CN113880459A - Polyamide acid enhanced basalt fiber impregnating compound and synthetic method thereof - Google Patents
Polyamide acid enhanced basalt fiber impregnating compound and synthetic method thereof Download PDFInfo
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- CN113880459A CN113880459A CN202111369419.0A CN202111369419A CN113880459A CN 113880459 A CN113880459 A CN 113880459A CN 202111369419 A CN202111369419 A CN 202111369419A CN 113880459 A CN113880459 A CN 113880459A
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- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims abstract description 16
- 239000004952 Polyamide Substances 0.000 title claims abstract description 15
- 229920002647 polyamide Polymers 0.000 title claims abstract description 15
- 238000010189 synthetic method Methods 0.000 title description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- -1 dimethyl diphenyl ether Chemical compound 0.000 claims abstract description 22
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 10
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229940113088 dimethylacetamide Drugs 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 11
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 239000000243 solution Substances 0.000 abstract description 89
- 230000000694 effects Effects 0.000 abstract description 4
- 229920001721 polyimide Polymers 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000004642 Polyimide Substances 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to the technical field of preparation and application of basalt fibers, and particularly relates to a polyamide acid enhanced basalt fiber impregnating compound and a synthesis method thereof. The polyamide acid film-forming agent is prepared by compounding a synthetic polyamide acid film-forming agent and gamma-glycidyl ether oxypropyl trimethoxy silane, wherein the film-forming agent comprises 2-4% of pyromellitic dianhydride, 2-4% of dimethyl diphenyl ether, 38-42% of dimethylacetamide, 0.5-1.5% of triethylamine and the balance of water in percentage by mass; the impregnating compound comprises, by mass, 10-20% of a film-forming agent, 0.2-1.2% of gamma-glycidyl ether oxypropyl trimethoxysilane and the balance of deionized water. The alkali-resistant enhanced basalt fiber impregnating compound provided by the invention is prepared by adding pyromellitic dianhydride and dimethyl diphenyl ether into dimethylacetamide, uniformly dispersing, carrying out low-temperature polycondensation for 8-12 h to obtain a precursor solution, adding triethylamine and deionized water to react to obtain a polyamide acid film-forming agent, and finally compounding with gamma-glycidyl ether oxypropyl trimethoxysilane. The main component of the impregnating compound is polyamic acid, and a large number of hydrophilic group carboxyl exists in functional groups of the impregnating compound, so that a high polymer aqueous solution is formed; and polyimide obtained by thermal imidization of polyamic acid has great enhancement effect on basalt fiber.
Description
Technical Field
The invention belongs to the technical field of basalt fiber preparation, and particularly relates to a polyamide acid enhanced basalt fiber impregnating compound and a synthesis method thereof.
Background
With the increasing environmental protection in the world, new environmental protection materials are receiving more attention. The basalt fiber is used as a novel inorganic environment-friendly high-performance material in the 21 st century, the raw material mineral resources of the basalt fiber are abundant in China, and the basalt fiber is listed as one of four major fibers which are mainly developed in China, so that the industrial production is realized.
In basalt fiber production enterprises, basalt fibers are almost subjected to impregnating compound (also called sizing agent) coating and drying treatment. The impregnating compound plays an important role in the fiber manufacturing and subsequent application processes, not only lubricates parts of a drawing process, but also integrates hundreds of and even thousands of fiber monofilaments into a bundle; not only prevents the fiber from generating filoplume in the subsequent process, but also enables the resin to quickly infiltrate the surface of the fiber and even generates certain chemical bonds at the interface. The sizing agents can be classified into textile type sizing agents, reinforcing textile type sizing agents and reinforcing type sizing agents according to the purpose of the fiber. The main components of the impregnating compound are a film forming agent, a coupling agent and the like, wherein the film forming agent accounts for the largest proportion in the formula of the impregnating compound, and the film forming agent has the largest influence on fibers and interfaces, so that the impregnating compound is the key point for the research of the impregnating compound.
The main reason of using the polyamic acid as the film forming agent in the impregnating compound is that the polyamic acid has a hydrophilic group carboxyl group and can be dissolved in water, so that the possibility is provided for preparing the water-based high polymer film forming agent; and the product polyimide after thermal imidization has excellent physical and chemical properties. Because polyamic acid is used as an organic film forming agent and is weakly combined with an inorganic material basalt fiber interface, a silane coupling agent can be introduced to be used as a medium to establish a Si-O-C bond bridge, and the optimal basalt fiber surface modification is achieved by regulating and controlling the proportion of the film forming agent and the coupling agent.
