CN116814078A - Light high-strength film material based on unidirectional fibers, preparation and application methods thereof - Google Patents
Light high-strength film material based on unidirectional fibers, preparation and application methods thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000000835 fiber Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 79
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 238000000071 blow moulding Methods 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 13
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 30
- 239000008213 purified water Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 23
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 20
- -1 methanol triethoxysilane Chemical compound 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 19
- 238000002074 melt spinning Methods 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 13
- 230000003712 anti-aging effect Effects 0.000 claims description 12
- 229920003235 aromatic polyamide Polymers 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- UQRLKWGPEVNVHT-UHFFFAOYSA-N 3,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC(Cl)=C1 UQRLKWGPEVNVHT-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 claims description 10
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- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 230000009194 climbing Effects 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
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- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 3
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
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- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- JSKQRADCWGNYQD-UHFFFAOYSA-N N.O.[Na] Chemical compound N.O.[Na] JSKQRADCWGNYQD-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
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- 238000007873 sieving Methods 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a light high-strength film material based on unidirectional fibers, a preparation method and an application method thereof, which belong to the technical field of film preparation, wherein modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives are subjected to blow molding by a blow molding machine after being extruded by a double screw extruder according to the dosage ratio of 20g to 0.3g to 7g to 5g to 3 g.
Description
Technical Field
The invention relates to the technical field of film preparation, in particular to a light high-strength film material based on unidirectional fibers, and a preparation method and an application method thereof.
Background
The film is a thin, soft transparent sheet. Mainly made of plastic, adhesive, rubber or other materials. The light high-strength film material has wide application potential in the fields of modern science and technology and engineering, has good mechanical strength and lower density, and is widely applied to the fields of aerospace, automobile manufacturing, construction and the like. Unidirectional fibers are a fibrous material having high strength and high rigidity, and the direction of fiber alignment exhibits linear unidirectional properties. This means that the strength and rigidity of the fiber is significantly higher than in the transverse direction in the length direction of the fiber.
The film in the prior art is usually formed by melting and blowing plastic or other materials by a blowing machine, but the existing film has poor mechanical properties and is easily damaged by external force, especially in high-temperature and low-temperature environments, the structure of the film is changed, so that the mechanical properties of the film are reduced, the film is more easily damaged in high-temperature or low-temperature environments, and the aramid fiber is a common unidirectional fiber which has excellent properties such as light weight, heat resistance, chemical resistance and the like, but has hard texture and certain brittleness, is difficult to process, modifies the aramid fiber, and can be used for preparing a composite aramid fiber with good flexibility. These materials have not only excellent mechanical properties but also excellent chemical resistance and heat resistance.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a light high-strength film material based on unidirectional fibers and a preparation method thereof, which are used for solving the technical problems that the existing film in the prior art has poor mechanical properties, is easily damaged by external force, particularly in high-temperature and low-temperature environments, the structure of the film is changed to lower the mechanical properties, and in high-temperature or low-temperature environments, the film is more easily damaged, the texture of the traditional aramid fibers is hard, and the film has a certain brittleness and is difficult to process.
The aim of the invention can be achieved by the following technical scheme:
a light high-strength film material based on unidirectional fibers is formed by blow molding of a blow molding machine after extrusion of modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives in a dosage ratio of 20g to 0.3g to 7g to 5g to 3g by a double-screw extruder;
the modified resin is prepared by performing polycondensation reaction on methanol triethoxysilane, diethoxymethylsilane and tetraethoxysilane in an ethanol environment to generate an intermediate I with hydroxyl end capping, performing esterification condensation on hydroxyl on the intermediate I and carboxyl on 5-amino isophthalic acid to prepare an intermediate II, performing further reaction on glycerol serving as a chain extender and the intermediate II to generate an intermediate III, and performing polycondensation reaction on epichlorohydrin and active functional groups on the intermediate III under the action of a catalyst to obtain the modified resin;
the composite aramid fiber is prepared by carrying out dehydration condensation on hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol, 3, 5-dichloroaniline and bisphenol A under the action of a catalyst to prepare a composite aramid crude product, reprocessing the composite aramid crude product to prepare the composite aramid, and preparing the composite aramid fiber by melt spinning.
Further, the additive consists of a plasticizer, a dispersing agent, a lubricant, an anti-aging agent and an antistatic agent according to the dosage ratio of 1g to 2g to 1g, wherein the plasticizer is one or more of dioctyl phthalate, diester phthalate, diisodecyl phthalate and tricresyl phosphate, the dispersing agent is one or more of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant is one of oleamide and microcrystalline paraffin, the anti-aging agent is one or two of an anti-aging agent DPPD, an anti-aging agent PPD and an anti-aging agent H, the antistatic agent is one or two of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and sodium p-nonylphenoxy propyl sulfonate, the temperature of 6 temperature sections from a feeding end to a discharging end of the twin-screw extruder is sequentially set to be 250 ℃, 260 ℃, 265 ℃ and the spindle rotation speed of the twin-screw extruder is 14r/min.
