CN100473689C - Continuous fibre reinforced thermoplastic composite material - Google Patents
Continuous fibre reinforced thermoplastic composite material Download PDFInfo
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- CN100473689C CN100473689C CNB031153542A CN03115354A CN100473689C CN 100473689 C CN100473689 C CN 100473689C CN B031153542 A CNB031153542 A CN B031153542A CN 03115354 A CN03115354 A CN 03115354A CN 100473689 C CN100473689 C CN 100473689C
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Abstract
The present invention provides one kind of continuous fiber reinforced thermoplastic composite material including thermoplastic resin as base material and continuous fiber distributed in the base material. The preparation process of the said composite material is also provided and includes providing continuous fiber, providing monomer with viscosity of 0.1-5 Pa.s, soaking the continuous fiber with the monomer, polymerizing the monomer to form the composition prepolymer, and soaking the continuous fiber with the prepolymer to form the composite material.
Description
Invention field
The present invention relates to continuous fibre enhanced thermoplastic composite, and relate to the preparation method of this matrix material.
Technical background
Existing continuous fibre reinforced composite materials mostly is continuous fibre enhanced thermosetting resin (as unsaturated polyester, Resins, epoxy an etc.) matrix material.Though this material has good performances such as intensity, the characteristic that its maximum shortcoming is a thermosetting material determines it to be difficult to recycle and reuse.Thereby be unfavorable for environment protection.
Because thermoplastic resin can reclaim the recycling of processing back, therefore need adopt the matrix material of being made by thermoplastic resin in some purposes.For the matrix material of thermoplastic resin, mostly coat at present by powder absorption, melt impregnation, film and method such as fiber sprinning blend make (for example, referring to United States Patent (USP) U.S4,640,861 and U.S 4,828,776).
Existing method is successful for the fibre composite of preparation resin-coated.But also there are many defectives in it, for example, existing method can not make thermoplastic resin impregnated in the tiny space that forms between fiber and the fiber, and can only be coated on the outside of fiber, be non-and the opposed side of another fiber, make fiber easily reel off raw silk from cocoons or fluff and influence the use of material.With the fiber rope is example, fiber rope generally forms by the multiply fiber is stranded, because the gap that forms between the stranded fiber of each strand is minimum, therefore existing method can not make thermoplastic resin fill this tiny space, and can only be coated on the outside surface of fiber rope (be described non-with the opposed side of another fiber) thus influence the intensity of the finished product.Another defective is to prepare cloth or fibrefelt reinforced composite materials, because resin is difficult to or can not be impregnated into the inside of cloth, fibrefelt, has limited the further application of this method greatly.
The United States Patent (USP) U.S 5,891,560 of Dow Chemical company discloses with can be at high temperature degradation and can be at the polyurethane preparation continuous long fiber enhanced thermoplastic composite of low temperature polymerization.But the kind of this material is limited, and the viscosity of resin can not regulated at will, is difficult to be widely used.
United States Patent (USP) 5,935,508 and European patent EP 0,290,849 the photopolymerization continuous fiber reinforced thermoplastic composite material that causes with UV-light is disclosed.But since the restriction of the penetrativity of light, the goods that very difficult preparation is thicker, and polyreaction also is difficult to carry out fully.
United States Patent (USP) 2,500,728,2,579,138,3,376,371 and the clear 43-6312 of Japanese Patent, clear 46-41602, clear 50-71787 the endless belt formula continuous polymerization technique of preparation poly (methyl methacrylate) plate is disclosed.Its mainly be by the methyl methacrylate performed polymer under the efficient cryogenic initiator, in the endless belt gap of two synchronous operations, finish polymerization, thermal treatment, cooling by the differing temps zone, successive obtains the sheet material of synthetic glass.
The general introduction of invention
The objective of the invention is in order to address the deficiencies of the prior art.
Therefore, the present invention relates to a kind of continuous fibre enhanced thermoplastic composite, it comprises thermoplastic resin base material and the continuous fibre that is distributed in this base material, and the described continuous fibre of each root is coated with described thermoplastic resin base material.
