CN109680505B - Surface modified aramid fiber and surface modification method and application thereof - Google Patents

Surface modified aramid fiber and surface modification method and application thereof Download PDF

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CN109680505B
CN109680505B CN201710974677.9A CN201710974677A CN109680505B CN 109680505 B CN109680505 B CN 109680505B CN 201710974677 A CN201710974677 A CN 201710974677A CN 109680505 B CN109680505 B CN 109680505B
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aramid fiber
tetraglycidyl
ring
epoxy resin
plasma
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CN109680505A (en
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张藕生
王洪学
余荣禄
姚斌
王芳
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • D—TEXTILES; PAPER
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

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Abstract

The invention relates to a surface modified aramid fiber and a surface modification method and application thereof, and mainly solves the technical problems that the interface shear strength of aramid fiber and epoxy resin is low and the surface of the aramid fiber subjected to plasma treatment is easy to inactivate. The surface-modified aramid fiber comprises aramid fiber and a surface treating agent, and is characterized in that the surface treating agent is epoxy resin containing N-glycidyl groups, and the content of the surface treating agent in the surface-modified aramid fiber is 0.2-5%; the technical scheme that the aramid fiber is subjected to plasma surface treatment before the surface treatment agent is treated better solves the problem, the interfacial shear strength of the aramid fiber and the epoxy resin after modification is improved by more than 30% compared with that before modification, and the aramid fiber modified surface treatment method can be used for industrial production of surface-modified aramid fiber.

Description

Surface modified aramid fiber and surface modification method and application thereof
Technical Field
The invention belongs to the field of fiber surface modification, and particularly relates to surface-modified aramid fiber, a surface modification method and application thereof.
Background
Aramid fiber is known as aromatic polyamide fiber, is one of three high-performance synthetic fibers acknowledged in the world at present, and is widely applied to various fields such as national defense and military industry, aerospace, rail transit, safety protection, environmental protection, electronic information and the like. Aramid fibers can be classified into meta-aramid and para-aramid according to their polymer structures. The meta-aramid fiber is mainly used as a high-temperature filtering material, a flame-retardant material, an electric insulating material and the like in a functional fiber form, and the para-aramid fiber has higher strength, modulus, heat resistance and dimensional stability due to high symmetry of a macromolecular chain structure, and is mainly used as a reinforcing material, such as optical cable and cable reinforcement, tire cord, a high-end protective material, a composite material and the like.
One of the major problems with aramid fibers for composites is the low interlaminar Shear strength (ILSS). The para-aramid fiber which is not subjected to surface treatment has a smooth surface, and due to the pi conjugation effect, the hydrogen activity in an amide group is poor, so that a good interface effect is difficult to form with a resin matrix. In order to improve the adhesion of the para-aramid to the resin matrix, the fiber surface must be modified.
Aramid fiber surface modification methods mainly fall into two categories: chemical modification and physical modification. Chemical modifications can be broadly divided into surface etching and surface grafting depending on the mode of action, while physical modifications are mainly surface coating, gamma radiation, ultrasonic immersion and plasma treatment. CN201210240025.X adopts hydrogen peroxide to activate the surface of aramid fiber, and the ILSS of the activated aramid fiber composite material is improved from about 40MPa to about 60MPa. CN201210290055.1 adopts fluorocarbon silane coupling agent to treat the surface of aramid fiber, and the ILSS of the modified aramid fiber composite material reaches 58 MPa. CN201010108510.2 adopts low molecular weight isocyanate or glycidyl ether to carry out graft modification on the surface of aramid fiber III, which can realize continuous treatment, but the ILSS of the modified aramid fiber composite material is only 50 MPa. CN200610150924.5 adopts60Co is used as an irradiation source for aramid fiber surface modification, and the composite material ILSS reaches 72.9MPa and is improved by about 20 percent compared with the composite material before modification. However, the modification is carried out in a closed vessel, and it is difficult to realize continuous treatment. In addition, acetone or ethanol organic solvent is needed in the treatment engineering, so that the environmental protection problem exists. CN201210070232.5 uses amide organic solvent as ultrasonic processing medium to process the aramid fiber surface, but the ILSS of the aramid fiber composite material after processing is improved within 10 percent.