A preparation method of a light high-strength film material based on unidirectional fibers comprises the following steps:
s1, adding methanol triethoxysilane, diethoxymethylsilane, tetraethoxysilane and 10vt percent ethanol into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 45-55 ℃, adding triethylamine into the three-neck flask, adjusting the pH value of a system to be 8-9, carrying out heat preservation reaction for 4-6 hours, and carrying out post treatment to obtain an intermediate I;
the synthesis reaction principle of the intermediate I is as follows:
s2, adding the intermediate I, toluene, 5-amino isophthalic acid and a catalyst into a three-neck flask protected by nitrogen, stirring, heating the three-neck flask to 100-110 ℃, carrying out heat preservation reaction for 10-11h, and carrying out post treatment to obtain an intermediate II;
the synthesis reaction principle of the intermediate II is as follows:
s3, adding the intermediate II, glycerol, toluene and a catalyst into a three-neck flask, stirring, raising the temperature of the three-neck flask to 100-110 ℃, carrying out heat preservation reaction for 10-11h, and carrying out post treatment to obtain an intermediate III;
s4, adding the intermediate III and N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, adding a catalyst and epichlorohydrin into the three-neck flask, raising the temperature of the three-neck flask to 80-90 ℃, carrying out heat preservation reaction for 6-8h, and carrying out post treatment to obtain modified resin;
s5, adding the modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives into a double screw extruder, and transferring the mixture into a blow molding machine for blow molding after melt extrusion to obtain a film finished product.
Further, in the step S1, the dosage ratio of the triethoxysilane, the diethoxymethylsilane, the tetraethoxysilane and the 10vt percent ethanol is 1g to 5g to 6g to 20mL, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is increased to 60-80 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I.
Further, in the step S2, the dosage ratio of the intermediate I, toluene, 5-amino isophthalic acid and the catalyst is 2g:8mL:1.5g:0.3g, the catalyst is one of potassium carbonate and sodium carbonate, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, purified water is added into the three-neck flask, the three-neck flask is stirred for 10 to 15 minutes, and the three-neck flask is stood for liquid separation to obtain an intermediate II.
Further, in the step S3, the weight ratio of the intermediate II, glycerol, toluene and the catalyst is 10:1:25:0.1, the catalyst is one of potassium carbonate and sodium carbonate, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, purified water is added into the three-neck flask, the three-neck flask is stirred for 10 to 15 minutes, the three-neck flask is kept stand for liquid separation, an organic phase is transferred into a rotary evaporator, the water bath temperature is set to be 80 to 90 ℃, and the solvent is distilled off under reduced pressure, so that an intermediate III is obtained.
Further, in the step S4, the dosage ratio of the intermediate III, N-dimethylformamide to the epichlorohydrin is 1g to 3mL to 0.05g to 6g, the catalyst consists of tetrabutylammonium bromide and sodium hydroxide ammonium in a weight ratio of 1 to 4, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-neck flask is reduced to 30-50 ℃, suction filtration is carried out, the filtrate is distilled under reduced pressure until the filtrate is dried, a filter cake and purified water are added into a beaker according to the dosage ratio of 1g to 7mL, a large amount of solids are separated out, suction filtration is carried out, the filter cake is washed by the purified water and ethanol and then is transferred into a drying box with the temperature of 75-80 ℃, and vacuum drying is carried out until the weight is constant, thus obtaining the modified resin.
Further, the preparation method of the composite aramid fiber comprises the following steps:
a1, adding hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 3, 5-dichloroaniline, bisphenol A and N-methylpyrrolidone into a three-neck flask, stirring until the system is dissolved, adding toluene and a catalyst into the three-neck flask, increasing the temperature of the three-neck flask to 140-145 ℃, carrying out heat preservation reaction for 2-3 hours, increasing the temperature of the three-neck flask to 180-190 ℃, stirring, reacting until a pole climbing phenomenon appears, and carrying out aftertreatment to obtain a composite aramid crude product;
the synthesis reaction principle of the composite aramid crude product is as follows:
a2, adding 0.5M hydrochloric acid of the crude product of the composite aramid fiber into a three-neck flask, stirring, raising the temperature of the three-neck flask to 90-95 ℃, carrying out heat preservation treatment for 30-50min, carrying out suction filtration, leaching a filter cake with purified water, then carrying out suction drying, adding the filter cake and absolute ethyl alcohol into the three-neck flask, stirring, raising the temperature of the three-neck flask to 75-78 ℃, carrying out heat preservation treatment for 30-50min, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 60-70 ℃, and carrying out vacuum drying to constant weight to obtain the composite aramid fiber;
and A3, adding the composite aramid fiber into a melt spinning machine for melt spinning to prepare the composite aramid fiber.
Further, in the step A1, the molar ratio of hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol, 3, 5-dichloroaniline and bisphenol A is 17:4:24:3, the weight of the N-methylpyrrolidone is 6 times of that of the hydroquinone, the weight of the toluene is 0.3 times of that of the N-methylpyrrolidone, the catalyst is potassium carbonate, the weight of the catalyst is 0.01 times of that of the N-methylpyrrolidone, and the post-treatment operation comprises: adding purified water into a beaker, stirring, increasing the temperature of the beaker to 85-95 ℃, slowly adding the reaction system into the beaker, stirring for 30-50min, carrying out suction filtration, transferring a filter cake into a drying box with the temperature of 70-80 ℃, carrying out forced air drying to constant weight, crushing, and sieving with a 100-mesh screen to obtain a composite aramid crude product.
Further, in the step A2, the dosage ratio of the crude composite aramid fiber, the 0.5M hydrochloric acid and the ethanol is 1g:3mL:5mL.
Further, the application method of the light high-strength film material based on the unidirectional fibers comprises the steps of processing the film material into a film, uniformly coating an adhesive on the surface of the film, simultaneously arranging fiber filaments in the same direction and at the same angle, and bonding the fiber filaments under high pressure, wherein the pressure is set at 97-153 Pa, the pressure is gradually increased, and simultaneously, drying after compression to form the three-layer functional composite film.