The present invention relates to a kind of preparation method of continuous fibre enhanced thermoplastic composite on the other hand, and it comprises:
A) provide the successive fiber;
B) provide monomer, described monomeric viscosity is 0.1-3Pas;
C) flood described continuous fibre with described monomer; With
D) make described monomer polymerization, form described matrix material.
Make described monomer polymerization become prepolymer at one of the present invention earlier preferably in the example, flood described continuous fibre with prepolymer subsequently, form matrix material.
The accompanying drawing summary
Fig. 1 is synoptic diagram of making the fibre composite example of the present invention.
Below in conjunction with example the present invention is described in more detail.
The detailed description of invention
The present invention relates to the thermoplastic composite that a kind of continuous fiber strengthens, it comprises thermoplastic resin base material and the continuous fiber that is distributed in this base material.
The thermoplastic resin base material
Being used for thermoplastic resin base material of the present invention is the thermoplastic resin that is polymerized by various thermoplastic resin monomer monomers. Applicable monomer is without particular limitation, can be the various monomers that can form thermoplastic. In a better example of the present invention, the monomer of use is vinyl monomer. The non-limiting example of described monomer has (methyl) esters of acrylic acid, for example: (methyl) acrylic acid C1-12The alkane ester, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid dodecane ester, (methyl) glycidyl acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid benzene methyl, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate; Maleic anhydride, furoate clothing etc. Also can be other alpha-olefin, as; The halides of the single functionality monomers such as styrene, acrylonitrile, vinylacetate, methyl styrene or above monomer. Can also be contain a certain amount of multi-functional monomer as: to divinylbenzene, glycol diacrylate, propylene glycol diacrylate, terephthalic acid (TPA) two propylenes and methyl acyl-oxygen propyl trimethoxy silicane, vinyltrimethoxy silane etc. contain the silane of two keys. Above-mentioned monomer can use separately or two or more are used in combination. Of the present invention another preferably in the example, described resin base material has certain degree of cross linking to improve the performances such as intensity of composite. Normally crosslinking agent forms by polyfunctional monomer or by adding for described resin base material crosslinked. Those of ordinary skill in the art can easily determine kind and the consumption of suitable polyfunctional monomer or crosslinking agent according to the purposes of composite.
In the present invention, term " (methyl) acrylate " comprises acrylate and methacrylate.
Continuous fiber
Term " continuous fiber " refers to the fiber that infinite in length is long; Described length refers to the length with the stretching rear measurement of fiber, and is irrelevant with its residing state (for example being crooked, coiling or straight line) in composite.
At continuous fiber described in the composite of the present invention thermoplastic matrix is played humidification. It is without particular limitation to be applicable to continuous fiber of the present invention, as long as it can play humidification to the thermoplastic resin base material. The non-limiting example that is applicable to continuous fiber of the present invention comprises: glass fibre, carbon fiber, high polymer fibre, as: polyster fibre, nylon fiber, Kevlar fiber etc., metallic fiber and various metal oxide are (such as Al2O
3) fiber etc.
According to the purposes of final matrix material, the continuous fibre that the present invention uses can constitute different shape.For example, the fibrous bundle that can use the straight fiber that is parallel to each other to constitute is made bar-shaped matrix material: can fibrage be become the cloth (as woven fiber glass etc.) of two dimension with conventional fibrage technology, thereby make plane matrix material; Perhaps fibrage is become three-dimensional fibrefelt etc., thereby form matrix material with three-dimensional shape with conventional fibrage technology.
The diameter of the continuous fibre that the present invention uses is without particular limitation.But the too little consumption (number of share of stock) that must increase fiber of diameter just can reach predetermined enhancing purpose.Those of ordinary skill in the art can easily determine the suitable Fibre diameter and the consumption of fiber according to end-use.