Kuzmin K L and the like carry out surface modification on basalt fibers by using a silane coupling agent and nano silicon dioxide, and the tensile strength of the fiber is improved by 23% after silane modification, which shows that silane plays an important role in maintaining the strength of the basalt fibers. (Kuzmin K L, Timoshkin I A, Gutnikov S I, et al. Effect of silane/nano-silicon on the mechanical properties of basic transformed epoxy compositions [ J]Composite Interfaces,2017,24(1): 13-34) but the increased tensile strength is not significant enough to support basalt fibers to stand out in the resin-based Composite field. The Cao hailin and the like adopt a sol-gel technology to prepare organic/inorganic nano hybrid coating materials, and the synthesized nano hybrid slurry is used for carrying out surface modification on basalt fibers, so that the fiber surface roughness can be effectively increased, the tensile strength of fiber multifilament is improved, and the interface bonding strength of a composite material is improved. (Caohalin, Zhanhong, Zhanzhi, etc.. basalt fiber surface coating modification study [ J]The aeronautical materials journal, 2007,27(5): 6) but the method has the disadvantages that the raw materials are mostly synthesized by organic matters, which is not favorable for the environmental protection concept; long reaction period, high cost and the like. Wuzhiren et al propose polyacrylamide/water-based epoxy resin/nano SiO2Composite emulsion para-concentrated H2SO4/H2O2The basalt fiber after the mixed solution and the hydrochloric acid etching is subjected to surface coating modification, so that the basalt fiber can be quickly and effectively modified, and the surface roughness of the basalt fiber is obviously increased. (Wuzhiren, Zhang Xiaoying, Tong Wen, etc. A preparation method and application of basalt fiber surface modified coating, CN107640913A [ P ]]But the method utilizes acid etching to remove the surface activity of the basalt fiber, destroys the inherent property of the basalt fiber and has great damage to the fiber.
At present, most of basalt fiber impregnating compounds adopt glass fiber impregnating compounds, so that the development of the impregnating compounds special for the basalt fiber is limited, and the impregnating compounds have adverse effects on the application field of the basalt fiber in high-performance fiber. The polyamic acid impregnating compound is used as a high-performance material after thermal curing, great advantage is given to the surface modification of the basalt fiber, and the surface roughness and the bundling property of the basalt fiber after sizing are enhanced by uniform dispersion of the polyamic acid in water. The synthesis method provided by the invention has the advantages of easily available raw materials, simple process, low cost and environmental protection, and provides a new scheme with low cost for the basalt fiber impregnating compound for selective industrial production in the future.
Disclosure of Invention
Aiming at the defects that most of the conventional basalt fiber impregnating compounds adopt glass fiber impregnating compounds, the tensile strength is not remarkably improved, the environment is not good enough, the performance of the fiber is damaged, and the like, the invention aims to solve the technical problem of providing the enhanced basalt fiber impregnating compound and the synthetic method thereof, which are environment-friendly. When the polyamic acid is used as a film forming agent, a reinforced polyimide film can be formed on the surface of the fiber, so that the bundling property and the surface roughness of the fiber are possible; the coupling agent is used as a medium bridge and enhances the bonding strength between the fiber and the film through Si-O-C bonds. The water-based polymer impregnating compound can effectively wet the surface of the basalt fiber, is more suitable for industrialization, and is simple, convenient and feasible.
The polyamide acid reinforced basalt fiber impregnating compound comprises the following synthetic steps:
A. adopting a low-temperature polycondensation method to synthesize a polyamic acid film-forming agent;
(1) the main raw materials comprise 2-4% of pyromellitic dianhydride, 2-4% of dimethyl diphenyl ether, 38-42% of dimethylacetamide, 0.5-1.5% of triethylamine and the balance of deionized water;
(2) adding dimethyl diphenyl ether into dimethyl acetamide, and stirring at room temperature for 3-5 min until the dimethyl diphenyl ether is fully dissolved to obtain a solution I;
(3) adding pyromellitic dianhydride into the solution I at the ambient temperature of 10-20 ℃ under the stirring condition of 300-500 r/min, and continuously stirring for 8-12 h to obtain a precursor solution II;
(4) after the temperature of the solution II is recovered to the room temperature, adding triethylamine into the solution II, and continuing stirring for 30min to obtain a solution III;
(5) and adding deionized water into the solution (c), and stirring at an ambient temperature of 20-30 ℃ and a rotating speed of 500-700 r/min for 30-90 min to obtain the polyamic acid film-forming agent.
B. And D, compounding the polyamic acid film forming agent obtained in the step A and gamma-glycidyl ether oxypropyl trimethoxy silane to obtain the polyamic acid impregnating compound.