The invention has the following beneficial effects:
1. when the film material is prepared, after methanol triethoxysilane, diethoxymethylsilane and tetraethoxysilane are dispersed in an ethanol environment, in an alkaline environment, after siloxane bonds are hydrolyzed and broken, silane molecules are condensed through siloxane bonds to generate a hydroxyl-terminated intermediate I with a reticular cross-linking structure, hydroxyl on the intermediate I and carboxyl on 5-amino isophthalic acid are subjected to esterification and condensation, 5-amino isophthalic acid is grafted to the end part of the intermediate I, glycerol is used as a chain extender to react, hydroxyl is subjected to further esterification and condensation with polycondensation to generate an intermediate III, and the intermediate III is subjected to condensation with an active functional group on the intermediate III under the action of a catalyst to generate modified resin with the reticular cross-linking structure; the modified resin contains a large number of silicon-oxygen bonds, the thermal expansion coefficient of polysiloxane is low, and the volume expansion or contraction degree is relatively small when the temperature is changed, so that the modified resin maintains the dimensional stability under the conditions of high temperature and low temperature, and the deformation and stress caused by the temperature change are reduced, so that the film material shows good mechanical properties in the high temperature and low temperature environment; epoxy resin generated by polycondensation of epichlorohydrin under the action of a catalyst is crosslinked with polysiloxane through chemical bonds, so that the compatibility of the polysiloxane and the epoxy resin is effectively improved, and a polysiloxane chain segment in the modified resin has good flexibility and high and low temperature resistance and is matched with the epoxy resin, so that the high-strength modified resin is prepared, and the strength of the film material is further improved.
2. When the film material is prepared, the composite aramid fiber with a highly symmetrical structure is prepared by carrying out dehydration condensation on hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol, 3, 5-dichloroaniline and bisphenol A under the action of a catalyst, the crystallization temperature of the composite aramid fiber reaches 323+/-3 ℃, the high temperature resistance of the composite aramid fiber is improved, the composite aramid fiber is in a high temperature environment, the composite aramid fiber can still maintain good mechanical properties, a large amount of 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol is introduced into the composite aramid fiber, and a long straight-chain siloxane chain segment is used as a flexible chain segment of the composite aramid fiber, so that the softness of the composite aramid fiber is effectively improved, and the siloxane shows stable mechanical properties in a low-temperature environment, so that the composite aramid fiber still has good mechanical properties in the low-temperature environment; the composite aramid fiber and the modified resin both contain a large amount of silica chain segments, so that the structural similarity is improved, the composite aramid fiber can be fully mixed with the modified resin, the weak interface property of the mixed composite aramid fiber is reduced, and the composite aramid fiber, the modified resin and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid all contain amino or carboxyl and other active functional groups, and in a molten state, the isocyanate groups on toluene-2, 4-diisocyanate can react with the active functional groups, so that the crosslinking of the composite aramid fiber and the modified resin is improved, the strength of the film is further improved, the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid is a good antioxidant, and the mixed composite aramid fiber, the modified resin and the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid contain a large amount of aromatic rings, so that the percentage content of the aromatic rings on the film material is effectively improved, and the high temperature resistance and the oxidation resistance of the film material are further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of the synthesis of the high wear resistant film material of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a light high-strength film material based on unidirectional fibers, which comprises the following steps:
s1, preparing modified resin
Weighing: 10g of methanol triethoxysilane, 50g of diethoxymethylsilane, 60g of tetraethoxysilane and 200mL of 10vt percent ethanol are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 45 ℃, triethylamine is added into the three-neck flask, the pH=8 of the system is regulated, the temperature is kept for 4 hours for reaction, the temperature of the three-neck flask is increased to 60 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: 200g of intermediate I, 800mL of toluene, 150g of 5-amino isophthalic acid and 30g of potassium carbonate are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 100 ℃, the reaction is carried out for 10-11h under the heat preservation, water is separated by a water separator in the reaction process, the temperature of the three-neck flask is reduced to room temperature, 600mL of purified water is added into the three-neck flask, the three-neck flask is stirred for 10min, and the intermediate II is obtained after standing and liquid separation;
weighing: 1000g of intermediate II, 100g of glycerol, 2500g of toluene and 10g of potassium carbonate are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to 100 ℃, the three-neck flask is kept for reaction for 10 hours, the temperature of the three-neck flask is reduced to room temperature, 1000mL of purified water is added into the three-neck flask, the three-neck flask is stirred for 10 minutes, the three-neck flask is kept stand for liquid separation, an organic phase is transferred into a rotary evaporator, the water bath temperature is set to be 80 ℃, the solvent is distilled off under reduced pressure, and the intermediate III is obtained;
weighing: 50g of intermediate III and 150mL of N, N-dimethylformamide are added into a three-neck flask, stirred until the system is dissolved, 0.05g of tetrabutylammonium bromide, 0.20g of sodium hydroxide and 300g of epichlorohydrin are added into the three-neck flask, the temperature of the three-neck flask is increased to 80 ℃, the temperature of the three-neck flask is kept for 6 hours, the temperature of the three-neck flask is reduced to 30 ℃, the filtrate is distilled to dryness under reduced pressure, a filter cake and purified water are added into a beaker according to the dosage ratio of 1g to 7mL, a large amount of solids are separated out, the filtration is carried out, the filter cake is washed by the purified water and ethanol and then is transferred into a drying box with the temperature of 75 ℃, and the drying box is dried to constant weight under vacuum, thus obtaining the modified resin.