Disclosure of Invention
One of the technical problems to be solved by the invention is the technical problem that in the prior art, after the aramid fiber is subjected to plasma treatment, the fiber surface active points are easy to inactivate, so that the Interfacial Shear strength (IFSS) of the aramid fiber and the epoxy resin matrix is low.
The second technical problem to be solved by the invention is the technical problem that the surface active points of fibers are easy to inactivate after the aramid fibers are treated by plasma in the prior art, which corresponds to one of the technical problems, so that the interfacial shear strength (IFSS) of the aramid fibers and the epoxy resin matrix is low.
The invention provides an application method of surface modified aramid fiber corresponding to the solution of the technical problem.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a surface modified aramid fiber comprises aramid fiber and a surface treating agent, wherein the surface treating agent is epoxy resin containing N-glycidyl groups, and the mass content of the surface treating agent in the surface modified aramid fiber is 0.2-5%; wherein, the aramid fiber is subjected to plasma surface treatment before being treated by the surface treating agent.
In the above-mentioned embodiment, the nitrogen atom of the N-glycidyl group in the N-glycidyl group-containing epoxy resin is bonded to an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring directly or via a methylene group, and is preferably an epoxy resin containing not less than 2N-glycidyl groups, and more preferably N, N-diglycidylaniline, N-diglycidylnaphthylamine, N-diglycidyl p-aminophenol glycidyl ether, N-diglycidyl m-aminophenol glycidyl ether, N-diglycidyl o-aminophenol glycidyl ether, 1, 2-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane, Tetraglycidyl p-phenylenediamine, tetraglycidyl m-phenylenediamine, tetraglycidyl o-phenylenediamine, tetraglycidyl diphenyldiamine, tetraglycidyl aminodiphenylmethane, tetraglycidyl aminodiphenylpropane, tetraglycidyl aminodiphenylsulfone, tetraglycidyl aminodiphenylether, and derivatives thereof in which a substituent such as a methyl group, an ethyl group, or a halogen atom is present in an aromatic ring, a biphenyl ring, a naphthalene ring, or an alicyclic ring.
In the above technical solution, the aramid fiber is not particularly limited, and for example, but not limited to, chopped aramid fiber, continuous aramid fiber, or aramid fiber fabric.
In the technical scheme, the mass content of the surface treatment agent in the surface modified aramid fiber is preferably 1.0-2.5%.
In order to solve the second technical problem, the invention adopts the following technical scheme: a surface modification method of aramid fiber comprises the following steps:
(1) heating and drying the aramid fiber to remove adsorbed water;
(2) carrying out plasma surface treatment on the dried aramid fiber;
(3) and soaking the aramid fiber subjected to the plasma surface treatment in a surface treatment agent or a solution of the surface treatment agent to ensure that the mass content of the surface treatment agent in the surface modified aramid fiber is 0.2-5 percent, thereby obtaining the surface modified aramid fiber.
In the above technical solution, the plasma treatment is vacuum plasma treatment, and the process conditions are preferably: the processing medium is air, oxygen, nitrogen or argon, and the gas flow is 10cm3/min～100cm3The plasma generating power is 50 w-600 w, and the processing time is 5 s-600 s.
In the above-mentioned embodiment, the nitrogen atom of the N-glycidyl group in the N-glycidyl group-containing epoxy resin is bonded to an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring directly or via a methylene group, and is preferably an epoxy resin containing not less than 2N-glycidyl groups, and more preferably N, N-diglycidylaniline, N-diglycidylnaphthylamine, N-diglycidyl p-aminophenol glycidyl ether, N-diglycidyl m-aminophenol glycidyl ether, N-diglycidyl o-aminophenol glycidyl ether, 1, 2-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane, Tetraglycidyl p-phenylenediamine, tetraglycidyl m-phenylenediamine, tetraglycidyl o-phenylenediamine, tetraglycidyl diphenyldiamine, tetraglycidyl aminodiphenylmethane, tetraglycidyl aminodiphenylpropane, tetraglycidyl aminodiphenylsulfone, tetraglycidyl aminodiphenylether, and derivatives thereof in which a substituent such as a methyl group, an ethyl group, or a halogen atom is present in an aromatic ring, a biphenyl ring, a naphthalene ring, or an alicyclic ring.
