CN103724813B - Continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material and preparation method - Google Patents

Continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material and preparation method Download PDF

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CN103724813B
CN103724813B CN201210393343.XA CN201210393343A CN103724813B CN 103724813 B CN103724813 B CN 103724813B CN 201210393343 A CN201210393343 A CN 201210393343A CN 103724813 B CN103724813 B CN 103724813B
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continuous fiber
parts
retardant
composite material
fiber
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CN103724813A (en
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康楠
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LIAONING LIAOJIE TECHNOLOGY Co Ltd
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LIAONING LIAOJIE TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/18—Separating or spreading
    • 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
    • C08K2201/017—Additives being an antistatic agent
    • 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
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • 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
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Abstract

The invention belongs to field of high polymer material processing, it is related to a kind of continuous fiber reinforced thermoplastic composite material and preparation method thereof.The continuous fiber reinforced thermoplastic composite material is made of the component comprising following parts by weight：45 55 parts of modified resin, 45 55 parts of continuous fiber.Compared with the prior art, this method overcomes the mobility of resin and the wellability with fiber, and not only intensity is high for the prepreg produced, and has good anti-flammability and antistatic property, has higher applicability.

Description

Continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material and preparation method
Technical field
The invention belongs to field of high polymer material processing, it is related to a kind of continuous fiber reinforced thermoplastic composite material and its system Preparation Method.
Background technology
Continuous fiber reinforced thermoplastic prepreg composite China's automobile, machinery, electronics, electrical, chemical industry, building materials and The fields such as military project are applied widely, instead of a large amount of non-ferrous metal component, or even instead of some ferrous metal parts, As Chinese patent CN102295792A discloses a kind of continuous fiber enhanced thermoplastic antiflaming presoaking belt composite material and its preparation Method is made of modified resin and continuous fiber, although the composite material flame retardant property and shock resistance are all fine, Application in China coal industry is but restricted, and reason is mainly that engineering plastic surface resistance is big, easy to produce static electricity, such as Fruit using necessarily will produce danger, therefore develops the MT113-85 that flame-retardant and anti-static performance compound coal portion formulates in underground coal mine Standard《Underground mine use nonmetallic materials inspection specification》It is required that continuous lod prepreg composite it is imperative.
In continuous lod prepreg composite, since fiber content is higher, prepreg it is fire-retardant, it is antistatic and carry High material mechanical performance is the key of Materials.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide it is a kind of it is fire-retardant, antistatic, High intensity continuous fiber reinforced thermoplastic composite material and preparation method thereof.
To achieve the above object, the present invention uses following technical scheme：
A kind of continuous fiber reinforced thermoplastic composite material is made of the component comprising following parts by weight：
45-55 parts of modified resin,
45-55 parts of continuous fiber.
One kind in glass fibre, carbon fiber, boron fibre or aromatic polyamide fibre of the continuous fiber or More than one.
The continuous fiber is by the continuous fiber of tension force, fiber without abrasion expansion processing, through overtension control The surface density reduction by 15 ~ 55% of system and the continuous fiber handled without abrasion expansion, the specific steps are continuous fiber is passed through textile strand Frame introduces fiber and opens up silk system, and fiber passes through continuous rolling, carries out tension adjustment so that fiber is opened up on the original basis Width, exhibition is thin to be obtained by tension force, continuous fiber of the fiber without abrasion expansion processing.
In a preferred embodiment, untreated glass fibre surface density is 1200g/m2, through overtension control It makes and is reduced to 800-1000g/m without glass fibre surface density after abrasion expansion processing2。
In another preferred embodiment, the surface density of untreated carbon fiber is 300g/m2, through overtension control After making and being handled without abrasion expansion, the surface density of carbon fiber is reduced to 140-180g/m2。
The modified resin is made of the component including following parts by weight：
55-60 parts of thermoplastic resin,
30-40 parts of fire retardant,
3-5 parts of grafting agent,
1-3 parts of coupling agent,
5-10 parts of antistatic agent,
0.2-0.4 parts of antioxidant,
0.5-1 parts of light stabilizer.
One or more of the thermoplasticity modeling fat in polyolefin, polyamide or makrolon.
