CN105400144B - Pultrusion prepares light curing compound material, its preparation method and application - Google Patents
Pultrusion prepares light curing compound material, its preparation method and application Download PDFInfo
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- CN105400144B CN105400144B CN201510921305.0A CN201510921305A CN105400144B CN 105400144 B CN105400144 B CN 105400144B CN 201510921305 A CN201510921305 A CN 201510921305A CN 105400144 B CN105400144 B CN 105400144B
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- 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
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- 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
- C08K7/14—Glass
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
Pultrusion prepares the technical field that light curing compound material, its preparation method and application belong to ultraviolet light solidification quick molding method.Method and step：(1) oligomer and cation light initiator are well mixed by a certain percentage；Stirred under ultraviolet light, make cation light initiator photodissociation, obtain uniform liquid A；(2) epoxy resin, reactive diluent are mixed with auxiliary agent, obtains uniform liquid B；(3) two kinds of materials of liquid A and liquid B are delivered into main frame from charging basket via respective mateiral pump respectively to be measured, pressurize, be then sent to spray gun, by being sprayed onto fiber or its product surface after spray gun mixing；The mass fraction of liquid A accounts for the 0.1%wt 50wt% of liquid after mixing；(4) temperature of pultrusion die is regulated and controled in the range of 15 DEG C 200 DEG C, photocuring fibre reinforced composites will curing molding in a mold.During Illumination of the present invention and forming process are completely separable, and to mould and reinforcing material, whether printing opacity does not require in forming process；Energy-conserving and environment-protective, laser curing velocity is fast, and shaping speed is faster.
Description
Technical field
The invention belongs to the technical field of ultraviolet light solidification quick molding method, and in particular to utilize pultrusion to one kind
Method prepare light curing compound material and its application.
Background technology
Composite is the material with very big vitality for answering development of modern scientific technology to emerge, and it is by two kinds or two
The different material of kind above property, is combined by various process meanses.Each composition material of composite is in performance
Synergy is played, obtains the incomparable superior combination property of homogenous material, it has turned into a kind of present age new engineering material
Material.Composite has the advantages of rigidity is big, intensity is high, in light weight, and can be designed according to the requirement of use condition and
Manufacture, to meet various specific uses, so as to greatly improve the efficiency of engineering structure.
The advantages that polymer matrix composites can be designed with its lightweight, high intensity, mechanical property and be widely used in aviation
In the structural material in the fields such as space flight, chemical industry, shipbuilding, machinery, building materials, particularly carbon fibre composite, due to carbon fiber
Mechanical property is best in current all fibres material, significantly larger than glass fibre, compound to related base material, can be significantly
The comprehensive mechanical performance of composite is improved, it is of great interest.But existing composite material process planning there is
The defects of production cycle length, low production efficiency, while serious pollution also be present, therefore industrially need a kind of green
The technology of stereolithography resin based composites.
Pultrusion is a kind of special process in composite material process planning, and its advantage is:1. production process is completely real
Existing Automated condtrol, production efficiency are high；2. fiber content may be up to 80% in pultrusion product, impregnation is carried out under tension,
The effect of reinforcing material can be given full play to, product strength is high；3. product vertical, horizontal intensity can be adjusted arbitrarily, difference can be met
The requirement of mechanical property product；4. without leftover bits in production process, product is not required to post-processing, therefore more other techniques save
Work, raw material is saved, save energy consumption；5. quality of item is stable, reproducible, length can arbitrary cut-off.
The characteristics of photocuring technology is mainly that energy-conserving and environment-protective and curing rate are fast.But prepared using photocuring technology compound
Material is there is also certain limitation, particularly photocuring technology needs curing molding under illumination condition, therefore it is required that shaping
Mould is transparent, also limit the species and size of reinforcing material, therefore existing photocuring technology can only be molded very thin (3mm
Left and right) glass fiber compound material, carbon fibre composite can be hardly molded, this makes photocuring technology be led in composite
The application in domain is limited by very large.
The present invention is combined using photocuring technology with pultrusion, i.e., based on photo-curing mechanism and technology, but illumination
Journey is completely separable with forming process, and to mould and reinforcing material, whether printing opacity does not require in forming process；Whole process can
To complete at ambient temperature, energy-conserving and environment-protective；The curing rate of photocuring technology is fast, can significantly improve pultrusion into
Type speed, shaping speed is faster；Whole process needs not move through glue groove, and the resin that system needs is sprayed by metering, not only may be used
Effectively to alleviate resin lower flow problem caused by gravity, and whole process hardly has scrap rubber generation.