In the technical scheme, the mass content of the surface treatment agent in the surface modified aramid fiber is preferably 1.0-2.5%
In the above technical solution, the aramid fiber is not particularly limited, and for example, but not limited to, chopped aramid fiber, continuous aramid fiber, or aramid fiber fabric.
In order to solve the third technical problem, the invention adopts the following technical scheme: an application of surface modified aramid fiber.
In the above technical solutions, the application method is not particularly limited, and those skilled in the art can use the surface-modified aramid fiber of the present invention according to the prior art, for example, but not limited to, aramid fiber reinforced resin-based composite material.
The content determination of the surface treating agent in the invention comprises the following steps: and repeatedly cleaning the modified surface-modified aramid fiber with acetone for 5 times, drying, measuring the mass of the aramid fiber before and after cleaning, and calculating the mass content of the surface treating agent according to the following formula.
Figure BDA0001438270560000031
In the formula: m is0、m1The quality of the surface modified aramid fiber before and after cleaning.
The surface modified aramid fiber and the surface modification method thereof provided by the invention have the advantages that:
1) the composite modification process of plasma treatment and surface modifier is adopted, the problem that the surface active points of the aramid fiber are easy to inactivate after the plasma treatment is solved, and the modified aramid fiber can still form high interface shear strength with an epoxy resin matrix after long-time room temperature storage.
2) The surface treating agent adopted by the invention contains the epoxy resin of the N-glycidyl group, which not only has good wettability and affinity to the fiber surface after plasma treatment, but also has good compatibility to the epoxy resin matrix, and has better effect than the single plasma treatment.
3) The surface modification method provided by the invention is simple to operate and easy for industrial treatment.
By adopting the technical scheme of the invention, the interface shear strength (IFSS) of the surface modified aramid fiber and the epoxy resin matrix is high, the ILSS can reach 77MPa, the ILSS can be improved by more than 30 percent, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The invention discloses a surface modification method of aramid fiber, which comprises the following steps:
(1) heating and drying the aramid fiber to remove adsorbed moisture;
(2) carrying out plasma surface treatment on the dried aramid fiber;
(3) and soaking the aramid fiber subjected to the plasma surface treatment in a surface treatment agent or a solution of the surface treatment agent to ensure that the mass content of the surface treatment agent in the surface modified aramid fiber is 0.2-5 percent, thereby obtaining the surface modified aramid fiber.
Drying aramid fibers before plasma treatment is necessary because aramid fibers have certain water absorption properties, and the presence of moisture has a significant effect on the effect of plasma treatment. The drying conditions depend on the size of the fiber spindle or fabric, and it is usually appropriate to treat the fiber in a forced air oven at 80 ℃ to 120 ℃ for 4h to 12 h.
There are many ways of plasma treatment, including high temperature plasma and low temperature plasma. The high-temperature plasma is not suitable for the surface treatment of the organic fiber due to overhigh temperature; the low-temperature plasma is generally divided into vacuum plasma and atmospheric plasma, the vacuum plasma is formed by ionizing thin gas through a high-voltage electric field in an environment close to vacuum, and the low-temperature plasma is suitable for laboratory research; the atmospheric plasma is formed by directly ionizing medium gas in the air environment, and is suitable for industrial online treatment. The principle of the two plasma treatment modes is similar, and the vacuum plasma is selected for surface treatment.
The vacuum plasma treatment conditions are as follows: the processing medium is air, oxygen, nitrogen or argon, and the gas flow is 10cm3/min～100cm3The plasma generating power is 50 w-600 w, and the processing time is 5 s-600 s.
The active points formed on the surface of the fiber after plasma treatment have timeliness, and the time for which the active points exist is related to factors such as the material and the environment of the fiber. The activated fiber should be used in time or the surface treating agent should be used to react with the active site first and then react with the resin matrix.