In general, the net shape of continuous fibre strongthener of the present invention depends primarily on the shape that continuous fibre is configured to.What for example, form behind the multifibre heat of immersion thermoplastic resin monomer with straight parallel placement mainly is bar-shaped matrix material.But, persons of ordinary skill in the art may appreciate that the net shape of matrix material of the present invention might not be consistent with the shape that continuous fibre is configured to.
In the thermoplastic resin base material, described continuous fibre can be equally distributed regularly, can be irregular non-uniform Distribution also, depends on the final purposes and the cost of matrix material.
In the present invention, term " the described continuous fibre of each root is coated with described thermoplastic resin base material " is meant that thermoplastic resin enters the tiny space that forms between fiber and the fiber, thereby each root fiber and other fiber are separated, thereby coat each root successive fiber.
The manufacture method of matrix material
The manufacture method of continuous fibre reinforced composite materials of the present invention comprises the steps:
A) provide the successive fiber;
B) provide monomer, described monomeric viscosity is 0.5-3Pas; With
C) flood described continuous fibre with described monomer; With
D) make described monomer polymerization, form described matrix material.
The continuous fibre that the inventive method is used can be above-mentioned various known continuous fibre.Those of ordinary skill in the art can easily determine suitable continuous fibre according to required purposes.
In order to improve the consistency between described continuous fibre and the thermoplastic resin base material, increase its bonding strength, can carry out surface treatment to described continuous fibre.It is well-known in the art that continuous fibre is carried out the surface-treated method.In a better example of the present invention, described continuous fibre is carried out chemical surface treatment, the chemical surface treatment agent of using can be a silane coupling agent, as γ-(methacryloxy) propyl trimethoxy silicane (KH-570 is available from dawn chemical plant, Nanjing), vinyltrimethoxy silane etc.
The monomer that the inventive method is used can be various thermoplastic resin alicyclic monomers, vinyl monomer for example recited above.Described monomer should have certain viscosity, if viscosity is too low, then monomer is difficult to coat continuous fibre, can not form resin base material.If viscosity is too high, then monomer is difficult to flood the gap between the infiltrated fiber, thereby influences the intensity of final matrix material.Described monomeric viscosity is generally 0.1-2.0Pas, is preferably 0.5-1.0Pas.
Dipping time to continuous fibre is without particular limitation, as long as space between the complete infiltrated fiber of described monomer.Persons of ordinary skill in the art may appreciate that the required time of dipping is relevant with the arrangement mode of monomeric viscosity and continuous fibre.In a better example of the present invention, the monomer dipping time was generally 0.5-5 minute, was preferably 1-2 minute.
In order after being immersed on the fiber, to make monomer polymerization, also can in monomer, add polymerization starter.Be applicable to that initiator of the present invention can be an azo type free agent initiating radical, as high temperature initiators such as Diisopropyl azodicarboxylates, or efficient cryogenic initiator such as 2,2'-Azobis(2,4-dimethylvaleronitrile).Can be various peroxidation class initiators, as peroxidation such as dibenzoyl peroxide two acyl classes, peroxy dicarbonates such as di-isopropyl peroxydicarbonate, peroxyesters such as the peroxidation isocaprylic acid tert-butyl ester, also can be initiator such as the dibenzoyl peroxide and the N of oil soluble redox system, N '-xylidine, methylethyl ketone peroxide and quadrol etc.
(as toughness of matrix material etc.) as requested, steeping fluid of the present invention can be a single monomer, also can be two or more monomeric mixture.
In order to boost productivity, can carry out pre-polymerization to monomer, use the prepolymer that obtains as steeping fluid then.Contingent incomplete polymerism after using prepolymer can reduce or avoid monomer to be immersed on the fiber as steeping fluid.
Prepolymer as steeping fluid should have suitable viscosity, so that improve the wetting property of described fiber, improves bonding mutually between fiber and the resin base material. and those of ordinary skill in the art can easily determine suitable prepolymerization degree according to viscosity.In a better example of the present invention, the viscosity of prepolymer is 0.5-3Pas, is preferably 1-2Pas.