S2, preparing composite aramid fiber
Weighing: 187.2g of hydroquinone, 125.8g of 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 388.8g of 3, 5-dichlorophenylamine, 68.5g of bisphenol A and 1123.2g of N-methylpyrrolidone are added into a three-neck flask and stirred until the system is dissolved, 337g of toluene and 11.23g of potassium carbonate are added into the three-neck flask, the temperature of the three-neck flask is increased to 140-145 ℃, the reaction is kept for 2-3h, water serving as a byproduct is separated through a water separator in the reaction process, the temperature of the three-neck flask is increased to 180 ℃, stirring is carried out until the pole climbing phenomenon occurs, a beaker is taken, 7300g of purified water is added into the beaker and stirred, the temperature of the beaker is increased to 85 ℃, the reaction system is slowly added into the beaker, stirring is carried out for 30min, a suction filtration is carried out, the filter cake is transferred into a drying box with the temperature of 70 ℃, the drying box with blast and is dried to constant weight, and crushed, and a 100 screen is passed through to obtain a crude product of the composite aramid fiber;
weighing: adding 100g of a crude product of the composite aramid fiber and 300mL of 0.5M hydrochloric acid into a three-neck flask, stirring, heating the three-neck flask to 90 ℃, carrying out heat preservation treatment for 30min, carrying out suction filtration, leaching a filter cake with purified water, then carrying out suction drying, adding 500mL of absolute ethyl alcohol and the filter cake into the three-neck flask, stirring, heating the three-neck flask to 75 ℃, carrying out heat preservation treatment for 30min, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 60 ℃, and carrying out vacuum drying to constant weight to obtain the composite aramid fiber;
adding the composite aramid fiber into a melt spinning machine for melt spinning, cooling the melt spinning machine by adopting an air cooling mode, wherein the melting temperature of the melt spinning machine is 700 ℃, the size of a spinning die hole is 0.2mm, and the stretching speed is 400mm/min, so as to prepare the composite aramid fiber with the diameter of 10-12 mu m.
S3, preparing a film
Uniformly mixing dioctyl phthalate, calcium stearate, oleamide, an anti-aging agent DPPD and octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate according to the dosage ratio of 1g to 2g to 1g to obtain an additive;
the modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives are added into a double-screw extruder according to the dosage ratio of 20g to 0.3g to 7g to 5g to 3g, the temperature of 6 temperature sections from a feed end to a discharge end of the double-screw extruder is set to 250 ℃, 260 ℃, 265 ℃ and 265 ℃ in sequence, the spindle rotation speed of the double-screw extruder is 14r/min, the materials are extruded by the double-screw extruder and then enter a blow molding machine for blow molding, and the film material with the thickness of 0.1+/-0.01 mm is obtained, and multiple layers of film materials can be arranged.
Example 2
The embodiment provides a preparation method of a light high-strength film material based on unidirectional fibers, which comprises the following steps:
s1, preparing modified resin
Weighing: 10g of methanol triethoxysilane, 50g of diethoxymethylsilane, 60g of tetraethoxysilane and 200mL of 10vt percent ethanol are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 50 ℃, triethylamine is added into the three-neck flask, the pH=8.5 of the system is regulated, the temperature is kept for 5 hours for reaction, the temperature of the three-neck flask is increased to 70 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: 200g of intermediate I, 800mL of toluene, 150g of 5-amino isophthalic acid and 30g of sodium carbonate are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 105 ℃, the reaction is carried out for 10.5h under the heat preservation, water is separated by a water separator in the reaction process, the temperature of the three-neck flask is reduced to room temperature, 600mL of purified water is added into the three-neck flask, the three-neck flask is stirred for 10-15min, and the intermediate II is obtained after standing and liquid separation;
weighing: 1000g of intermediate II, 100g of glycerol, 2500g of toluene and 10g of sodium carbonate are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to 100-110 ℃, the temperature of the three-neck flask is kept for 10-11h, the temperature of the three-neck flask is reduced to room temperature, 1000mL of purified water is added into the three-neck flask to be stirred for 10-15min, the mixture is kept stand and separated, an organic phase is transferred into a rotary evaporator, the water bath temperature is set to be 85 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate III;
weighing: 50g of intermediate III and 150mL of N, N-dimethylformamide are added into a three-neck flask, stirred until the system is dissolved, 0.05g of tetrabutylammonium bromide, 0.20g of sodium hydroxide and 300g of epichlorohydrin are added into the three-neck flask, the temperature of the three-neck flask is increased to 85 ℃, the temperature of the three-neck flask is kept for 7 hours, the temperature of the three-neck flask is reduced to 40 ℃, the filtrate is distilled to dryness under reduced pressure, a filter cake and purified water are added into a beaker according to the dosage ratio of 1g to 7mL, a large amount of solids are separated out, the filtration is carried out, the filter cake is washed by the purified water and ethanol and then is transferred into a drying box with the temperature of 78 ℃, and the drying box is dried to constant weight under vacuum, thus obtaining the modified resin.