The surface treatment agent used in the present invention is an N-glycidyl group-containing epoxy resin in which the nitrogen atom of the N-glycidyl group is bonded to an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring directly or via a methylene group, and is preferably an epoxy resin containing not less than 2N-glycidyl groups, and more preferably N, N-diglycidylaniline, N-diglycidylnaphthylamine, N-diglycidylparabinophenol glycidyl ether, N-diglycidylmethaminophenol glycidyl ether, N-diglycidyloaminophenol glycidyl ether, 1, 2-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N-diglycidylaminomethyl-cyclohexane, 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane, tetraglycidyl p-phenylenediamine, tetraglycidyl m-phenylenediamine, tetraglycidyl o-phenylenediamine, tetraglycidyl diphenyldiamine, tetraglycidyl aminodiphenylmethane, tetraglycidyl aminodiphenylpropane, tetraglycidyl aminodiphenylsulfone, tetraglycidyl aminodiphenylether, and derivatives thereof in which a substituent such as a methyl group, an ethyl group, a halogen atom or the like is present in the aromatic ring, the biphenyl ring, the naphthalene ring or the alicyclic ring.
The viscosity of the surface treatment agent has an obvious influence on the infiltration effect. To obtain a good wetting effect, it is necessary to reduce the viscosity of the surface treatment agent by heating or to use a solution configured as the surface treatment agent.
In order to further understand the present invention, the surface modification method of the aramid fiber provided by the present invention and the surface-modified aramid fiber obtained thereby are specifically described below with reference to examples.
[ example 1 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) N, N-diglycidyl m-aminophenol glycidyl ether epoxy resin (epoxy value of 0.85mol/100g) was poured into an upper oil bath, heated to 70 ℃ and having a viscosity of 35mPa.s (Brookfield DV-III rotational viscometer, rotor model SC4-18, rotation speed of 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber. The mass content of the surface treatment agent in this example was 1.5%.
The interfacial shear strength (IFSS) of the surface-modified aramid and the epoxy resin is determined by a micro-debonding method: IFSS test was carried out on an HM-410 fiber interface characteristic measuring instrument of Tortoise industries, Japan. Firstly, a monofilament is separated from an aramid fiber bundle without damage, the monofilament is adhered to an instrument-dedicated arch-shaped clamp by using strong glue, then self-made epoxy resin glue (DER 354: DER 332: DDM is 50:50:26) is coated on the monofilament, and the glue forms liquid drops under the action of surface tension. And (3) putting the monofilament coated with the glue and the clamp into a drying oven for heating to cure the epoxy resin glue, wherein the curing condition is 100 ℃/2h +150 ℃/2 h. After the solidification is finished, the clamp is fixed on an instrument, the positions of the upper cutter and the lower cutter are adjusted to be just clamped on the left side of the resin microsphere, the fiber is moved leftwards through a transmission device with a sensor, the embedding length of the fiber in the resin microsphere and the tension displayed by the sensor are recorded, and the IFSS is calculated by using the following formula.
Figure BDA0001438270560000061
In the formula: f is the tensile force (mN) born by the fiber, d is the monofilament diameter (mum) of the fiber, and l is the embedding length (mum) of the fiber in the resin microsphere.
The IFSS of the surface-modified aramid and epoxy resin in this example was 59 MPa.
Determination of interlaminar shear strength (ILSS) of the surface modified aramid composite material: the aramid continuous fiber bundles impregnated with the self-made epoxy resin glue (DER 354: DER 332: DDM is 50:50:26) are laid in parallel in a self-made ILSS sample band mold, a female mold and a male mold are locked, and the obtained product is placed into an oven for curing under the conditions of 80 ℃/1h +100 ℃/2h +150 ℃/2 h. After the curing is finished, the sample bars are taken out, cut and polished into standard sample bars, and tested according to JC/T773-. ILSS was measured to be 74 MPa.