The content of the invention
It is an object of the invention to provide a kind of light curing compound material, its preparation method and application, this technology preparation technology
Simply, solidification rate is fast, and production efficiency is high, can substitute traditional composite production technology.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of preparation method of the photocuring fibre reinforced composites of pultrusion, comprises the following steps：
(1) oligomer and cation light initiator are well mixed by a certain percentage；Stirred under ultraviolet light, make sun
Ionic photoinitiator photodissociation, obtain uniform liquid A；The mass fraction of the cation light initiator accounts for uniform liquid A's
0.1wt%-80wt%；
(2) resin, reactive diluent are mixed with auxiliary agent, obtains uniform liquid B；The quality of reactive diluent liquid B point
Number is 0-80wt%, and the mass fraction that auxiliary agent accounts for liquid B is 0-10wt%；
(3) two kinds of materials of liquid A and liquid B are delivered into main frame from charging basket via respective mateiral pump respectively to be counted
Amount, pressurization, is then sent to spray gun, by being sprayed onto fiber or its product surface after spray gun mixing；The mass fraction of liquid A accounts for mixed
The 0.1%wt-50wt% of liquid after conjunction；
(4) temperature of pultrusion die is regulated and controled in the range of -15 DEG C -200 DEG C, photocuring fibre reinforced composites will be in mould
Curing molding in tool.
Resin in the step of above-mentioned preparation method (1) is polyether polyols alcohols, polyglycols ethers, polyethylene glycol, polyoxy
Glycerine.
Cation light initiator described in the step of above-mentioned preparation method (1) includes salt compounded of iodine, sulfosalt and iron arene
In one or more.
Resin in the step of above-mentioned preparation method (2) includes epoxy resin, in vinyl ethers and oxygen helerocyclics
It is one or more of；Epoxy resin is bisphenol A epoxide resin, or bisphenol F epoxy resin, or novolac epoxy resin, or diepoxide
Polyolefin compound, or naphthalene system epoxy resin, or aliphatic epoxy resin, or cycloaliphatic epoxy resin.
Reactive diluent in the step of above-mentioned preparation method (2) is epoxy monomer, vinyl ether monomers and oxa- ring list
Body.
The mass fraction that auxiliary agent described in the step of above-mentioned preparation method (2) accounts for liquid B is 0-10wt%, and auxiliary agent can root
According to being actually needed addition wax, silane coupler, pigment etc..
The mass fraction that cation light initiator described in the step of above-mentioned preparation method (1) accounts for liquid A is 0.5wt%-
80wt%.
Temperature conditionss described in the step of above-mentioned preparation method (4) are >=-15 DEG C, and preferably >=15 DEG C, temperature is higher, and it is solid
Changing speed will be faster.
Fiber described in the step of above-mentioned preparation method (3) can be carbon fiber, glass fibre, nylon fiber, poly- third
Alkene fiber, metallic fiber etc..
Thickness≤5mm of fiber and its products described in the step of above-mentioned preparation method (3), preferably≤2mm, its thickness
In the case of relatively thin, it is easier to make the uniform wetting fibre of resin and its product；Control thickness also helps reduction unit area
Quantity for spray, can effectively alleviate resin lower flow problem caused by gravity.
In above-mentioned preparation method, described in step (1) is to make the cationic photopolymerization in system with the purpose of ultraviolet light
The complete photodissociation of initiator.
Light polymerization process of the present invention is cationic photopolymerization, there is solidify afterwards behavior, can be by curing molding
Composite carry out high temperature post cure processing to improve its performance.
In the preparation method of the present invention, the species and dosage of the auxiliary agent, the shape of composite, the technique of shaping is to this
It is readily apparent that for art personnel.
Invention additionally discloses a kind of light curing compound material, is prepared using above-mentioned preparation method.
The present invention relates to above-mentioned light curing compound material application field with using conventional method prepare composite wood
The application field of material is consistent.
The present invention technological principle be：The present invention is by not volatile low of cation light initiator and polyether polyols alcohols etc.
Polymers is mixed, and its photodissociation (obtaining photoinitiator system PI) is made in the form of stirring illumination；The active group generated after photodissociation is equal
It is even it is scattered in a liquid, the oligomer such as polyether polyols alcohols serves as chain-transferring agent in system, makes the cation group of generation
Activity be stabilized always；Solve the problems, such as to be unfavorable for store for a long time.
It is overall to consolidate with cationic photopolymerization after cation light initiator mixes with not volatile oligomer such as polyether polyols alcohols
Changing the dissolubility of resin can improve, it is easier to and it is quick well mixed, solve its deliquescent problem.