The polyolefin is copolymer polypropylene, and the polyamide is selected from polyamide 6, polyamide 66, polyamide 1010 Or the one or more in polyamide 1212.
The fire retardant is the one or more in halogenated flame retardant or phosphorus flame retardant；
One or more of the halogenated flame retardant in decabromodiphenylethane or vinyl chloride；
The phosphorus flame retardant is selected from three（2,2- bis- bromomethyl -3- bromopropyl phosphonates）, resorcinol two banks fat （RDP）, bisphenol-A two（Diphenyl）Phosphonates（BPAPP）Or the one or more in red phosphorus.
The grafting agent is polypropylene grafted maleic anhydride.
The coupling agent is selected from Y- aminopropyl triethoxysilanes, Y- glycydoxy trimethoxy silicon Alkane, the one or more in Y- methacryloxypropyl front three model machine silane.
The antistatic agent is the agent of polymer electrolyte permanent anti-static or conductive agglomerate antistatic agent.
The polymer electrolyte permanent anti-static agent is selected from the copolymer of ethylene oxide and its derivative, the preferred ring Oxidative ethane derivative is monoethylene glycol amine, diethyleneglycolamin or triethylene glycol amine.
The conductive agglomerate is conductive black master batch；The conductive black master batch be superconductive carbon black, resin and Processing aid by master batch made of blending extrusion, the preferably DH801 of Qingdao Wei Dongke rubber and plastics Science and Technology Ltd. production, M2011U etc..
The antioxidant is selected from four（β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid）Pentaerythritol ester, three（2.4- Di-tert-butyl-phenyl）It is phosphite ester, 2,6- three-level butyl -4- methylphenols, double（3,5- three-level butyl -4- hydroxy phenyls）Sulphur Ether, N, N '-is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or thio-2 acid dibasic acid esters in one kind Or more than one.
It is steady that the light stabilizer is selected from salicylic acid lipid light stabilizer, hindered amine light stabilizer or benzophenone light Determine agent.
The salicylic acid lipid light stabilizer is divided into septichen phenyl ester.
The hindered amine light stabilizer is N, N'- is bis--(2,2,6,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines Or 1,1,3,3- tetramethyl butylamine.
The benzophenone light stabilizer is 2-hydroxy-4-n-octoxybenzophenone.
A kind of preparation method of above-mentioned continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, this method includes following Step：
（1）55-60 parts of thermoplastic, 30-40 parts of fire retardant, 3-5 parts of grafting agent, coupling agent are weighed by above-mentioned parts by weight 1-3 parts, 5-10 parts of antistatic agent, 0.2-0.4 parts of antioxidant, 0.5-1 parts of light stabilizer after fully mixed, pass through twin-screw Extruder carries out extruding pelletization, and modified resin is made；
（2）Continuous fiber is introduced into fiber by creel of weaving and opens up silk system, fiber passes through continuous rolling, carries out tension tune Section so that for fiber on the original basis into line broadening, exhibition is thin, is then preheated by heating system, after preheating Continuous fiber by tension-adjusting gear carry out second of tension adjustment, obtain pretreated continuous fiber, preheating temperature It is 180-200 DEG C, preheating time 3-5s；
（3）The modified resin of 45-55 parts by weight is added in extruder, by interlocking, retractable double extrusion die groups are squeezed Go out, the pretreated continuous fiber with 55-45 parts by weight is infiltrated；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 50-70 DEG C；
（5）By cooling continuous fiber belt by flattening, it is fire-retardant anti-quiet to wind obtained continuous fiber reinforced thermoplastic for cutting edge Composite.
The step（1）In, pre-heating temperature is 180-200 DEG C, preheating time 3-5s.
The step（2）Middle exhibition silk system is realized for the different mirror-smooth roller of several roller diameters to continuous fiber Broadening passes through the spacing of regulating roller, cladding area and cladding angle so that fiber moves freely between regulating roller, arranges again Row are physical change, can be by fiber exhibition silk to 2 ~ 3 times of former width in the case where ensureing fibre property.
The step（3）Middle extruder is that single extruder is fed double extrusion dies by runner.
The step（5）Continuous fiber reinforced thermoplastic composite material thickness obtained is 0.2-0.27mm.