[ example 2 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) N, N-diglycidyl para-aminophenol glycidyl ether epoxy resin (epoxy value of 0.83mol/100g) was poured into an oil-feeding tank, heated to 70 ℃ and having a viscosity of 35mPa.s (Brookfield DV-III type rotational viscometer, rotor model SC4-18, rotation speed of 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ example 3 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) N, N-diglycidyl ortho-aminophenol glycidyl ether epoxy resin (epoxy value 0.84mol/100g) was poured into an upper oil bath and heated to 70 ℃ with a viscosity of 40mPa.s (Brookfield DV-III rotational viscometer, rotor model SC4-18, rotation speed 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ examples 4 to 11 ]
The difference between the embodiments 4-11 and the embodiment 2 lies in that the plasma generating power, the plasma processing time, the processing medium and other ion processing process conditions are changed, other process steps are kept unchanged, and specific process parameters and test results are shown in the attached table 1.
[ example 12 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) Tetraglycidaminodiphenylmethane (epoxy value of 0.80mol/100g) was prepared into an acetone solution with a mass concentration of 30%, and poured into an upper oil tank. And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove, and drying to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ COMPARATIVE EXAMPLE 1 ]
And (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h. The dried aramid was tested for IFSS and ILSS as in example 1 and the results are shown in attached table 1.
[ COMPARATIVE EXAMPLE 2 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
The plasma treated aramid fibers were tested for IFSS and ILSS as in example 1 and the results are shown in table 1.
[ COMPARATIVE EXAMPLE 3 ]
(1) And (3) putting the continuous aramid fiber in a blast oven, and drying for 12 hours at the temperature of 80 ℃.
(2) N, N-diglycidyl para-aminophenol glycidyl ether epoxy resin (epoxy value of 0.83mol/100g) was poured into an oil-feeding tank, heated to 70 ℃ and having a viscosity of 35mPa.s (Brookfield DV-III type rotational viscometer, rotor model SC4-18, rotation speed of 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ COMPARATIVE EXAMPLE 4 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) Liquid bisphenol A type epoxy resin (epoxy value 0.54mol/100g) was poured into an oil-feeding tank and heated to 80 ℃ and a viscosity of 60mPa.s (Brookfield DV-III rotational viscometer, rotor model SC4-18, rotation speed 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ COMPARATIVE EXAMPLE 5 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber between a positive electrode and a negative electrode of a vacuum plasma processor, wherein the processing medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) 4, 5-Oxirane-1, 2-dicarboxylic acid diglycidyl ester (epoxy value 0.88mol/100g) was poured into an oil-feeding tank and heated to 70 ℃ and a viscosity of 52mPa.s (Brookfield DV-III rotational viscometer, rotor model SC4-18, rotation speed 10 rpm). And enabling the aramid fiber after the plasma treatment to continuously pass through an upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
[ COMPARATIVE EXAMPLE 6 ]
Surface modification of aramid fiber:
(1) and (3) putting the continuous aramid fiber in a blast oven, and drying at 80 ℃ for 12 h.
(2) Uniformly placing the dried continuous aramid fiber on a vacuum plasma processorBetween the negative electrodes, the treating medium is air, and the gas flow is 50cm3And (4) min, wherein the plasma generation power is 400w, and the treatment time is 60s, so that the aramid fiber after plasma treatment is obtained.
(3) And (3) pouring polypropylene glycol diglycidyl ether (with the epoxy value of 0.35mol/100g) into an upper oil groove, and enabling the aramid fiber after plasma treatment to continuously pass through the upper oil groove to obtain the surface-modified aramid fiber.
The methods for measuring the mass content of the surface treatment agent, IFSS and ILSS were the same as in example 1, and the test results are shown in table 1.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Attached table 1
Figure BDA0001438270560000101

Claims (8)

1. The surface-modified aramid fiber comprises aramid fiber and a surface treating agent, and is characterized in that the surface treating agent is epoxy resin containing N-glycidyl groups, and the mass content of the surface treating agent in the surface-modified aramid fiber is 0.2-5%; the aramid fiber is subjected to plasma surface treatment before being treated by the surface treatment agent, the plasma surface treatment is vacuum plasma surface treatment, and the vacuum plasma treatment conditions are as follows: the processing medium is air, oxygen, nitrogen or argon, and the gas flow is 10cm3/min~100 cm3The plasma generating power is 50 w-600 w, and the processing time is 5 s-600 s;
the N-glycidyl nitrogen atom in the epoxy resin containing the N-glycidyl is directly connected with an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring or is connected with the aromatic ring, the biphenyl ring, the naphthalene ring or the alicyclic ring through a methylene;
the epoxy resin containing N-glycidyl groups is an epoxy resin containing not less than 2N-glycidyl groups.