Active group has been evenly spread in the oligomer such as polyether polyols alcohols, reduces the concentration of active group, so as to
Photoinitiator system PI will not occur gel group moment, simultaneously with light-cured resin mixed process, there is longer induction period
The reaction speed of whole system and induction period can be controlled by control system temperature, photocuring tree is completed in stage induction period
Infiltration of the fat to fibre reinforced materials, and bubble that may be present in exclusion system；After induction period terminates, whole system will be fast
Speed reaction, the composite needed.Meanwhile contain hydroxyl in the oligomer such as polyether polyols alcohols, eventually with epoxy radicals
Group combines, therefore does not have solvent volatilization in whole process；After induction period terminates, the speed of its reaction speed and Stereolithography
Similar, the composite property being finally prepared and the conventional curing method composite property for solidifying to obtain are similar even more
Add excellent.
Measured, pressurizeed by the way that liquid A and liquid B are delivered into main frame from charging basket via respective mateiral pump respectively,
Spray gun is delivered to, is sprayed after spray gun mixing, whole process can design resin in composite by strict measure control
Content, not only can effectively alleviate resin lower flow problem caused by gravity, and avoid the generation of scrap rubber, both carry
The high performance of composite, saves raw material again.
The performance that polymer matrix composites both ensure that composite is prepared using the technology, while also there is photocuring skill
Art is quick, energy-conservation, it is environmentally friendly the advantages that, further shorten the production cycle of polymer matrix composites, improve production efficiency, work
Skill is simple, alternative traditional composite material process planning.
Brief description of the drawings：
Fig. 1 is pultrusion molding process flow chart in the present invention；
In figure：1st, yarn wheel；2nd, fibre bundle, fiber cloth, needled mat etc.；3rd, threading board；4th, shower nozzle；5th, pultrusion die.
Embodiment
Technical scheme is described further below by preferred embodiment, following examples contribute to ability
The technical staff in domain further understands the present invention, but should not be construed as limiting the scope of the invention.It should be understood that
, it will be apparent to those skilled in the art that without departing from the inventive concept of the premise, some deformations can also be made and changed
Enter.These are belonged within protection scope of the present invention.
Embodiment 1：
Step 1, addition mass fraction is that (mass fraction is the matter for accounting for liquid A to 5wt% in polyethylene glycol (Mn=200)
Measure fraction) triaryl hexafluoro-antimonic acid sulfosalt, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity prolonged exposure
30min, stirring illumination obtain uniform liquid A after terminating；
Step 2, by bisphenol A epoxide resin and oxetanes in mass ratio 4:1 ratio is well mixed, and obtains uniform liquid
Body B；
Step 3, under the pulling force of hauling machine, the glass fiber bundle that acidic treatment is crossed is extracted out from the yarn axle of creel, control
The thickness of fibre bundle processed is 0.1mm, width 20cm, drafting rate 1m/min；
Step 4, with mateiral pump by A, B presses 1:9 mass ratio is delivered to main frame from charging basket respectively, pressurization, in the showerhead
It is well mixed, hybrid resin is uniformly sprayed on fiber by 18.5g/min speed；
Step 5, the temperature of setting pultrusion die are 30 DEG C, by material disposal molding in pultrusion die；
Step 6, cleaved machine-cut cut to obtain the composite of predetermined length, then place it in 120 DEG C of environment
Solidify afterwards handle 2h.
Embodiment 2：
Step 1, addition mass fraction is 10wt% in polyoxy glycerine (mass fraction is the mass fraction for accounting for liquid A)
Diaryl hexafluoro-antimonic acid sulfosalt, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity prolonged exposure 30min,
Stirring illumination injects A charging baskets after terminating；
Step 2, by bisphenol A epoxide resin, cycloaliphatic epoxy resin and oxetanes in mass ratio 7:1:2 ratio is mixed
Close uniform, injection B charging baskets；
Step 3, under the pulling force of hauling machine, by carbon fiber woven cloth (thickness 0.5mm, the width Jing Guo acidic treatment
For 20cm) extraction width is 20cm, drafting rate 1m/min from the yarn axle of creel；Step 4, with mateiral pump by A, B presses 2:8
Mass ratio be delivered to main frame from charging basket, pressurize, be well mixed in the showerhead, it is by 87g/min speed that hybrid resin is equal
Even is sprayed on fiber；
Step 5, the temperature of three sections of pultrusion dies of setting are respectively 25 DEG C, 140 DEG C, 200 DEG C, will in pultrusion die
Composite disposal solidifying is molded；
Embodiment 3：
Step 1, (mass fraction is the mass fraction for accounting for liquid A) that mass fraction is 5wt% is added in polypropylene glycol
Triaryl hexafluorophosphoric acid salt compounded of iodine, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity prolonged exposure 30min,
Stirring illumination obtains uniform liquid A after terminating；
Step 2, by bisphenol A epoxide resin and oxetanes in mass ratio 4:1 ratio is well mixed, and obtains uniform liquid
Body B；
Step 3, under the pulling force of hauling machine, the carbon fiber bundle that acidic treatment is crossed is extracted out from the yarn axle of creel, control
The thickness of fibre bundle is 0.1mm, width 20cm, drafting rate 1m/min；
Step 4, with mateiral pump by A, B presses 2:8 mass ratio is delivered to main frame from charging basket, pressurization, mixes in the showerhead
Uniformly, hybrid resin is uniformly sprayed on fiber by 16g/min speed；
Step 5, the temperature of setting pultrusion die are 30 DEG C, by material disposal molding in pultrusion die；
Step 6, cleaved machine-cut cut to obtain the composite of predetermined length, then place it in 160 DEG C of environment
Solidify afterwards handle 2h.