S2, preparing composite aramid fiber
Weighing: 187.2g of hydroquinone, 125.8g of 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 388.8g of 3, 5-dichlorophenylamine, 68.5g of bisphenol A and 1123.2g of N-methylpyrrolidone are added into a three-neck flask and stirred until the system is dissolved, 337g of toluene and 11.23g of potassium carbonate are added into the three-neck flask, the temperature of the three-neck flask is increased to 143 ℃, the reaction is carried out for 2.5h while maintaining, the water by-product is separated through a water separator during the reaction, the temperature of the three-neck flask is increased to 185 ℃, the stirring reaction is carried out until the phenomenon of climbing rods appears, a beaker is taken, 7300g of purified water is added into the beaker and stirred, the temperature is increased to 90 ℃, the reaction system is slowly added into the beaker, the stirring is carried out for 40min, the suction filtration is carried out, the filter cake is transferred into a drying box with the temperature of 75 ℃ and is dried to constant weight by blowing, and crushed, and 100 screens are passed through to obtain a crude product of the composite aramid fiber;
weighing: adding 100g of a crude product of the composite aramid fiber and 300mL of 0.5M hydrochloric acid into a three-neck flask, stirring, raising the temperature of the three-neck flask to 93 ℃, carrying out heat preservation treatment for 40min, carrying out suction filtration, leaching a filter cake with purified water, then carrying out suction drying, adding 500mL of absolute ethyl alcohol and the filter cake into the three-neck flask, stirring, raising the temperature of the three-neck flask to 77 ℃, carrying out heat preservation treatment for 40min, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 65 ℃, and carrying out vacuum drying to constant weight to obtain the composite aramid fiber;
adding the composite aramid fiber into a melt spinning machine for melt spinning, cooling the melt spinning machine by adopting an air cooling mode, wherein the melting temperature of the melt spinning machine is 715 ℃, the size of a spinning die hole is 0.2-0.3mm, and the stretching speed is 430m/min, so as to prepare the composite aramid fiber with the diameter of 10-12 mu m.
S3, preparing a film
Uniformly mixing phthalic diester, zinc stearate, microcrystalline paraffin, an antioxidant PPD and sodium p-nonylphenoxy propyl sulfonate according to the dosage ratio of 1g to 2g to 1g to obtain an additive;
the modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additive are added into a double-screw extruder according to the dosage ratio of 20g to 0.3g to 7g to 5g to 3g, the temperature of 6 temperature sections from a feed end to a discharge end of the double-screw extruder is set to 250 ℃, 260 ℃, 265 ℃ and 265 ℃ in sequence, the spindle rotation speed of the double-screw extruder is 14r/min, and the materials are extruded by the double-screw extruder and then enter a blow molding machine for blow molding, so that the film material with the thickness of 0.1+/-0.01 mm is obtained.
Example 3
The embodiment provides a preparation method of a light high-strength film material based on unidirectional fibers, which comprises the following steps:
s1, preparing modified resin
Weighing: 10g of methanol triethoxysilane, 50g of diethoxymethylsilane, 60g of tetraethoxysilane and 200mL of 10vt percent ethanol are added into a three-neck flask for stirring, the temperature of the three-neck flask is increased to 55 ℃, triethylamine is added into the three-neck flask, the pH=9 of the system is regulated, the temperature is kept for 6 hours for reaction, the temperature of the three-neck flask is increased to 80 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: 200g of intermediate I, 800mL of toluene, 150g of 5-amino isophthalic acid and 30g of potassium carbonate are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 110 ℃, the reaction is carried out for 11 hours under heat preservation, water is separated by a water separator in the reaction process, the temperature of the three-neck flask is reduced to room temperature, 600mL of purified water is added into the three-neck flask, the three-neck flask is stirred for 15 minutes, and the three-neck flask is kept stand for liquid separation to obtain an intermediate II;
weighing: 1000g of intermediate II, 100g of glycerol, 2500g of toluene and 10g of sodium carbonate are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to 110 ℃, the three-neck flask is kept for reaction for 11 hours, the temperature of the three-neck flask is reduced to room temperature, 1000mL of purified water is added into the three-neck flask, the three-neck flask is stirred for 15 minutes, the three-neck flask is kept stand for liquid separation, an organic phase is transferred into a rotary evaporator, the water bath temperature is set to be 90 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate III;
weighing: 50g of intermediate III and 150mL of N, N-dimethylformamide are added into a three-neck flask, stirred until the system is dissolved, 0.05g of tetrabutylammonium bromide, 0.20g of sodium hydroxide and 300g of epichlorohydrin are added into the three-neck flask, the temperature of the three-neck flask is increased to 90 ℃, the temperature of the three-neck flask is kept for reaction for 8 hours, the temperature of the three-neck flask is reduced to 50 ℃, the filtrate is distilled to dryness under reduced pressure, a filter cake and purified water are added into a beaker according to the dosage ratio of 1g to 7mL, a large amount of solids are separated out, the filtration is carried out, the filter cake is washed by the purified water and ethanol and then is transferred into a drying box with the temperature of 80 ℃, and the drying box is dried in vacuum until the weight is constant, thus obtaining the modified resin.
