CN110128646A - A kind of composite material and preparation method thereof based on vinylite treated basalt fiber - Google Patents
A kind of composite material and preparation method thereof based on vinylite treated basalt fiber Download PDFInfo
- Publication number
- CN110128646A CN110128646A CN201910410926.0A CN201910410926A CN110128646A CN 110128646 A CN110128646 A CN 110128646A CN 201910410926 A CN201910410926 A CN 201910410926A CN 110128646 A CN110128646 A CN 110128646A
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- vinylite
- preparation
- composite material
- resin
- basalt fiber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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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
- C08K7/10—Silicon-containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of composite material and preparation method thereofs based on vinylite treated basalt fiber, belong to high molecular polymer field.It include: the pretreatment of basalt fibre, the preparation of vinylite material, preparation, absorption and the solidification of modifier and five parts of shaping.One aspect of the present invention is reacted the aziridine vinylite of synthesis by aziridines substance as modifier with monocarboxylic acid, reacts fixation with silane coupling agent K560 is connected on basalt fibre；On the other hand by optimization solidification, absorbing process medium vinyl resin, promotor, initiator proportion, optimize immobilization technology, further increase the binding ability of organic resin and basalt fibre；The raising production efficiency of basalt fiber composite material is substantially increased while guaranteeing modified solidified effect using custom mold simultaneously.
Description
Technical field
The invention belongs to glass fiber compound material fields, especially a kind of to be based on vinylite treated basalt fiber
Composite material and preparation method thereof.
Background technique
Vinylite refers generally to epoxy vingl ester resin, the molecule last-in-chain(LIC) prepared using epoxy resin and acrylic acid as raw material
End or side group contain the function macromolecular of unsaturated double-bond, industrially need to be dissolved in styrene monomer when in use,
One side styrene can effectively reduce resin viscosity, and another aspect styrene can will be above-mentioned in resin solidification as cross-linking monomer
Function macromolecular is actively linked with each other.
The glass fibre that basalt fibre is drawn with natural basalt passes through platinum rhodium after 1450 DEG C~1500 DEG C meltings
Continuous fiber made of alloy bushing, high speed pulling.Not only intensity is high, but also has electrical isolation, corrosion-resistant, high temperature resistant
Etc. a variety of excellent properties.Meanwhile and a kind of environment-friendly type, green new fiber materials.
In existing basalt fibre production process, fiber has been coated one layer of insoluble oil compound or Nano-meter SiO_22
Particle, so as to improve the degree of roughness of fibrous outer surfaces.On the one hand, surface increases Nano-meter SiO_22The higher cost of particle, therefore
The popularity of the technique is smaller；On the other hand, since basalt fibre surface is more smooth, surface can be lower, and mostly organic
Combination degree between object is inadequate, causes the service life for coating the not basalt fibre of capacitive lipidic compounds shorter.Therefore,
Basalt fiber surface modification is even more important on the influence of the performance of composite material.
Summary of the invention
Goal of the invention: providing a kind of composite material and preparation method thereof based on vinylite treated basalt fiber, with solution
Organic resin is inadequate with fiber bonding in certainly existing Basalt fiber surface modification production process, and composite material is caused to use
Service life shorter problem.
Technical solution: a kind of composite material and preparation method thereof based on vinylite treated basalt fiber, including it is as follows
Step:
Step S1, the pretreatment of basalt fibre: according to bath raio 1:(3~4) basalt fibre product is put into be placed with silane idol
In the treatment fluid for joining agent；It after immersion treatment 30min, is put into 105 DEG C of air dry oven, dry 30~45h is cooling stand-by；
Step S2, the preparation of vinylite material:
Step S201, ingredient:
30 ~ 45wt% of tri (propylene glycol) diacrylate；
8 ~ 20wt of acrylic acid %；
30 ~ 60wt of aziridine %；
Tert-butyl hydroquinone 200-500ppm；
Step S202, esters of unsaturated carboxylic acids, unsaturated carboxylic acid and polymerization inhibitor are sequentially added into reaction kettle；
Step S203, under room temperature, aziridines substance is added drop-wise in reaction kettle, is stirred when being added dropwise, makes aziridines substance
With unsaturated monocarboxylic acid energy homogeneous reaction, keep exothermic heat of reaction uniform, this process will strictly monitor material temperature in kettle, such as more than 60
DEG C, then it should lead to cooling water and cool down, discharge after 6h filling；
Step S3, the preparation of modifier: the consumption proportion according to vinylite, promotor, initiator is 100:2:1,
In ice-water bath, 15min is sufficiently stirred, 60min is stood, until the bubble in resin is sufficiently discharged；
Step S4, absorption, solidification: pretreated basalt fibre neatly, is uniformly placed in custom mold, closing is fixed
Molding jig is uniformly passed through resin modified in custom mold, until being completely exhausted out the air in custom mold；Slider box is pushed, until
Custom mold volume is the 2/3 of original volume；2~3h of room temperature;
Step S5, shaping: taking out the basalt fibre in grinding tool, makes simple finishing reason to the solidified resin of surrounding.