(1) The main raw materials comprise a polyamide acid film forming agent, gamma-glycidyl ether oxygen propyl trimethoxy silane and water, wherein the mass ratio of the raw materials is 10-20% of the polyamide acid film forming agent, 0.2-1.2% of the gamma-glycidyl ether oxygen propyl trimethoxy silane and the balance of deionized water;
(2) diluting gamma-glycidoxypropyltrimethoxysilane by 20-30 times by using deionized water, adding glacial acetic acid, adjusting the pH value of the solution to 3-4, stirring for 1-3 h, and then adjusting the pH value of the solution to 6-7 to obtain a solution (r);
(3) adding the solution (IV) and a polyamic acid film forming agent into deionized water, and stirring for 1-3 hours to obtain a polyamic acid impregnating compound
The technology provides a synthetic method of a polyamide acid enhanced basalt fiber impregnating compound. The polyamide acid is used as a film forming agent, so that the basalt fiber can be effectively enhanced; meanwhile, the synthesis process is simpler, green and environment-friendly, saves cost, has the characteristics of good parallelism, repeatability, operability and the like, has better practicability, and has wide industrial application value.
Drawings
FIG. 1 is an FTIR spectrum of a polyamic acid impregnating agent synthesized in example 1;
FIG. 2 is an SEM photograph of an un-surface modified basalt fiber;
FIG. 3 is an SEM photograph of the surface modified basalt fiber of the polyamic acid impregnating agent synthesized in example 1;
fig. 4 is a comparison of tensile strength of basalt fiber before and after coating with the sizing agent.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
3.3848g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 3.6966g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 400r/min at the ambient temperature of 10 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1.5ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the room temperature for 1h at the rotating speed of 550r/min to form the polyamic acid film-forming agent. 0.5944g of gamma-glycidoxypropyltrimethoxysilane is weighed, 18.0214g of deionized water is added to dilute by 30 times, glacial acetic acid is added, the pH value of the solution is adjusted to be 3.4, and after stirring for 1 hour, the pH value of the solution is 6.6, and a solution (r) is obtained. Adding the solution (r) and 15.0112g of polyamic acid film forming agent into 66.4215g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
Example 2
3.3896g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 3.6917g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 350r/min at the ambient temperature of 12 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1.3ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the rotating speed of 600r/min for 1h at room temperature to form the polyamic acid film-forming agent. Weighing 0.6023g of gamma-glycidoxypropyltrimethoxysilane, adding 17.9965g of deionized water to dilute by 30 times, adding glacial acetic acid, adjusting the pH value of the solution to 3.2, stirring for 1h, and then adjusting the pH value of the solution to 6.8 to obtain a solution ((r)). Adding the solution (r) and 15.0076g of polyamic acid film forming agent into 66.4036g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
Example 3
3.3864g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 3.6906g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 420r/min at the ambient temperature of 16 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1.5ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the room temperature for 1h at the rotating speed of 650r/min to form the polyamic acid film-forming agent. 0.4024g of gamma-glycidoxypropyltrimethoxysilane is weighed, 7.9986g of deionized water is added to dilute the gamma-glycidoxypropyltrimethoxysilane by 20 times, glacial acetic acid is added, the pH value of the solution is adjusted to be 3.6, and after stirring for 1 hour, the pH value of the solution is 6.7, so that a solution (r) is obtained. Adding solution (r) and 13.6024g of polyamic acid film forming agent into 78.6031g of deionized water, and stirring for 1h to obtain polyamic acid impregnating compound
Example 4
3.3902g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 3.6803g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 380r/min at the ambient temperature of 12 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1.2ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the rotating speed of 620r/min for 1h at room temperature to form the polyamic acid film-forming agent. Weighing 1.0025g of gamma-glycidoxypropyltrimethoxysilane, adding 30.0014g of deionized water to dilute by 30 times, adding glacial acetic acid, adjusting the pH value of the solution to 3.8, stirring for 1h, and then adjusting the pH value of the solution to 6.9 to obtain a solution. Adding the solution (r) and 14.0164g of polyamic acid film forming agent into 55.0046g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
Example 5
3.3821g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 3.6902g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 450r/min at the ambient temperature of 13 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1.4ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the room temperature for 1h at the rotating speed of 550r/min to form the polyamic acid film-forming agent. 0.8011g of gamma-glycidoxypropyltrimethoxysilane is weighed, 20.0136g of deionized water is added to dilute the gamma-glycidoxypropyltrimethoxysilane by 25 times, glacial acetic acid is added, the pH value of the solution is adjusted to be 3.2, and after stirring for 1 hour, the pH value of the solution is 6.6, so that a solution (r) is obtained. Adding the solution (r) and 15.0112g of polyamic acid film forming agent into 64.2012g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