Embodiment 4：
Step 1, add in PPG mass fraction be 20wt% (mass fraction is the quality point for accounting for liquid A
Number) triaryl hexafluoro-antimonic acid sulfosalt, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity prolonged exposure
30min, stirring illumination obtain uniform liquid A after terminating；
Step 2, by bisphenol A epoxide resin and oxetanes in mass ratio 4:1 ratio is well mixed, and obtains uniform liquid
Body B；
Step 3, under the pulling force of hauling machine, the glass fiber bundle that acidic treatment is crossed is extracted out from the yarn axle of creel, control
The thickness of fibre bundle processed is 0.1mm, width 20cm, drafting rate 1m/min；
Step 4, with mateiral pump by A, B presses 1:15 mass ratio is delivered to main frame from charging basket respectively, pressurization, in the showerhead
It is well mixed, hybrid resin is uniformly sprayed on fiber by 18.5g/min speed；
Step 5, set pultrusion die temperature be 60 DEG C, 180 DEG C, in pultrusion die by material disposably into
Type；
Embodiment 5：
Step 1, add in the polyethylene glycol (Mn=200) mass fraction be 80wt% (mass fraction accounts for liquid A
Mass fraction) triaryl hexafluoro-antimonic acid sulfosalt, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity persistently shine
30min is penetrated, stirring illumination obtains uniform liquid A after terminating；
Step 2, by bisphenol A epoxide resin and oxetanes in mass ratio 4:1 ratio is well mixed, and obtains uniform liquid
Body B；
Step 3, under the pulling force of hauling machine, the nylon fiber beam that acidic treatment is crossed is extracted out from the yarn axle of creel, control
The thickness of fibre bundle processed is 0.1mm, width 20cm, drafting rate 1m/min；
Step 4, with mateiral pump by A, B presses 1:20 mass ratio is delivered to main frame from charging basket respectively, pressurization, in the showerhead
It is well mixed, hybrid resin is uniformly sprayed on fiber by 18.5g/min speed；
Step 5, the temperature of setting pultrusion die are 100 DEG C, by material disposal molding in pultrusion die；
Embodiment 6：
Step 1, add in the polyethylene glycol (Mn=200) mass fraction be 5wt% (mass fraction accounts for liquid A
Mass fraction) triaryl hexafluoro-antimonic acid sulfosalt, stir while using high-pressure sodium lamp with 100mw/cm2Light intensity persistently shine
30min is penetrated, stirring illumination obtains uniform liquid A after terminating；
Step 2, by bisphenol A epoxide resin and oxetanes in mass ratio 4:1 ratio is well mixed, and obtains uniform liquid
Body B；
Step 3, under the pulling force of hauling machine, the glass fabric that acidic treatment is crossed is extracted out from the yarn axle of creel, glass
The thickness of glass fiber cloth is 0.3mm, width 20cm, drafting rate 1m/min；
Step 4, with mateiral pump by A, B presses 1:9 mass ratio is delivered to main frame from charging basket respectively, pressurization, in the showerhead
It is well mixed, hybrid resin is uniformly sprayed on fiber by 65g/min speed；
Step 5, the temperature of setting pultrusion die are 10 DEG C, by material disposal molding in pultrusion die；
In the other embodiment of light curing compound material of the present invention, unlike the embodiments above is resin types with matching somebody with somebody
Than can be formulated by skilled worker according to modification is actually needed；Unlike the embodiments above is that fibre bundle can also be through peracid
Property processing carbon fiber, nylon fiber, polypropylene fibre, metallic fiber etc., wherein fibre bundle can also be thin fiber cloth, pin
Knit felt etc.；Unlike the embodiments above, spray rate in step 4 can need to change its spray according to using field
Apply speed；It is unlike the embodiments above, the temperature of pultrusion die can be changed as needed in steps of 5；With above-mentioned reality
Apply unlike example, in step 6 can be without high-temperature post-treatment.