In a further embodiment, the aziridines substance and monocarboxylic acid reaction product structural formula such as following figure institute
Show:
R is C1-C6The alkyl containing various different isomerization forms, R1 be-H or-CH3, R2 be-H or-CH3；X be 0 or 1 it is whole
Number, the integer that y is 0~20, the integer that z is 0~10；The integer that m is 2 or 3.
In a further embodiment, the configuration method of the treatment fluid of the silane coupling agent are as follows: by isopropanol and distillation
Then water weighs quantitative silane coupling agent K560 according to the ratio mixing for standby use of 1:2, isopropanol is added and distilled water dissolves,
Then the solution of 0.05mol/L is configured to by volumetric flask constant volume.
In a further embodiment, the basalt fibre is various fabrics made of the braiding of various basalt fibres,
Specially yarn, felt, knitted fabric.
In a further embodiment, the custom mold includes: the lower die that inner surface is coated with one layer of permanent release agent
Tool, the slider box being slidably mounted on the lower mold are arranged in the ambilateral resin inlet of the lower die and resin outlet, if
Set the triple valve on institute resin inlet and resin outlet；Wherein, resin inlet is connected with the glue bucket equipped with modifier；
Resin outlet is connected with vacuum pump；Layer and the poly- opening of lower die are lined between basalt fibre after the completion of slider box and placement
The sheet glass to match.
It in a further embodiment, can be by the multiple customization when basalt fiber composite material is mass produced
Mold is cascaded, while processing to multiple custom molds.
In a further embodiment, the initiator is specially oxidation -2- butanone, cyclohexanone peroxide, peroxidating uncle
Pentanoic acid tert-butyl ester.
In a further embodiment, the promotor is specially epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, zinc Isoocatanoate.
The utility model has the advantages that the present invention relates to a kind of composite material preparation sides based on vinylite treated basalt fiber
Method reacts the aziridine vinylite of synthesis as modifier with monocarboxylic acid by aziridines substance；Wherein, nitrogen
Third piperidinyl group is to connect on silane coupling agent K560 on dipole moment containing carboxylic acid systems biggish electron-withdrawing group, with basalt fibre
Electron-donating group between, have stronger binding ability；On the other hand pass through optimization solidification, absorbing process medium vinyl tree
Rouge, promotor, initiator proportion, optimize immobilization technology, further increase the binding ability of organic resin and basalt fibre；
The raising production efficiency of basalt fibre is greatly improved while guaranteeing modified solidified effect using custom mold simultaneously.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of custom mold in the present invention.
Fig. 2 is that the embodiment of the present invention 1, embodiment 4 and other comparative experimentss are promoted agent/vinylite quality
Resin quality percentage in percentage and fixative/vinylite mass percent and basalt fiber composite material finished product
Change curve.
Fig. 3 is the washing fastness and rub resistance of resin in basalt fiber composite material that the embodiment of the present invention 1~4 obtains
Fastness data.
Specific embodiment
In the following description, a large amount of concrete details are given so as to provide a more thorough understanding of the present invention.So
And it is obvious to the skilled person that the present invention may not need one or more of these details and be able to
Implement.In other examples, in order to avoid confusion with the present invention, for some technical characteristics well known in the art not into
Row description.
Applicant's rear discovery on carefully studying the prior art: in existing basalt fibre production process, fiber surface quilt
It is coated with one layer of not capacitive lipidic compounds or Nano-meter SiO_22Particle, so as to improve the degree of roughness of fibrous outer surfaces.On the one hand,
Surface increases Nano-meter SiO_22The higher cost of particle, therefore the popularity of the technique is smaller；On the other hand, due to basalt fibre
Dimension table face is more smooth, and surface can be lower, and the combination degree mostly between organic matter is inadequate, leads to coating not capacitive grease chemical combination
The service life of the basalt fibre of object is shorter.Therefore, Basalt fiber surface modification influences especially the performance of composite material
It is important.