Example 6
2.0028g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 2.1829g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 350r/min at the ambient temperature of 20 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 0.5ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the room temperature at the rotating speed of 500r/min for 1h to form the polyamic acid film-forming agent. 0.2011g of gamma-glycidoxypropyltrimethoxysilane is weighed, 6.0125g of deionized water is added to dilute by 30 times, glacial acetic acid is added, the pH value of the solution is adjusted to be 3.2, and after stirring for 1 hour, the pH value of the solution is 6.6, so that a solution (r) is obtained. Adding the solution (r) and 19.9986g of polyamic acid film forming agent into 73.8022g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
Example 7
2.0045g of dimethyl diphenyl ether (the content of dimethyl diphenyl ether is 99 wt%) is weighed, 40ml of dimethylacetamide (the content of dimethylacetamide is 99 wt%) is added, and the mixture is stirred at room temperature for 3min to obtain a solution (r). 2.2004g of pyromellitic dianhydride (the content of the pyromellitic dianhydride is 99 wt%) is weighed and added into the solution I, and the mixture is stirred for 8 hours at the stirring speed of 350r/min at the ambient temperature of 10 ℃ to obtain a precursor solution II. And (3) after the temperature of the solution II is returned to the room temperature, adding 1ml of triethylamine into the solution II, and continuously stirring for 30min to obtain a solution III. And adding 60ml of deionized water into the solution (c), and stirring at the room temperature for 1h at the rotating speed of 550r/min to form the polyamic acid film-forming agent. 1.2012g of gamma-glycidoxypropyltrimethoxysilane is weighed, 36.0016g of deionized water is added to dilute by 30 times, glacial acetic acid is added, the pH value of the solution is adjusted to be 3.0, and after stirring for 1 hour, the pH value of the solution is 6.9, so that a solution (r) is obtained. Adding the solution (r) and 20.0122g of polyamic acid film forming agent into 42.0068g of deionized water, and stirring for 1h to obtain the polyamic acid impregnating compound.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (4)
1. A polyamide acid enhanced basalt fiber impregnating compound is characterized in that: the color of the impregnating compound is milky yellow.
2. The polyamic acid enhanced basalt fiber sizing agent according to claim 1, wherein the synthesis method comprises the following steps:
A. adopting a low-temperature polycondensation method to synthesize a polyamic acid film-forming agent;
B. and D, compounding the polyamic acid film forming agent obtained in the step A and gamma-glycidyl ether oxypropyl trimethoxy silane to obtain the polyamic acid impregnating compound.
3. The method for synthesizing the polyamic acid enhanced basalt fiber sizing agent according to claim 2, wherein the step A of synthesizing the polyamic acid film forming agent specifically comprises the following steps:
(1) the main raw materials comprise 2-4% of pyromellitic dianhydride, 2-4% of dimethyl diphenyl ether, 38-42% of dimethylacetamide, 0.5-1.5% of triethylamine and the balance of deionized water;
(2) adding dimethyl diphenyl ether into dimethyl acetamide, and stirring at room temperature until the dimethyl diphenyl ether is fully dissolved to obtain a solution I;
(3) adding pyromellitic dianhydride into the solution I at the ambient temperature of 10-20 ℃ under the stirring condition of 300-500 r/min, and continuously stirring for 8-12 h to obtain a precursor solution II;
(4) after the temperature of the solution II is recovered to the room temperature, adding triethylamine into the solution II, and continuously stirring to obtain a solution III;
(5) and adding deionized water into the solution (c), and stirring at an ambient temperature of 20-30 ℃ and a rotating speed of 500-700 r/min for 30-90 min to obtain the polyamic acid film-forming agent.
4. The method for synthesizing the polyamic acid material-reinforced basalt fiber-dedicated sizing agent according to claim 2, wherein the polyamic acid sizing agent of step B specifically comprises the steps of:
(1) the main raw materials comprise a polyamide acid film forming agent, gamma-glycidyl ether oxygen propyl trimethoxy silane and water, wherein the mass ratio of the raw materials is 10-20% of the polyamide acid film forming agent, 0.2-1.2% of the gamma-glycidyl ether oxygen propyl trimethoxy silane and the balance of deionized water;
(2) diluting gamma-glycidoxypropyltrimethoxysilane by 20-30 times by using deionized water, adding glacial acetic acid, adjusting the pH value of the solution to 3-4, stirring for 1-3 h, and then adjusting the pH value of the solution to 6-7 to obtain a solution (r);
(3) and adding the solution (IV) and the polyamic acid film forming agent into deionized water, and stirring for 1-3 h to obtain the polyamic acid impregnating compound.
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