The invention has the advantages that：
Compared with prior art, the present invention sets about in terms of Resin Flow and the fine infiltration of equipment exhibition, passes through auxiliary agent Addition increase the mobility of resin, exhibition silk system makes fiber open up wider thinner, improves effect of impregnation, solve leaching Stain is difficult so that the fiber architecture in prepreg exists with and without dry yarn phenomenon, and the thermoplastic composite produced has Excellent in mechanical performance, intensity is high, fire-retardant, anlistatig advantage.
Simultaneously permanent antistatic agent, degree of scatter and dispersion of the antistatic agent in resin are added in formula makes State has a significant impact resin antistatic property.In the present invention, permanent antistatic agent mainly forms core shell knot in parent Structure, and electrostatic charge is revealed as access, permanent antistatic agent is mainly distributed on product in the form of fine stratiform or tendon shape Surface, and it is less in central part and mainly exist with graininess.
The present invention passes through shear rate and processing temperature control by the way that grafting agent is added using twin-screw blending and modifying technique The melt viscosity difference and ratio of viscosities of matrix resin and permanent antistatic agent processed, improve permanent antistatic agent and matrix resin Compatibility.In use, the mobility and its processing that will not influence resin itself because of the dosage for increasing antistatic agent are special Property.
Description of the drawings
Fig. 1 is the process flow chart in the embodiment of the present invention.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention will be further described, unless otherwise specified, the component in embodiment It is parts by weight.
Part material source used is shown in Table 1 in embodiment.
Table 1
Embodiment 1
A kind of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, preparation process are as shown in Figure 1：
（1）Weigh by weight 55 parts of polypropylene, 30 parts of flame retardant decabromodiphenylethane, 5 parts of grafting agent 9903b, 10 parts Conductive black, 0.2 part of irgasfos 168,0.2 part of antioxidant 1010,1 part of light stabilizer, 944,1 parts of Kh550 parts of coupling agents are through overcharging After dividing mixing, passes through double screw extruder and carry out extruding pelletization, modified resin is made.
（2）Continuous glass fibre is introduced into fiber by creel of weaving and opens up silk system, fiber passes through continuous rolling, opened Power is adjusted so that for fiber on the original basis into line broadening, exhibition is thin, is then preheated by infrared baking oven, obtains pre- place The continuous fiber managed, preheating temperature are 180 DEG C, and preheating time 3s, the glass after preheating is filled by tension adjustment It sets, adjusts tension to ensure product last uniformity and invariance.
Wherein exhibition silk system is the different mirror-smooth roller of multiple roller diameters come the broadening for realizing to continuous fiber, passes through adjusting The spacing cladding area and cladding angle of roller so that fiber moves freely between regulating roller, rearranges, and is physical change, Precursor width is 3.5mm, surface density 1200g/m2, width becomes 7mm after opening up silk（By fiber exhibition silk to 2 times of former width）, Surface density is 800g/m2；
（3）The modified resin of 45 parts by weight is added, double extrusion dies are fed by runner by single extruder Extruder in, by interlocking, retractable double extrusion die groups squeeze out, the pretreated continuous glass fibre with 55 parts by weight Row infiltration；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 70 DEG C or less；
（5）By cooling continuous fiber belt by flattening, cutting edge winds the continuous fibre for being made that thickness is 0.22 ~ 0.23mm Dimension enhancing thermoplastic flame-proof anti-static composite material.