S2, preparing composite aramid fiber
Weighing: 187.2g of hydroquinone, 125.8g of 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 388.8g of 3, 5-dichlorophenylamine, 68.5g of bisphenol A and 1123.2g of N-methylpyrrolidone are added into a three-neck flask and stirred until the system is dissolved, 337g of toluene and 11.23g of potassium carbonate are added into the three-neck flask, the temperature of the three-neck flask is increased to 145 ℃, the reaction is kept for 3 hours, byproduct water is separated through a water separator during the reaction, the temperature of the three-neck flask is increased to 190 ℃, stirring is carried out until the pole climbing phenomenon appears, a beaker is taken, 7300g of purified water is added into the beaker and stirred, the beaker is slowly added into the reaction system, stirring is carried out for 50min, suction filtration is carried out, the filter cake is transferred into a drying box with the temperature of 80 ℃ and is dried to a constant weight by blast, and crushed and passes through a 100 screen mesh to obtain a crude compound aramid product;
weighing: adding 100g of a crude product of the composite aramid fiber and 300mL of 0.5M hydrochloric acid into a three-neck flask, stirring, raising the temperature of the three-neck flask to 95 ℃, carrying out heat preservation treatment for 50min, carrying out suction filtration, leaching a filter cake with purified water, then carrying out suction drying, adding 500mL of absolute ethyl alcohol and the filter cake into the three-neck flask, stirring, raising the temperature of the three-neck flask to 78 ℃, carrying out heat preservation treatment for 50min, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 70 ℃, and carrying out vacuum drying to constant weight to obtain the composite aramid fiber;
adding the composite aramid fiber into a melt spinning machine for melt spinning, cooling the melt spinning machine by adopting an air cooling mode, wherein the melting temperature of the melt spinning machine is 730 ℃, the size of a spinning die hole is 0.3mm, and the stretching speed is 460m/min, so as to prepare the composite aramid fiber with the diameter of 10-12 mu m.
S3, preparing a film
Uniformly mixing diisodecyl phthalate, magnesium stearate, oleamide, an anti-aging agent H and octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate according to the dosage ratio of 1g to 2g to 1g to obtain an additive;
the modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additive are added into a double-screw extruder according to the dosage ratio of 20g to 0.3g to 7g to 5g to 3g, the temperature of 6 temperature sections from a feed end to a discharge end of the double-screw extruder is set to 250 ℃, 260 ℃, 265 ℃ and 265 ℃ in sequence, the spindle rotation speed of the double-screw extruder is 14r/min, and the materials are extruded by the double-screw extruder and then enter a blow molding machine for blow molding, so that the film material with the thickness of 0.1+/-0.01 mm is obtained.
Comparative example 1
The present comparative example differs from example 1 in that the modified epoxy resin in step S1 was replaced by bisphenol A type epoxy resin (E-44) in equal amount.
Comparative example 2
This comparative example differs from example 1 in that 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol was not added in step S2.
Comparative example 3
This comparative example differs from example 1 in that toluene-2, 4-diisocyanate was not added in step S3.
Performance test:
the mechanical properties and the high and low temperature resistance of the film materials prepared in examples 1 to 3 and comparative examples 1 to 3 were tested, wherein the mechanical properties were referred to the standard GB/T1040.1-2018 "determination of Plastic tensile Properties section 1: general rules determination of tensile Strength, tensile Strain and reference Standard GB/T16578.1-2008 "determination of tear resistance of Plastic films and sheets part 1: the trouser tearing method is used for measuring the tearing strength of a sample, the high temperature resistance is the mechanical property of the test piece at the temperature of 90 ℃, the low temperature resistance is the mechanical property of the test piece at the temperature of-10 ℃, and the specific test results are shown in the following table:
data analysis:
by analyzing the data of examples 1-3, the tensile strength of the film material prepared by the invention reaches 163.8MPa, the tensile strain reaches 457%, the tearing strength reaches 66.3kN/m, and the retention rate of various mechanical properties is higher in the environment of high temperature 90 ℃ and low temperature-10 ℃, which indicates that the film material prepared by the invention has good tensile strength, tensile strain, tearing strength and excellent high and low temperature resistance;
the data of the comparative example 1 and the data of the examples 1-3 are compared and analyzed, and the retention rate of each mechanical property of the comparative example 1 is lower than that of the test data of the examples 1-3 under the environment of high temperature of 90 ℃ and low temperature of-10 ℃, so that the compounding effect between the modified resin and the composite aramid fiber prepared by the invention is more outstanding in each mechanical property and high and low temperature resistance than that of the bisphenol A epoxy resin (E-44) and the composite aramid fiber;
the comparative example 2 and the data of examples 1-3 are compared and analyzed, and the retention rate of each mechanical property of the comparative example 2 is lower than that of the test data of examples 1-3 in the environment of high temperature 90 ℃ and low temperature-10 ℃, but the retention rate is better than that of the test data of comparative example 1, which shows that the influence of the composite aramid fiber on the film material performance is lower than that of the modified resin, and the mechanical property and the high and low temperature resistance of the composite aramid fiber can be effectively improved by adding 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol into the composite aramid fiber;
the comparative example 3 and the data of examples 1-3 are compared and analyzed, and the test data of each mechanical property of the comparative example 3 is lower than the test data of examples 1-3, but the retention rate of each mechanical property of the comparative example is not greatly different from that of examples 1-3 under the environment of high temperature of 90 ℃ and low temperature of-10 ℃, but the overall retention rate is lower than that of examples 1-3, which shows that the addition of substances containing polyisocyanate functional groups in the melting process can promote the crosslinking of the modified resin and the composite aramid fiber, and the mechanical property and the high and low temperature resistance of the film material are improved.