Table 1：
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to embodiment for pipe, those of ordinary skills in the art should understand that：Still can be with
The embodiment of the present invention is modified or equivalent substitution is carried out to some technical characteristics；Without departing from skill of the present invention
The spirit of art scheme, it all should cover among the claimed technical scheme scope of the present invention.
Claims (9)
1. a kind of preparation method of the photocuring fibre reinforced composites of pultrusion, comprises the following steps：
(1) oligomer and cation light initiator are well mixed by a certain percentage；Stirred under ultraviolet light, make cation
Light trigger photodissociation, obtain uniform liquid A；The mass fraction of the cation light initiator accounts for uniform liquid A 0.1wt%-
80wt%；Oligomer is polyether polyols alcohols；
(2) resin, reactive diluent are mixed with auxiliary agent, obtains uniform liquid B；Reactive diluent accounts for the mass fraction of liquid B
For 0-80wt%, the mass fraction that auxiliary agent accounts for liquid B is 0-10wt%；
(3) two kinds of materials of liquid A and liquid B are delivered into main frame from charging basket via respective mateiral pump respectively to be measured, added
Pressure, is then sent to spray gun, by being sprayed onto fiber or its product surface after spray gun mixing；After the mass fraction of liquid A accounts for mixing
The 0.1wt%-50wt% of liquid；
(4) temperature of pultrusion die is regulated and controled in the range of -15 DEG C -200 DEG C, photocuring fibre reinforced composites will in a mold
Curing molding.
2. preparation method according to claim 1, it is characterised in that the polyether polyols alcohols in step (1) includes poly- two
Alcohol ethers or polyoxy glycerine.
3. preparation method according to claim 1, it is characterised in that the cation light initiator bag described in step (1)
Include salt compounded of iodine, the one or more in sulfosalt and iron arene.
4. preparation method according to claim 1, it is characterised in that the resin in step (2) includes epoxy resin, ethene
One or more in base ether and oxygen helerocyclics.
5. preparation method according to claim 4, it is characterised in that epoxy resin is bisphenol A epoxide resin, or Bisphenol F
Epoxy resin, or novolac epoxy resin, or diepoxide polyolefin compound, or naphthalene system epoxy resin, or aliphatic epoxy tree
Fat, or cycloaliphatic epoxy resin.
6. preparation method according to claim 1, it is characterised in that reactive diluent described in step (2) is epoxy list
One or more in body, vinyl ether monomers or oxygen heterocyclic monomer.
7. preparation method according to claim 1, it is characterised in that the thickness of fiber or its product described in step (3)
Degree≤5mm.
8. the composite prepared by preparation method described in application claim 1-7 any one.
9. the composite prepared by preparation method according to claim 1-7 any one is as photocuring fiber reinforcement
The application of material.
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| CN108485184B (en) * | 2018-02-11 | 2020-11-24 | 东莞爱的合成材料科技有限公司 | High-temperature-resistant transparent photosensitive resin for clinical medicine and preparation method thereof |
| CN110549648A (en) * | 2018-05-30 | 2019-12-10 | 江苏海川新材料科技有限公司 | High-efficient environmental protection low energy consumption FRP muscle production water line |
| CN113334806A (en) * | 2021-07-06 | 2021-09-03 | 江苏德晴新材股份有限公司 | Pultrusion process of continuous ultrahigh-speed fiber reinforced composite material |
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| CN101915970A (en) * | 2010-06-30 | 2010-12-15 | 上海晓宝增强塑料有限公司 | Optical cable, fiber reinforced plastics used thereby and preparation method thereof |
| CN102504496A (en) * | 2010-06-30 | 2012-06-20 | 上海晓宝增强塑料有限公司 | Preparation method of fiber-reinforced plastic |
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| CN101915970A (en) * | 2010-06-30 | 2010-12-15 | 上海晓宝增强塑料有限公司 | Optical cable, fiber reinforced plastics used thereby and preparation method thereof |
| CN102504496A (en) * | 2010-06-30 | 2012-06-20 | 上海晓宝增强塑料有限公司 | Preparation method of fiber-reinforced plastic |
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