Embodiment 2
A kind of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, prepares according to the following steps：
（1）Weigh by weight 60 parts of polyamide 6s, 30 parts of red phosphorus, 3.5 parts of grafting agent kh550,0.3 part of antioxidant 1098, 0.1 part of antioxidant 1010,1 part of light stabilizer, 944,5 parts of antistatic agent SAS93,3 parts of coupling agent Y- aminopropyl triethoxysilanes After fully mixed, extruding pelletization is carried out by double screw extruder, modified resin is made；
（2）Continuous carbon fibre is introduced into fiber by creel of weaving and opens up silk system, carbon fiber passes through continuous rolling, opened Power is adjusted so that for fiber on the original basis into line broadening, exhibition is thin, is then preheated by infrared baking oven, obtains pre- place The continuous fiber managed, preheating temperature are 180 DEG C, preheating time 3-5s, and the carbon fiber after preheating passes through tension tune Regulating device adjusts tension to ensure product last uniformity and invariance；
Wherein exhibition silk system is the different mirror-smooth roller of multiple roller diameters come the broadening for realizing to continuous fiber, passes through adjusting The spacing cladding area and cladding angle of roller so that fiber moves freely between regulating roller, rearranges, and is physical change, Precursor width is 5mm, surface density 300g/m2, width becomes 15mm after opening up silk（By fiber exhibition silk to 3 times of former width）, face Density is 140g/m2；
（3）The modified resin of 55 parts by weight is added, double extrusion dies are fed by runner by single extruder Extruder in, by interlocking, retractable double extrusion die groups squeeze out, the pretreated continuous carbon fibre row with 45 parts by weight Infiltration；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 70 DEG C or less；
（5）By cooling continuous fiber belt by flattening, cutting edge winds the continuous fibre for being made that thickness is 0.25 ~ 0.26mm Dimension enhancing thermoplastic flame-proof anti-static composite material.
Embodiment 3
A kind of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, prepares according to the following steps：
（1）60 parts of thermoplastic polyamide 1010 is weighed by weight, fire retardant is 20 parts（Three（2,2- dibromo first Base -3- bromopropyl phosphonates）With 20 parts of resorcinol two banks fat parts, 3 parts of grafting agent polypropylene grafted maleic anhydride, coupling agents 3 parts of Y- aminopropyl triethoxysilanes, 5 parts of antistatic agent ethylene oxide, antioxidant are double（3,5- three-level butyl -4- hydroxy phenyls） 0.2 part of thioether, 0.5 part of light stabilizer septichen phenyl ester after fully mixed, are squeezed by double screw extruder Go out to be granulated, modified resin is made；
（2）By continuous fiber（Aromatic polyamide fibre）Fiber is introduced by creel of weaving and opens up silk system, and fiber passes through Continuous rolling carries out tension adjustment so that for fiber on the original basis into line broadening, exhibition is thin, then passes through heating system and carries out Preheating, the continuous fiber after preheating carry out second of tension adjustment by tension-adjusting gear, obtain pretreated Continuous fiber, preheating temperature be 200 DEG C, preheating time 5s；
The exhibition silk system is the different mirror-smooth roller of multiple roller diameters come the broadening for realizing to continuous fiber, passes through tune Save the spacing cladding area and cladding angle of roller so that fiber moves freely between regulating roller, rearranges, and becomes for physics Change.Precursor width is 8mm, surface density 200g/m2, width becomes 16mm after opening up silk（By fiber exhibition silk to 2 times of former width）, Surface density is 90g/m2, surface density reduction by 55%；
（3）The modified resin of 50 parts by weight is added, double extrusion dies are carried out in feed extruder by runner, led to It crosses staggeredly retractable double extrusion die groups to squeeze out, the pretreated continuous fiber with 50 parts by weight is infiltrated；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 50 DEG C；
（5）By cooling continuous fiber belt by flattening, cutting edge, it is 0.2mm continuous lod heat to wind and thickness is made Plasticity flame-retardant and anti-static composite material.