Applicant is carefully studying and is verifying discovery by Experimental comparison: being reacted by aziridines substance with monocarboxylic acid
The aziridine vinylite of synthesis has the function of more powerful as cooperation between modifier and silane coupling agent K560
Power；Wherein, aziridine group is the silane connected on dipole moment containing carboxylic acid systems biggish electron-withdrawing group, with basalt fibre
The active force between electron-donating group on coupling agent K560, the effect between significantly larger than other resinoids and basalt fibre
Power, so as to improve the service life of basalt fibre.Meanwhile applicant also passes through optimization solidification, absorbing process medium vinyl tree
Rouge, promotor, initiator proportion, optimize immobilization technology, further increase the binding ability of organic resin and basalt fibre；
Finally, applicant improves existing mold according to the preparation characteristic of this basalt fibre, it can not only using custom mold
Enough while guaranteeing modified solidified effect, and greatly improve the raising production efficiency of basalt fibre.
The example of the embodiment of the embodiment described is intended to explain the present invention, and is not considered as limiting the invention,
Particular technique and reaction condition person are not specified in embodiment, it can described technology or conditions or production according to the literature in the art
Product specification carries out.All reagents or instrument that manufacturer is not specified, can pass through commercially available acquisition.
Embodiment 1
A kind of composite material and preparation method thereof based on vinylite treated basalt fiber, synthesis step are specific as follows:
Step S1, the pretreatment of basalt fibre: basalt fibre product is put into according to bath raio 1:3 and is placed with silane coupling agent
In treatment fluid；It after immersion treatment 30min, is put into 105 DEG C of air dry oven, dry 45h is cooling stand-by；
Step S2, the preparation of vinylite material: 450g tri (propylene glycol) diacrylate is weighed, 200g is added thereto
Acrylic acid and 0.5g(500ppm) it tert-butyl hydroquinone and is uniformly mixed, 350g aziridine (structure such as following figure institute is slowly added dropwise
Show), pale yellow viscous liquid is obtained after 6h is reacted after being added dropwise to complete.
Step S3, the preparation of modifier: according to vinylite, epoxyeicosatrienoic acid cobalt, oxidation -2- butanone consumption proportion
15min is sufficiently stirred in ice-water bath for 100:2:1,60min is stood, until the bubble in resin is sufficiently discharged；
Step S4, absorption, solidification: pretreated basalt fibre neatly, is uniformly placed in custom mold, closing is fixed
Molding jig is uniformly passed through resin modified in custom mold, until being completely exhausted out the air in custom mold；Slider box is pushed, until
Custom mold volume is the 2/3 of original volume；2~3h of room temperature;
Step S5, shaping: taking out the basalt fibre in grinding tool, makes simple finishing reason to the solidified resin of surrounding.
Aziridine vinylite structure:
Wherein, x=1, y=0, z=0, m=3, R: R1:-CH3, R2:-H
As a preferred embodiment, the configuration method of the treatment fluid of the silane coupling agent are as follows: by isopropanol and distilled water according to
Then the ratio mixing for standby use of 1:2 weighs quantitative silane coupling agent K560, isopropanol is added and distilled water dissolves, then leads to
Overcapacity bottle constant volume is configured to the solution of 0.05mol/L.The basalt fibre is each made of the braiding of various basalt fibres
Kind fabric, specially yarn, felt, knitted fabric.
The custom mold includes: lower mold 1, slider box 2, resin inlet 3, resin outlet 4, triple valve 5, sheet glass 6.