When forming performed polymer by monomer, initiator amount is generally 0.02～0.3 weight % of monomer consumption, is preferably 0.04～0.1 weight %.When the initiator that uses during as high-temperature initiator (as Diisopropyl azodicarboxylate, dibenzoyl peroxide etc.), prepolymerized temperature is generally 60～90 ℃.
Steeping fluid of the present invention also can be the liquid that polymkeric substance (as organic glass, polystyrene etc.) is dissolved in the modest viscosity that is made in the polymerization single polymerization monomer.These polymkeric substance are generally the homopolymer or copolymer of polymethylmethacrylate and derivative thereof, the homopolymer of polystyrene and derivative thereof or performed polymer, or other can be dissolved in the vinyl polymerization polymer of monomers.In a better example of the present invention, use synthetic glass (polymethylmethacrylate) to be 0.5-3Pas in the methyl methacrylate monomer medium viscosity, the solution that is preferably 1-2Pas is as steeping fluid.
Can add fillers such as auxiliary agents such as oxidation inhibitor, fire retardant, photostabilizer, lubricant, releasing agent or silicon-dioxide, lime carbonate, clay in the steeping fluid of the present invention.To satisfy the different requirements of material, as ageing resistance, flame retardant resistance, anti-shrinkability etc.According to the purposes of final matrix material, those of ordinary skill in the art can easily select above-mentioned additive and consumption thereof for use.
Dipping time to continuous fibre is without particular limitation, as long as space between the complete infiltrated fiber of described prepolymer.The arrangement mode that persons of ordinary skill in the art may appreciate that the viscosity of required time of dipping and prepolymer and continuous fibre is relevant.In a better example of the present invention, the prepolymer dipping time was generally 0.5-5 minute, was preferably 1-2 minute.
In a better example of the present invention; the high reactivity initiator that in performed polymer, adds 0.01～3 weight % that is about amount of monomer; as di-isopropyl peroxydicarbonate, dibenzoyl peroxide or N, N ' thereby-xylidine redox initiator and composition thereof. polyreaction can be carried out below the monomer boiling point fast and stably.In addition, can also in steeping fluid, add the high-temperature initiator of a small amount of (for example accounting for about 0.01-0.5 weight % of amount of monomer), as: Diisopropyl azodicarboxylate etc.Adding high-temperature initiator helps making monomer reaction complete in post-processing stages.
In the pultrusion process of the inventive method, can adopt the sectional polymerization temperature. polymerization procedure can be divided into several stages such as prepolymerization, thermal treatment, mould shape, cooling.The temperature of prepolymerization section is generally 60～100 ℃, and optimum temps is 70～90 ℃.The temperature of thermal treatment section is generally 110～140 ℃, and optimum temps is about 120 ℃.The temperature of mould is generally at 160～220 ℃, and optimum temps is about 180 ℃.Cooling section can be water cooling, also can be air cooling.
Can the resulting matrix material of the present invention be carried out pelletizing by desired length,, carry out the blend extrusion moulding with other polymkeric substance as extruding intermediate.Like this through the fiber of resin-coated, can keep former length and further do not cut off and obtain long fine reinforced composite materials.Also can design difform mould, that pultrusion goes out is bar-shaped, the matrix material of sheet material, profiled material or other shapes.
In order further to improve the intensity of final matrix material, can in steeping fluid, add linking agent to form crosslinked resin base material.When steeping fluid contains linking agent (as Vinylstyrene class linking agent), better use warm air or steam-treated fibre composite, so that bring into play cross-linking effect well through the shaper typing.In the example of a fibre-reinforced thermoplastic resin rope of manufacturing, described shaper has a cylindrical cavity usually.This cavity has predetermined diameter.The rope of finalizing the design has the diameter identical with this cavity after this shaper typing, and has slick surface.