Example 4, a method of application of a unidirectional fiber-based lightweight high strength film material; processing a light high-strength film material into a film, uniformly coating an adhesive on the surface of the film, setting fiber filaments according to the same direction and the same angle, carrying out high-pressure bonding on the fiber filaments, and carrying out compression ratio of 55-152, wherein the pressure is set at 97-153 Pa, the pressure is gradually increased, and simultaneously, drying is carried out after compression to form a three-layer functional composite film, namely a film layer, an adhesive layer and a fiber layer, in the process, customers can set according to the application scene of needs to produce different requirements of different thicknesses, and can also replace different fiber filaments and angles of the fiber filaments according to the requirements of the customers, thereby realizing customization, the angles of the fiber filaments are mostly set in the same direction, and simultaneously, changing the film and adapting and selecting the corresponding adhesive according to the requirements of customization, wherein the dried temperature is correspondingly matched according to the process requirements to achieve the optimal use effect, and the thickness of the composite functional film is ensured to be lower when the strength of the composite functional film is enhanced through double fibers at 60-120 ℃.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A light high-strength film material based on unidirectional fibers is characterized in that modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives are subjected to blow molding by a blow molding machine after being extruded by a double screw extruder according to the dosage ratio of 20g to 0.3g to 7g to 5g to 3 g;
the modified resin is prepared by performing polycondensation reaction on methanol triethoxysilane, diethoxymethylsilane and tetraethoxysilane in an ethanol environment to generate an intermediate I with hydroxyl end capping, performing esterification condensation on hydroxyl on the intermediate I and carboxyl on 5-amino isophthalic acid to prepare an intermediate II, performing further reaction on glycerol serving as a chain extender and the intermediate II to generate an intermediate III, and performing polycondensation reaction on epichlorohydrin and active functional groups on the intermediate III under the action of a catalyst to obtain the modified resin;
the composite aramid fiber is prepared by carrying out dehydration condensation on hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxydiol, 3, 5-dichloroaniline and bisphenol A under the action of a catalyst to prepare a composite aramid crude product, reprocessing the composite aramid crude product to prepare the composite aramid, and preparing the composite aramid fiber by melt spinning.
2. The unidirectional fiber-based light high-strength film material according to claim 1, wherein the additive consists of a plasticizer, a dispersing agent, a lubricant, an anti-aging agent and an antistatic agent according to the dosage ratio of 1g to 2g to 1g, wherein the plasticizer is one or more of dioctyl phthalate, di-phthalate, diisodecyl phthalate and tricresyl phosphate, the dispersing agent is one or more of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant oleamide and microcrystalline paraffin wax, the anti-aging agent is one or two of an anti-aging agent DPPD, an anti-aging agent PPD and an anti-aging agent H, the antistatic agent is one or two of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and sodium p-nonylphenoxy propyl sulfonate, the temperature of 6 temperature sections from a feeding end to a discharging end of the twin-screw extruder is set to 250 ℃, 260 ℃, 265 ℃ in sequence, and the main shaft rotation speed of the twin-screw extruder is 14r/min.
3. The preparation method of the light high-strength film material based on the unidirectional fibers is characterized by comprising the following steps of:
s1, adding methanol triethoxysilane, diethoxymethylsilane, tetraethoxysilane and 10vt percent ethanol into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 45-55 ℃, adding triethylamine into the three-neck flask, adjusting the pH value of a system to be 8-9, carrying out heat preservation reaction for 4-6 hours, and carrying out post treatment to obtain an intermediate I;
s2, adding the intermediate I, toluene, 5-amino isophthalic acid and a catalyst into a three-neck flask protected by nitrogen, stirring, heating the three-neck flask to 100-110 ℃, carrying out heat preservation reaction for 10-11h, and carrying out post treatment to obtain an intermediate II;
s3, adding the intermediate II, glycerol, toluene and a catalyst into a three-neck flask, stirring, raising the temperature of the three-neck flask to 100-110 ℃, carrying out heat preservation reaction for 10-11h, and carrying out post treatment to obtain an intermediate III;
s4, adding the intermediate III and N, N-dimethylformamide into a three-neck flask, stirring until the system is dissolved, adding a catalyst and epichlorohydrin into the three-neck flask, raising the temperature of the three-neck flask to 80-90 ℃, carrying out heat preservation reaction for 6-8h, and carrying out post treatment to obtain modified resin;
s5, adding the modified resin, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, composite aramid fiber, toluene-2, 4-diisocyanate and additives into a double screw extruder, and transferring the mixture into a blow molding machine for blow molding after melt extrusion to obtain a film finished product.
4. The method for preparing a unidirectional fiber-based light high-strength film material according to claim 3, wherein the dosage ratio of methanol triethoxysilane, diethoxymethylsilane, tetraethoxysilane, 10vt% ethanol in step S1 is 1g:5g:6g:20ml, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is increased to 60-80 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I.
5. The method for preparing a unidirectional fiber-based light high-strength film material according to claim 3, wherein the dosage ratio of the intermediate I, toluene, 5-aminoisophthalic acid and the catalyst in the step S2 is 2g:8ml:1.5g:0.3g, the catalyst is one of potassium carbonate and sodium carbonate, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, purified water is added into the three-neck flask, the three-neck flask is stirred for 10 to 15 minutes, and the three-neck flask is stood for liquid separation to obtain an intermediate II.
6. The method for preparing a unidirectional fiber-based light high-strength film material according to claim 3, wherein in the step S3, the weight ratio of the intermediate II, glycerol, toluene and the catalyst is 10:1:25:0.1, the catalyst is one of potassium carbonate and sodium carbonate, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, purified water is added into the three-neck flask, the three-neck flask is stirred for 10 to 15 minutes, the three-neck flask is kept stand for liquid separation, an organic phase is transferred into a rotary evaporator, the water bath temperature is set to be 80 to 90 ℃, and the solvent is distilled off under reduced pressure, so that an intermediate III is obtained.