It is coated with one layer of permanent release agent in the inner surface of lower mold 1, slider box 2 is slidably fitted on the lower mold 1, pushes and slides
Dynamic frame 2, thus it is possible to vary the volume size of custom mold.Lower 1 two sides of mold are provided with resin inlet 3 and resin outlet 4,
Triple valve 5 is installed on institute's resin inlet 3 and resin outlet 4, triple valve 5 plays the role of a resin modified liquid distribution,
Change the flow rate of resin modified also for being driven the quickening of resin modified liquid, carrys out more uniform the assigning of resin.Wherein, it sets
Rouge entrance 3 is connected with the glue bucket equipped with modifier；Resin outlet 4 is connected with vacuum pump；During pushing, in order to make
The upper surface of basalt fibre 7 keeps flatness, therefore is lined with layer between the basalt fibre 7 after the completion of slider box 2 and placement
The sheet glass 6 to match with the poly- opening of lower die.It, can will be described more in large-scale serial production 7 composite material of basalt fibre
A custom mold is cascaded, while processing to multiple custom molds.By sharing a glue bucket and vacuum pump control
The homogeneity of the mobility of resin modified liquid in each custom mold can not only greatly improve the production function of basalt fibre 7
Rate, moreover it is possible to reduce the otherness with batch products.
Embodiment 2
The present embodiment is difference from example 1 is that step S1: used silane coupling agent is fertile blue treatment fluid.Remaining
Step is same as Example 1.
Embodiment 3
The present embodiment is difference from example 1 is that step S2: " preparation of vinylite material " replaces with " phenolic aldehyde
The preparation of resin " can directly be bought on the market.Remaining step is same as Example 1.
Embodiment 4
The present embodiment is difference from example 1 is that step S3: the preparation of modifier, by vinylite, promotes
Agent, initiator consumption proportion replace with 100:1:1.Remaining step is same as Example 1.
Experimental result is as shown in attached drawing 2~3.
Wherein, by comparative example 1, embodiment 4 and other comparative experimentss (in control according to vinylite, ring
Oxygen acid cobalt, oxidation -2- butanone consumption proportion be 100:X:1 or 100:2:Y, adjust separately the ratio of X, Y；Remaining step and reality
It is identical to apply example 1) be promoted agent/vinylite mass percent and fixative/vinylite mass percent with
The change curve of resin quality percentage in basalt fiber composite material finished product.
The ranking method of fastness to rubbing in the application are as follows: sample to be tested is placed on crock fastness instrument, in a level pressure
Rubbed in power with STANDARD ADJACENT FABRIC 200 numbers therewith, is carried out to the dosage for the modifier being stained on STANDARD ADJACENT FABRIC
Grading, resulting series is exactly surveyed colorfastness to rubbing, wherein up to 5 grades, contained resin changes on STANDARD ADJACENT FABRIC
Property agent content be sample to be tested contain the 0 ~ 5% of resin modified agent content；Minimum 1 grade, contained resin on STANDARD ADJACENT FABRIC
Modifier content is greater than sample to be tested and contains the 20% of resin modified agent content.
The ranking method of washing fastness in the application are as follows: sample to be tested and STANDARD ADJACENT FABRIC are stitched together,
Washed, cleaning and drying, are washed under scheduled temperature, basicity, bleaching and friction condition, are made in a relatively short period of time
Obtain test result.The rolling for the stainless shot for being 5cm by short liquor ratio and multiple diameters, the friction hit between fabric are made
With.Wherein, up to 5 grades, contained resin modified agent content is that sample to be tested contains modifier on STANDARD ADJACENT FABRIC
The 0 ~ 5% of content；Minimum 1 grade, contained resin modified agent content contains resin greater than sample to be tested and changes on STANDARD ADJACENT FABRIC
The 20% of property agent content.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
Claims (8)
1. a kind of composite material and preparation method thereof based on vinylite treated basalt fiber, which is characterized in that including as follows
Step:
Step S1, the pretreatment of basalt fibre: according to bath raio 1:(3~4) basalt fibre product is put into be placed with silane idol
In the treatment fluid for joining agent；It after immersion treatment 30min, is put into 105 DEG C of air dry oven, dry 30~45h is cooling stand-by；
Step S2, the preparation of vinylite material:
Step S201, ingredient:
30 ~ 45wt% of tri (propylene glycol) diacrylate；
8 ~ 20wt of acrylic acid %；
30 ~ 60wt of aziridine %；
Tert-butyl hydroquinone 200-500ppm；
Step S202, esters of unsaturated carboxylic acids, unsaturated carboxylic acid and polymerization inhibitor are sequentially added into reaction kettle；
Step S203, under room temperature, aziridines substance is added drop-wise in reaction kettle, is stirred when being added dropwise, makes aziridines substance
With unsaturated monocarboxylic acid energy homogeneous reaction, keep exothermic heat of reaction uniform, this process will strictly monitor material temperature in kettle, such as more than 60
DEG C, then it should lead to cooling water and cool down, discharge after 6h filling；
Step S3, the preparation of modifier: the consumption proportion according to vinylite, promotor, initiator is 100:2:1,
In ice-water bath, 15min is sufficiently stirred, 60min is stood, until the bubble in resin is sufficiently discharged；
Step S4, absorption, solidification: pretreated basalt fibre neatly, is uniformly placed in custom mold, closing is fixed
Molding jig is uniformly passed through resin modified in custom mold, until being completely exhausted out the air in custom mold；Slider box is pushed, until
Custom mold volume is the 2/3 of original volume；2~3h of room temperature;
Step S5, shaping: taking out the basalt fibre in grinding tool, makes simple finishing reason to the solidified resin of surrounding.
2. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is that the aziridines substance and monocarboxylic acid reaction product structural formula are as shown below:
R is C1-C6The alkyl containing various different isomerization forms, R1 be-H or-CH3, R2 is-H or-CH3；X be 0 or 1 it is whole
Number, the integer that y is 0~20, the integer that z is 0~10；The integer that m is 2 or 3.
3. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is, the configuration method of the treatment fluid of the silane coupling agent are as follows: mixes according to the ratio of 1:2 isopropanol and distilled water standby
With then weighing quantitative silane coupling agent K560, isopropanol be added and distilled water dissolves, then passes through volumetric flask constant volume configuration
At the solution of 0.05mol/L.
4. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is that the basalt fibre is various fabrics, specially yarn, felt, knitting made of the braiding of various basalt fibres
Object.
5. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is that the custom mold includes: the lower mold that inner surface is coated with one layer of permanent release agent, is slidably mounted on the lower die
Slider box on tool, setting are arranged in the ambilateral resin inlet of the lower die and resin outlet in institute's resin inlet and resin
Triple valve in outlet；Wherein, resin inlet is connected with the glue bucket equipped with modifier；Resin outlet is connected with vacuum pump
It connects；Layer and the poly- sheet glass to match that is open of lower die are lined between basalt fibre after the completion of slider box and placement.
6. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is, when basalt fiber composite material is mass produced, multiple custom molds can be cascaded, while to multiple
Custom mold is processed.
7. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is that the initiator is specially oxidation -2- butanone, cyclohexanone peroxide, peroxidating trimethylacetic acid tertiary butyl ester.
8. the composite material and preparation method thereof according to claim 1 based on vinylite treated basalt fiber, special
Sign is that the promotor is specially epoxyeicosatrienoic acid cobalt, cobalt iso-octoate, zinc Isoocatanoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410926.0A CN110128646A (en) | 2019-05-17 | 2019-05-17 | A kind of composite material and preparation method thereof based on vinylite treated basalt fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410926.0A CN110128646A (en) | 2019-05-17 | 2019-05-17 | A kind of composite material and preparation method thereof based on vinylite treated basalt fiber |
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| CN110128646A true CN110128646A (en) | 2019-08-16 |
Family
ID=67575013
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910410926.0A Withdrawn CN110128646A (en) | 2019-05-17 | 2019-05-17 | A kind of composite material and preparation method thereof based on vinylite treated basalt fiber |
Country Status (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154181A (en) * | 2019-12-19 | 2020-05-15 | 会通新材料股份有限公司 | Polypropylene composite material with high mechanical strength and low dielectric constant and preparation method thereof |
| CN111844795A (en) * | 2020-06-08 | 2020-10-30 | 安徽宏飞钓具有限公司 | Preparation method of leisure bionic equipment based on high-performance fiber composite material |
-
2019
- 2019-05-17 CN CN201910410926.0A patent/CN110128646A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154181A (en) * | 2019-12-19 | 2020-05-15 | 会通新材料股份有限公司 | Polypropylene composite material with high mechanical strength and low dielectric constant and preparation method thereof |
| CN111154181B (en) * | 2019-12-19 | 2022-07-08 | 会通新材料股份有限公司 | Polypropylene composite material with high mechanical strength and low dielectric constant and preparation method thereof |
| CN111844795A (en) * | 2020-06-08 | 2020-10-30 | 安徽宏飞钓具有限公司 | Preparation method of leisure bionic equipment based on high-performance fiber composite material |
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Application publication date: 20190816 |
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