Shown in Figure 1 is the synoptic diagram of the preparation continuous fiber reinforced thermoplastic resin composite material method of a better example of the present invention.As shown in Figure 1, drawing fibrous bundle on creel 1 under the traction of tractor (not shown); (not shown) oven dry back, drying chamber arrives impregnation chamber (2) dipping monomer or prepolymer; Continuous fibre behind the dipping enters first polymeric segment 3 (prepolymerization section) of polymerizing curable, the temperature of the described first pre-polymerization section is controlled at 60～100 ℃, fiber carries out polymerization through a few segment length 0.8-1 rice, an internal diameter 2-4 centimetre sealed at both ends stainless-steel pipe in polymeric segment 3: the rope after the polymerization enters second polymeric segment 4 and further carries out polymerization, the temperature of this polymeric segment is controlled at 110～140 ℃, so that make the unconverted monomer polymerization complete; Through shaper 5 typings, the temperature of described mould is controlled at 160～220 ℃ subsequently.Be added with under the situation of linking agent, behind shaper 5, also can randomly comprise a warm air or steam-treated section, so that make resin base material crosslinked better.Cool off by cooling section (6) then.The matrix material that makes as requested can be by dicing machine (7) pelletizing.
Further specify the present invention below by embodiment.
In 100 parts by weight of methylmethacrylate, add 0.06 weight part Diisopropyl azodicarboxylate (AIBN), under 80～90 ℃, be aggregated to the about 1Pas of viscosity, form the methyl methacrylate prepolymer., in performed polymer, add 0.2 weight part diisopropyl peroxydicarbonate (IPP) and add 0.01 weight part Diisopropyl azodicarboxylate as steeping fluid with performed polymer.Flood continuous glass fibre with performed polymer, dipping time is 1 minute.Use stage feeding polymerization method as shown in Figure 1, the temperature of the first prepolymerization section is controlled at 90 ℃, and the temperature of aftertreatment section is controlled at 130 ℃, and the temperature of mould is controlled at 200 ℃, and pulling speed is 0.6m/min.Obtain continuous glass fibre enhanced composite material of polymethyl methacrylate.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
Embodiment 2
In 100 parts by weight of styrene, add 0.05 weight part Diisopropyl azodicarboxylate, under 60～70 ℃, be aggregated to viscosity and reach 2Pss.As steeping fluid, in performed polymer, add dibenzoyl peroxide/N of 0.5 weight part 1:1 with performed polymer, N '-dimethyl benzene amine mixt, and add the Diisopropyl azodicarboxylate (AIBN) of 0.01 weight part.With performed polymer dipping successive glass fibre, dipping time is 2 minutes.Use stage feeding polymerization object space method shown in Figure 1, the temperature of the first prepolymerization section is controlled at 90 ℃, and the temperature of aftertreatment section is controlled at 130 ℃, and the temperature of mould is controlled at 160 ℃, and pulling speed is 0.5m/min.Obtain continuous glass fibre enhanced poly styrene composite material.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
Add the Diisopropyl azodicarboxylate of 0.05 part of weight in 100 parts by weight of acrylic dodecane esters, being aggregated to viscosity viscosity under 60～70 ℃ is 0.5Pas, obtains vinylformic acid dodecane ester prepolymer.As steeping fluid, in performed polymer, add dibenzoyl peroxide/N of 1: 1 of 0.5 weight part with this performed polymer, N '-and monomethylaniline, and add the Diisopropyl azodicarboxylate of 0.01 weight part.Flood continuous carbon fibre with performed polymer, dipping time is 1.5 minutes.Use stage feeding polymerization method as shown in Figure 1, the temperature of the first prepolymerization section is controlled at 90 ℃, and the temperature of aftertreatment section is controlled at 130 ℃, and the temperature of mould is controlled at 200 ℃, and pulling speed is 0.5m/min.Obtain continuous polyster fibre enhanced polypropylene acid dodecane ester matrix material.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
