (DEG C): ASTMD648
The performance of table 1PA6/ carbon fiber composite board
From table 1 it follows that PA6/ carbon fiber composite board B1-B12 all has preferable mechanical property.
Fibre reinforced successive reaction of the invention forms the characteristics of nylon composite materials preparation method and is: by oneself
Amide activated monomer quickly infiltrates carbon fibre fabric in reaction die head, and fast reaction forms big point between carbon fibre fabric
Sub- nylon 6/poly closes object, to prepare carbon fiber high degree of dispersion, nylon 6/poly closes the PA6/ carbon fiber that object sufficiently coats carbon fiber
Composite sheet；The continuous lamination of composite sheet is laid with molding preparation PA6/ carbon fiber composite board, it can be achieved that large-scale production；
The composite board have high intensity, high-modulus, light specific gravity, can secondary operation form, can be used for manufacturing automobile, rail vehicle
Body component can be used for manufacture laptop, desktop computer, phone housing, suitcase, briefcase and bag.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those skilled in the art to which the present invention belongs, it is not taking off
Under the premise of from present inventive concept, several equivalent substitute or obvious modifications can also be made, and performance or use is identical, all answered
When being considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of fibre reinforced successive reaction molding nylon composite materials, which is characterized in that including walking as follows
It is rapid:
The dehydration of S1, caprolactam；
The preparation of S2, caprolactam activated monomer: being separately added into dewatered caprolactam into A, B activation kettle, and to the A
Catalyst is added in activation kettle, co-catalyst is added into the B activation kettle, obtains A material and B material；
The preparation of S3, PA6/ carbon fiber composite sheet: by A material and B material, 1:1 is mixed after mixing by volume
Liquid is closed, and is continuously conveyed respectively with carbon fibre fabric to reacting and carries out reaction solidification in die head, is obtained through traction, cooling, winding
PA6/ carbon fiber composite sheet.
2. preparation method as described in claim 1, which is characterized in that the catalyst is NaOH, KOH, Na2CO3Or
NaHCO3, additional amount is 0.5~2.0%.
3. preparation method as described in claim 1, which is characterized in that the co-catalyst be toluene di-isocyanate(TDI) (TDI),
Methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or
Person's triphenylmethane triisocyanate (TTI), additional amount are 1.0~5.0%.
4. preparation method as described in claim 1, which is characterized in that the reaction temperature in the step S2 in A, B activation kettle
Respectively 110~160 DEG C, negative pressure is -0.05~-0.1MPa, and the reaction time is 20~40min.
5. preparation method as described in claim 1, which is characterized in that in the step S3 conveying capacity of mixed liquor be 0.5~
5.0kg/min, curing reaction temperature are 140~200 DEG C, and the curing reaction time is 2~10min；The carbon fibre fabric it is defeated
The amount of sending is 0.5~12kg/min, and draw-down rate is 1~4m/min, and residence time of the material in reaction die head is 2~10min.
6. preparation method as described in claim 1, which is characterized in that the carbon fibre fabric be plain weave or twills,
Wide cut is 400~1600mm, and grammes per square metre is 200~2000g/m2。
7. preparation method as described in claim 1, which is characterized in that in the carbon fibre fabric grade of fiber be T300~
T1000, specification are 6~24K.
8. such as the described in any item preparation methods of claim 1-7, which is characterized in that further include that the PA6/ carbon fiber is compound
The molding of sheet material continuous mould pressing, obtains composite board, and the continuous mould pressing moulding process includes unreeling, drawing, preheating, being molded, is cold
But, trimming, cutting and packaging, wherein hauling speed is 1~3m/min, and preheating temperature is 140~180 DEG C, and molding temperature is
200~250 DEG C, molding pressure is 1~5MPa, and clamp time is 1~10min, and cooling temperature is 60~100 DEG C, cooling time
For 2~10min.
9. a kind of fibre reinforced successive reaction molding nylon such as the described in any item preparation method preparations of claim 1-8 is multiple
Condensation material.