Embodiment 4
A kind of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, prepares according to the following steps：
（1）20 parts of 58 parts of polyamide 1212 of thermoplastic, fire retardant bisphenol-As two are weighed by weight（Diphenyl）Phosphonic acids Fat and 15 parts of resorcinol two banks fat, 4 parts of grafting agent polypropylene grafted maleic anhydride, coupling agent Y- methacryloxies third 2 parts, 7 parts antistatic agent conductive black master batch SH801, antioxidant N, N'- of base front three model machine silane are bis--(3- (bis- tertiary fourths of 3,5- Base -4- hydroxy phenyls) propiono) 0.3 part of hexamethylene diamine, 0.8 part of light stabilizer 2-hydroxy-4-n-octoxybenzophenone is through overcharging After dividing mixing, passes through double screw extruder and carry out extruding pelletization, modified resin is made；
（2）By continuous fiber（Aromatic polyamide fibre）Fiber is introduced by creel of weaving and opens up silk system, and fiber passes through Continuous rolling carries out tension adjustment so that for fiber on the original basis into line broadening, exhibition is thin, then passes through heating system and carries out Preheating, the continuous fiber after preheating carry out second of tension adjustment by tension-adjusting gear, obtain pretreated Continuous fiber, preheating temperature be 190 DEG C, preheating time 4s；
The exhibition silk system is the different mirror-smooth roller of multiple roller diameters come the broadening for realizing to continuous fiber, passes through tune Save the spacing cladding area and cladding angle of roller so that fiber moves freely between regulating roller, rearranges, and becomes for physics Change, precursor width is 8mm, surface density 200g/m2, width becomes 16mm after opening up silk（By fiber exhibition silk to 2 times of former width）, Surface density is 170g/m2, surface density reduction by 15%；
（3）The modified resin of 50 parts by weight is added, double extrusion dies are carried out in feed extruder by runner, led to It crosses staggeredly retractable double extrusion die groups to squeeze out, the pretreated continuous fiber with 50 parts by weight is infiltrated；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 60 DEG C；
（5）By cooling continuous fiber belt by flattening, cutting edge, it is 0.27mm continuous lod heat to wind and thickness is made Plasticity flame-retardant and anti-static composite material.
Embodiment 5
A kind of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, prepares according to the following steps：
（1）It weighs by weight between 58 parts of makrolon of thermoplastic, 20 parts of decabromodiphenylethane of fire retardant and 20 parts Benzenediol two banks fat, 4 parts of grafting agent polypropylene grafted maleic anhydride, coupling agent Y- methacryloxypropyl front three model machines 3 parts, 8 parts antistatic agent conductive black master batch SH801, antioxidant N, N'- of silane are bis--(3- (3,5- di-t-butyl -4- hydroxy benzenes Base) propiono) 0.3 part of hexamethylene diamine, 0.8 part of light stabilizer 2-hydroxy-4-n-octoxybenzophenone after fully mixed, lead to It crosses double screw extruder and carries out extruding pelletization, modified resin is made；
（2）By continuous fiber（Glass fibre）Fiber, which is introduced, by creel of weaving opens up silk system, fiber passes through continuous rolling, Carry out tension adjustment so that for fiber on the original basis into line broadening, exhibition is thin, is then preheated by heating system, passes through The continuous fiber crossed after preheating carries out second of tension adjustment by tension-adjusting gear, obtains pretreated continuous fibre Dimension, preheating temperature are 190 DEG C, preheating time 4s；
The exhibition silk system is the different mirror-smooth roller of multiple roller diameters come the broadening for realizing to continuous fiber, passes through tune Save the spacing cladding area and cladding angle of roller so that fiber moves freely between regulating roller, rearranges, and becomes for physics Change, precursor width is 8mm, surface density 1200g/m2, width becomes 22mm after opening up silk（Fiber is opened up into silk to the 2.75 of former width Times）, surface density 840g/m2, surface density reduction by 30%；
（3）The modified resin of 50 parts by weight is added, double extrusion dies are carried out in feed extruder by runner, led to It crosses staggeredly retractable double extrusion die groups to squeeze out, the pretreated continuous fiber with 50 parts by weight is infiltrated；
（4）Continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming It is cooled down by cold pressing roller, is cooled to 60 DEG C；
（5）By cooling continuous fiber belt by flattening, cutting edge, it is 0.23mm continuous lod heat to wind and thickness is made Plasticity flame-retardant and anti-static composite material.
Continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material obtained in embodiment 1 ~ 5 is tested for the property, Test result is shown in Table 2
Table 2
Tensile strength (MPa) Fire-retardant rank Surface resistivity（Ω）
Testing standard ASTMD 638 UL94 GB/T 15662
Embodiment 1 245 V0 1.3*105
Embodiment 2 546 V0 2.4*105
Embodiment 3 532 V0 2.0*106
Embodiment 4 488 V0 2.1*106
Embodiment 5 522 V0 2.3*107
From test result as can be seen that the resistance of continuous fiber reinforced thermolplastic flame-retardant and anti-static composite material prepared by the present invention It is good to fire performance, reaches UL94-V0 ranks, is provided simultaneously with preferable tensile strength and antistatic property.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be Within protection scope of the present invention.