100 weight part glycol diacrylates are mixed mutually with 0.05 weight part benzoyl peroxide (BPO), under about 98 ℃ temperature, make polymerization of mixtures to viscosity reach 3Pas.In prepolymer, add 0.4 weight part diisopropyl peroxydicarbonate (IPP), 3 weight part Vinylstyrenes and 0.02 weight part BPO subsequently, behind the uniform mixing as steeping fluid.Flood continuous polyster fibre with performed polymer, dipping time is 2 minutes.Use stage feeding polymerization method shown in Figure 1, the temperature of the first prepolymerization section is controlled at 90 ℃, the temperature of aftertreatment section is controlled at 130-140 ℃, the temperature of mould is controlled at 160-170 ℃, pulling speed is 0.5m/min, and making the rope by mould discharging is 102 ℃ steam-pipe through a segment length 0.8m, temperature, obtains continuous polyster fibre enhanced PET matrix material.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
100 weight part methyl acyl-oxygen oxypropyl trimethyl silane are mixed mutually with 0.08 weight part BPO, under about 98 ℃ temperature, make polymerization of mixtures to viscosity reach 0.5Pas.Add 0.5 weight part BPO, 0.4 weight part N subsequently in prepolymer, accelerine is with performed polymer dipping Kevler fiber (available from the nylon fiber of E.I.Du Pont Company).Dipping time is 1 minute.Use stage feeding polymerization method shown in Figure 1, the temperature of the first prepolymerization section is controlled at 90 ℃, and the temperature of aftertreatment section is controlled at 130 ℃, and the temperature of mould is controlled at 200 ℃, pulling speed is 0.6m/min, obtains the fibre-reinforced methyl acyl-oxygen of continuous Kevler oxypropyl trimethyl silane matrix material.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
With 100 weight part n-BMAs (PBMA), 0.08 weight part Diisopropyl azodicarboxylate (AIBN) and 20 weight part clays, be polymerized to the about 1.5Pas of viscosity at 80-90 ℃, form the n-BMA performed polymer.Add 0.3 weight part dipropyl peroxide two carbonic ethers (IPP) then, with the dipping body as steeping fluid, with the pulling speed of the 0.4m/min parallel glass fiber that to make 30 diameters be 0.5mm successively by steeping vat, pre-polymerization section, heat treated section and mould.Form the poly-n-butyl methacrylate matrix material of glass fibre enhanced clay filled.
0.5 meter of described dipping flute length is equipped with above-mentioned steeping fluid; 2.5 meters of described pre-polymerization segment lengths, temperature is controlled at 95 ℃; 0.5 meter of described heat treated segment length, temperature is controlled at 110 ℃; Long 0.2 meter of described mould, temperature is controlled at 160 ℃.
Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
Comparative example 1
Press United States Patent (USP) 5,935,508 described methods make polyacrylic acid monooctyl ester matrix material, and use therein continuous fibre is the glass fibre that uses of embodiment 6 (available from a Chinese Tongxiang megalith group).Measure the required minimum destructive force of this material fracture with the Instron trier, the results are shown in table 1.
Table 1
| Material | Minimum destructive force (MPa) |
| |
827 |
| Embodiment 2 | 671 |
| |
1270 |
| |
472 |
| |
872 |
| |
934 |
| Comparative example 1 | 621 |
Claims (9)
1. the preparation method of a continuous fibre enhanced thermoplastic composite, it comprises:
A) provide the successive fiber;
B) provide the thermoplastic resin alicyclic monomer, described monomer is selected from (methyl) vinylformic acid C
1-12Alkane ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid dimethylin ethyl ester, (methyl) vinylformic acid benzene methyl, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate; Maleic anhydride, furoate clothing, vinylbenzene, vinyl cyanide, vinyl acetate, vinyl toluene, to divinylbenzene, glycol diacrylate, propylene glycol diacrylate, terephthalic acid two propylene esters, methyl acyl-oxygen propyl trimethoxy silicane, vinyltrimethoxy silane or its mixture, described monomeric viscosity is 0.5-3Pas;
C) flood described continuous fibre with described monomer; With
D) make described monomer polymerization, form described matrix material.
2. the method for claim 1, it is characterized in that step (b) afterwards but step (c) it also comprises the described monomer of pre-polymerization before, forming viscosity is the step of the prepolymer of 0.5-3Pas, floods described continuous fibre with this prepolymer as steeping fluid subsequently.