7. A method for preparing a unidirectional fiber-based light high strength film material according to claim 3, wherein in step S4, the ratio of the intermediate III, N-dimethylformamide, catalyst to epichlorohydrin is 1g:3ml:0.05g:6g, the catalyst is composed of tetrabutylammonium bromide and sodium hydroxide ammonium in a weight ratio of 1:4, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-neck flask is reduced to 30-50 ℃, suction filtration is carried out, the filtrate is distilled under reduced pressure until the filtrate is dried, a filter cake and purified water are added into a beaker according to the dosage ratio of 1g to 7mL, a large amount of solids are separated out, suction filtration is carried out, the filter cake is washed by the purified water and ethanol and then is transferred into a drying box with the temperature of 75-80 ℃, and vacuum drying is carried out until the weight is constant, thus obtaining the modified resin.
8. The method for preparing the unidirectional fiber-based light high-strength film material according to claim 3, wherein the method for preparing the composite aramid fiber is as follows:
a1, adding hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 3, 5-dichloroaniline, bisphenol A and N-methylpyrrolidone into a three-neck flask, stirring until the system is dissolved, adding toluene and a catalyst into the three-neck flask, increasing the temperature of the three-neck flask to 140-145 ℃, carrying out heat preservation reaction for 2-3 hours, increasing the temperature of the three-neck flask to 180-190 ℃, stirring, reacting until a pole climbing phenomenon appears, and carrying out aftertreatment to obtain a composite aramid crude product;
a2, adding 0.5M hydrochloric acid of the crude product of the composite aramid fiber into a three-neck flask, stirring, raising the temperature of the three-neck flask to 90-95 ℃, carrying out heat preservation treatment for 30-50min, carrying out suction filtration, leaching a filter cake with purified water, then carrying out suction drying, adding the filter cake and absolute ethyl alcohol into the three-neck flask, stirring, raising the temperature of the three-neck flask to 75-78 ℃, carrying out heat preservation treatment for 30-50min, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 60-70 ℃, and carrying out vacuum drying to constant weight to obtain the composite aramid fiber; wherein the dosage ratio of the crude product of the composite aramid fiber, the 0.5M hydrochloric acid and the ethanol is 1g to 3mL to 5mL;
and A3, adding the composite aramid fiber into a melt spinning machine for melt spinning to prepare the composite aramid fiber.
9. The method for preparing a unidirectional fiber-based light high strength film material according to claim 8, wherein in the step A1, the molar ratio of hydroquinone, 1,3, 5, 7-octamethyl-1, 7-tetrasiloxane diol, 3, 5-dichloroaniline and bisphenol a is 17:4:24:3, the weight of the N-methylpyrrolidone is 6 times that of hydroquinone, the weight of the toluene is 0.3 times that of the N-methylpyrrolidone, the weight of the catalyst is potassium carbonate, and the weight of the catalyst is 0.01 times that of the N-methylpyrrolidone, the post-treatment operation comprises: adding purified water into a beaker, stirring, increasing the temperature of the beaker to 85-95 ℃, slowly adding the reaction system into the beaker, stirring for 30-50min, carrying out suction filtration, transferring a filter cake into a drying box with the temperature of 70-80 ℃, carrying out forced air drying to constant weight, crushing, and sieving with a 100-mesh screen to obtain a composite aramid crude product.
10. The application method of the light high-strength film material based on the unidirectional fiber is characterized by comprising the following steps of: processing a film material into a film, uniformly coating an adhesive on the surface of the film, simultaneously setting fiber filaments in the same direction and at the same angle, and bonding the fiber filaments under high pressure, wherein the pressure is set at 97-153 Pa, the pressure is gradually increased, and simultaneously drying after compression to form the three-layer functional composite film.
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| US20030153682A1 (en) * | 2002-02-01 | 2003-08-14 | Haruji Sakugawa | Elastomer-modified epoxy siloxane compositions |
| CN101532257A (en) * | 2009-04-23 | 2009-09-16 | 宁波登天氟材有限公司 | Processing method of waterproof and moisture permeable polytetrafluoroethylene millipore membrane laminated fabric |
| CN112092472A (en) * | 2020-10-16 | 2020-12-18 | 珠海市辉丰包装材料有限公司 | Biodegradable composite film material and preparation method and packaging bag thereof |
| CN116435022A (en) * | 2023-05-12 | 2023-07-14 | 广东澳通特种电缆有限公司 | Low-smoke flame-retardant cable and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153682A1 (en) * | 2002-02-01 | 2003-08-14 | Haruji Sakugawa | Elastomer-modified epoxy siloxane compositions |
| CN101532257A (en) * | 2009-04-23 | 2009-09-16 | 宁波登天氟材有限公司 | Processing method of waterproof and moisture permeable polytetrafluoroethylene millipore membrane laminated fabric |
| CN112092472A (en) * | 2020-10-16 | 2020-12-18 | 珠海市辉丰包装材料有限公司 | Biodegradable composite film material and preparation method and packaging bag thereof |
| CN116435022A (en) * | 2023-05-12 | 2023-07-14 | 广东澳通特种电缆有限公司 | Low-smoke flame-retardant cable and preparation method thereof |
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