10. a kind of fibre reinforced successive reaction molding nylon composite materials as claimed in claim 9 are in automobile, rail traffic
Application in terms of car body component, laptop computer, desktop computer, suitcase, briefcase or bag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810662591.7A CN108948345A (en) | 2018-06-25 | 2018-06-25 | Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810662591.7A CN108948345A (en) | 2018-06-25 | 2018-06-25 | Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108948345A true CN108948345A (en) | 2018-12-07 |
Family
ID=64486485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810662591.7A Pending CN108948345A (en) | 2018-06-25 | 2018-06-25 | Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108948345A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625436A (en) * | 2020-11-23 | 2021-04-09 | 安徽胜利精密制造科技有限公司 | Notebook shell processing raw material and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615215A (en) * | 2001-12-20 | 2005-05-11 | 埃姆斯化学品有限公司 | Method for producing composite materials using a thermoplastic matrix |
| CN1640936A (en) * | 2004-01-02 | 2005-07-20 | 上海杰事杰新材料股份有限公司 | Continuous long-fiber reaction-reinforced nylon resin and its making method |
| CN101525433A (en) * | 2009-04-03 | 2009-09-09 | 株洲时代新材料科技股份有限公司 | Fiber-reinforced modified-reaction injection-molding nylon sheet and preparation method thereof |
| CN102922751A (en) * | 2012-11-21 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Resin transfer molding glue injection machine for continuous fiber reinforced nylon 6 composite material |
| CN103534082A (en) * | 2011-03-03 | 2014-01-22 | 巴斯夫欧洲公司 | Method for producing fiber-reinforced, flat semi-finished products containing a polyamide matrix |
| CN103847053A (en) * | 2012-12-07 | 2014-06-11 | 苏州荣昌复合材料有限公司 | Method and device for forming continuous long fiber reinforced MC (Monomer Casting) nylon plate material |
| CN104693591A (en) * | 2013-12-06 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Continuous fiber reinforced thermoplastic resin composite material safety-shoe protective toecap and preparation method thereof |
| CN107033589A (en) * | 2017-06-12 | 2017-08-11 | 江苏科技大学 | A kind of preparation method of the composite of continuous fibre reinforced nylon 6 |
| CN107383364A (en) * | 2017-07-27 | 2017-11-24 | 株洲时代新材料科技股份有限公司 | A kind of protection means for automobile material and its preparation technology |
| CN107548339A (en) * | 2015-02-23 | 2018-01-05 | 巴斯夫欧洲公司 | The preparation method of fibre-reinforced components or semi-finished product |
-
2018
- 2018-06-25 CN CN201810662591.7A patent/CN108948345A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615215A (en) * | 2001-12-20 | 2005-05-11 | 埃姆斯化学品有限公司 | Method for producing composite materials using a thermoplastic matrix |
| CN1640936A (en) * | 2004-01-02 | 2005-07-20 | 上海杰事杰新材料股份有限公司 | Continuous long-fiber reaction-reinforced nylon resin and its making method |
| CN101525433A (en) * | 2009-04-03 | 2009-09-09 | 株洲时代新材料科技股份有限公司 | Fiber-reinforced modified-reaction injection-molding nylon sheet and preparation method thereof |
| CN103534082A (en) * | 2011-03-03 | 2014-01-22 | 巴斯夫欧洲公司 | Method for producing fiber-reinforced, flat semi-finished products containing a polyamide matrix |
| CN102922751A (en) * | 2012-11-21 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Resin transfer molding glue injection machine for continuous fiber reinforced nylon 6 composite material |
| CN103847053A (en) * | 2012-12-07 | 2014-06-11 | 苏州荣昌复合材料有限公司 | Method and device for forming continuous long fiber reinforced MC (Monomer Casting) nylon plate material |
| CN104693591A (en) * | 2013-12-06 | 2015-06-10 | 上海杰事杰新材料(集团)股份有限公司 | Continuous fiber reinforced thermoplastic resin composite material safety-shoe protective toecap and preparation method thereof |
| CN107548339A (en) * | 2015-02-23 | 2018-01-05 | 巴斯夫欧洲公司 | The preparation method of fibre-reinforced components or semi-finished product |
| CN107033589A (en) * | 2017-06-12 | 2017-08-11 | 江苏科技大学 | A kind of preparation method of the composite of continuous fibre reinforced nylon 6 |
| CN107383364A (en) * | 2017-07-27 | 2017-11-24 | 株洲时代新材料科技股份有限公司 | A kind of protection means for automobile material and its preparation technology |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625436A (en) * | 2020-11-23 | 2021-04-09 | 安徽胜利精密制造科技有限公司 | Notebook shell processing raw material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798711B (en) | Non-breakpoint direct spinning continuous production method of ultra-high molecular weight polyethylene fiber | |
| CN103802324B (en) | Composite storage apparatus and manufacturing process thereof | |
| CN111205596A (en) | Epoxy chopped carbon fiber mat prepreg for rapid prototyping and production process thereof | |
| CN102532872B (en) | Pultrusion production process for nylon-based fiber reinforced thermo plastics | |
| CN102173153A (en) | Preparation method of fiber reinforced composite material | |
| CN107033589B (en) | A kind of preparation method of 6 composite material of continuous fibre reinforced nylon | |
| CN102617984A (en) | Modified epoxy resin base material and modified epoxy resin matrix composite material | |
| CN102924741A (en) | Method for enhancing surface abrasion resistance of liquid molding composite material | |
| CN104017334A (en) | High-modulus sheet molding compound (SMC) and production method thereof | |
| CN106626439A (en) | Preparation method of low-cost and large-tow 48K carbon fiber preimpregnated cloth and composite material thereof | |
| CN108948345A (en) | Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application | |
| CN108277546A (en) | A kind of preparation method of anti-cutting polyethylene fibre | |
| KR102591171B1 (en) | Method for making fiber-reinforced polyamide matrix composite materials from reactive prepolymer precursor compositions | |
| CN114131785A (en) | Preparation method of high-temperature-resistant thermoplastic composite material unidirectional prepreg tape | |
| CN105482141A (en) | Continuous fiber reinforced thermosetting resin matrix composite material and preparation method thereof | |
| CN102558591B (en) | Preparation method of fiber-reinforced PCBT thermoplastic composite material bottom plate for electric vehicle | |
| CN106948210A (en) | A kind of method that foaming process prepares fibre reinforced composites | |
| CN103290505B (en) | Method for preparing high-strength high-modulus polyvinyl alcohol fibers | |
| CN105062017A (en) | Preparation method of carbon fiber enhanced polylactic acid composite product | |
| CN1284741C (en) | Reinforced concrete structure plate and its prepn process | |
| CN105619837A (en) | Pre-oxidized fiber reinforced thermoplastic composite material product for automobile and preparation method thereof | |
| CN106626535B (en) | Mono- polymer composites of a kind of high microsteping volume content PHBV and preparation method thereof | |
| Kanhere et al. | Carbon and glass fiber reinforced thermoplastic matrix composites | |
| CN100366419C (en) | Production for gradient firilla reinforced polycarbonate composite materials by solution immersion | |
| CN205529242U (en) | Fiber reinforcement thermoplasticity combined material is with mixing fine yarn |
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: 20181207 |