3. method as claimed in claim 1 or 2 is characterized in that described monomeric viscosity is 0.5-1Pas.
4. method as claimed in claim 2, the viscosity that it is characterized in that described prepolymer is 1-2Pas.
5. method as claimed in claim 1 or 2, it is characterized in that it also comprises with the chemical processing agent that is selected from γ-(methacryloxy) propyl trimethoxy silicane or vinyltrimethoxy silane carries out the surface-treated step to described continuous fibre.
6. method as claimed in claim 1 or 2 is characterized in that described polymerization is that segmentation is carried out, and it comprises prepolymerization, thermal treatment, mould shape and cooling step;
The temperature of described prepolymerization section is 60～100 ℃;
The temperature of described thermal treatment section is 110～140 ℃;
The temperature of described mould is 160～220 ℃;
Described cooling step is selected from water cooling or air cooling.
7. method as claimed in claim 1 or 2 is characterized in that described continuous fibre is selected from glass fibre, carbon fiber, polyster fibre, nylon fiber, kevlar fiber, steel fiber or metal-oxide fiber.
8. method as claimed in claim 1 or 2 is characterized in that the shape of described continuous fibre is selected from the two-dimensional fiber cloth of the fibrous bundle of the straight fiber formation that is parallel to each other, fibrage one-tenth or the three-dimensional fiber felt that fibrage becomes.
9. continuous fibre enhanced thermoplastic composite that makes with each described method among the claim 1-8, it comprises thermoplastic resin base material that is formed by the thermoplastic resin monomer polymerization and the continuous fibre that is distributed in this base material, and described continuous fibre is coated with described thermoplastic resin base material.
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| CN102069543B (en) * | 2009-11-20 | 2014-06-18 | 合肥杰事杰新材料股份有限公司 | Method for preparing bicycle frame from long-fiber reinforced thermoplastic composite material through on-line direct molding |
| CN102107534B (en) * | 2009-12-29 | 2013-06-26 | 合肥杰事杰新材料股份有限公司 | Method for manufacturing bicycle frame by using continuous fiber reinforced thermoplastic composite materials |
| CN102452203B (en) * | 2010-11-02 | 2015-07-08 | 上海杰事杰新材料(集团)股份有限公司 | Anti-skidding thermoplastic composite material |
| CN102477199B (en) * | 2010-11-25 | 2015-06-24 | 合肥杰事杰新材料股份有限公司 | Organic fiber cloth filled polymethylmethacrylate composite plate material and its preparation method |
| EP2659493B1 (en) * | 2010-12-29 | 2017-08-09 | Dow Global Technologies LLC | Method of making a cable strength member |
| CN102400381B (en) * | 2011-04-06 | 2014-07-23 | 东华大学 | Preparation method of spun yarn fabric for enhancing thermoplastic resin |
| CN102604303B (en) * | 2012-03-08 | 2014-01-22 | 北京英伟技术发展有限公司 | Method for coextrusion of glass fiber reinforced plastic |
| CN103568396A (en) * | 2012-08-02 | 2014-02-12 | 上海杰事杰新材料(集团)股份有限公司 | Light-weight and high-strength thermoplastic composite material sandwich board and production method thereof |
| CN105859930A (en) * | 2016-06-01 | 2016-08-17 | 东华大学 | Thermoplastic resin-based carbon fiber composite material and preparation method thereof |
| CN107501609B (en) * | 2017-07-26 | 2019-07-05 | 兰州蓝星纤维有限公司 | A kind of thermoplastic fibre composite material sheet and its preparation method and application product |
| CN111978459A (en) * | 2019-05-24 | 2020-11-24 | 汉能移动能源控股集团有限公司 | PMMA/glass fiber composite material and preparation method and application thereof |
| CN112574449A (en) * | 2020-12-02 | 2021-03-30 | 深圳市昌华生物医学工程有限公司 | Preparation method of continuous fiber reinforced composite material, continuous fiber reinforced composite material and medical instrument product |
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