Claims (4)

1. a kind of preparation method of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material, it is characterised in that：It include with Lower step：
(1) 55-60 parts of thermoplastic resin, 30-40 parts of fire retardant, 3-5 parts of grafting agent, 1-3 parts of coupling agent, antistatic agent 5- are weighed 0.5-1 parts of 10 parts, 0.2-0.4 parts of antioxidant and light stabilizer after fully mixed, are squeezed out by double screw extruder It is granulated, modified resin is made；
(2) continuous fiber is introduced into fiber by creel of weaving and opens up silk system, continuous fiber passes through continuous rolling, carries out tension tune Section so that for continuous fiber on the original basis into line broadening, exhibition is thin, is then preheated by heating system, by pre-add Continuous fiber after heat carries out second of tension adjustment by tension-adjusting gear, obtains pretreated continuous fiber；
(3) 45-55 parts of modified resins are added in extruder, by interlocking, retractable double extrusion die groups squeeze out, with 45-55 parts Pretreated continuous fiber is infiltrated；
(4) continuous fiber after dipping is imported into impregnated calender roll set and carries out roll-in, the continuous fiber belt after roll-forming is passed through Cold pressing roller cools down, and is cooled to 50-70 DEG C, obtains cooling continuous fiber belt；
(5) by cooling continuous fiber belt by flattening, it is multiple to wind obtained continuous fiber reinforced thermoplastic flame-retardant and anti-static for cutting edge Condensation material；
Fiber exhibition silk system is realized for several roller diameters different mirror-smooth rollers to continuous fiber in the step (2) Broadening, by the spacing, cladding area and the cladding angle that adjust mirror-smooth roller so that continuous fiber is adjusting mirror-smooth roller Between move freely, rearrange, continuous fiber can be opened up silk in the case where ensureing continuous fiber performance for physical change To 2~3 times of former width；
The thickness of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material obtained is 0.2- in the step (5) 0.27mm；
The continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material includes the component of following parts by weight：
45-55 parts of modified resin,
45-55 parts of pretreated continuous fiber；
The pretreated continuous fiber is selected from one or more of glass fibre or carbon fiber；
The surface density of untreated glass fibre is 1200g/m2, the surface density of pretreated glass fibre is reduced to 800-1000g/m2；
The surface density of untreated carbon fiber is 300g/m2, the surface density of pretreated carbon fiber is reduced to 140- 180g/m2；
The modified resin includes the component of following parts by weight：
The thermoplastic resin is selected from one or more of polyolefin, polyamide or makrolon；
The polyolefin is copolymer polypropylene；The polyamide is polyamide 1010；
The fire retardant is bisphenol-A two (diphenyl) phosphate；
The grafting agent is polypropylene grafted maleic anhydride；
The coupling agent is selected from Y- glycidyl ether oxypropyltrimethoxysilanes or Y- methacryloxypropyls three One or more of methoxy silane；
The antistatic agent is selected from superconductive carbon black, resin and processing aid by master batch made of blending extrusion；
The light stabilizer is selected from salicylate light stabilizer, hindered amine light stabilizer or benzophenone light and stablizes Agent；
The salicylate light stabilizer is septichen phenyl ester；
The hindered amine light stabilizer is selected from N, N'- is bis--(2,2,6,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines or 1,1,3,3- tetramethyl butylamine；
The benzophenone light stabilizer is 2-hydroxy-4-n-octoxybenzophenone.
2. the preparation method of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material according to claim 1, special Sign is：The antioxidant is selected from four (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol esters, three (2,4- Di-tert-butyl-phenyl) phosphite ester, 2,6- three-level butyl -4- methylphenols, bis- (3,5- three-level butyl -4- hydroxy phenyls) sulphur Ether, N, N'- is bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine or thio-2 acid dibasic acid esters in one kind More than.
3. the preparation method of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material according to claim 1, special Sign is：In the step (2), pre-warmed temperature is 180-200 DEG C, and the pre-warmed time is 3-5s.
4. the preparation method of continuous fiber reinforced thermoplastic flame-retardant and anti-static composite material according to claim 1, special Sign is：Extruder is that single extruder is fed double extrusion dies by runner in the step (3).
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