2. The surface-modified aramid fiber of claim 1 wherein the epoxy resin containing N-glycidyl groups is selected from the group consisting of N, N-diglycidylaniline, N-diglycidylnaphthylamine, N-diglycidylparabophenol glycidyl ether, N-diglycidm-aminophenol glycidyl ether, N-diglycidylphenol glycidyl ether, 1, 2-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane, tetraglycidyl p-phenylenediamine, tetraglycidyl m-phenylenediamine, tetraglycidyl o-phenylenediamine, tetraglycidyl biphenyldiamine, tetraglycidyl diphenyldiamine, Tetraglycidyl aminodiphenylmethane, tetraglycidyl aminodiphenylpropane, tetraglycidyl aminodiphenylsulfone, tetraglycidyl aminodiphenylether, and derivatives thereof having a substituent of a methyl group, an ethyl group or a halogen atom on an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring.
3. The surface-modified aramid fiber of claim 1, wherein the surface treating agent is present in the surface-modified aramid fiber in an amount of 1.0% to 2.5% by mass.
4. The surface-modified aramid fiber as claimed in claim 1, characterized in that the aramid fiber is chopped aramid fiber, continuous aramid fiber or aramid fiber fabric.
5. The surface modification method of aramid fiber is characterized by comprising the following steps:
(1) heating and drying the aramid fiber to remove adsorbed water;
(2) carrying out plasma surface treatment on the dried aramid fiber;
(3) soaking the aramid fiber subjected to the plasma surface treatment in a surface treatment agent or a solution of the surface treatment agent to ensure that the mass content of the surface treatment agent in the surface modified aramid fiber is 0.2-5 percent, so as to obtain the surface modified aramid fiber;
the plasma treatment is vacuum plasma treatment, and the process conditions are as follows: the processing medium is air, oxygen, nitrogen or argon, and the gas flow is 10cm3/min~100 cm3The plasma generating power is 50 w-600 w, and the processing time is 5 s-600 s;
the surface treatment agent is an epoxy resin containing N-glycidyl groups, nitrogen atoms of the N-glycidyl groups in the epoxy resin containing the N-glycidyl groups are directly connected with an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring or are connected with the aromatic ring, the biphenyl ring, the naphthalene ring or the alicyclic ring through methylene groups, and the epoxy resin containing the N-glycidyl groups is an epoxy resin containing not less than 2N-glycidyl groups.
6. The method for modifying the surface of an aramid fiber according to claim 5, wherein the epoxy resin containing an N-glycidyl group is N, N-diglycidylaniline, N-diglycidylnaphthylamine, N-diglycidylparabophenol glycidyl ether, N-diglycidm-aminophenol glycidyl ether, N-diglycidylphenol glycidyl ether, 1, 2-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1, 4-bis (N, N-diglycidylaminomethyl) cyclohexane, tetraglycidyl p-phenylenediamine, tetraglycidyl m-phenylenediamine, tetraglycidyl o-phenylenediamine, tetraglycidyl biphenyldiamine, Tetraglycidyl aminodiphenylmethane, tetraglycidyl aminodiphenylpropane, tetraglycidyl aminodiphenylsulfone, tetraglycidyl aminodiphenylether, and derivatives thereof having a substituent of a methyl group, an ethyl group or a halogen atom on an aromatic ring, a biphenyl ring, a naphthalene ring or an alicyclic ring.
7. The surface modification method of aramid fiber according to claim 5, characterized in that the mass content of the surface treatment agent in the surface-modified aramid fiber is 1.0-2.5%.
8. Use of the surface-modified aramid fiber as claimed in any one of claims 1 to 4.
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JPS62243622A (en) * 1986-04-16 1987-10-24 Asahi Chem Ind Co Ltd Production of modified aramid material
CN101580594A (en) * 2009-06-10 2009-11-18 沈阳航空工业学院 Method for modifying aramid fiber composite material interface by dielectric barrier discharge plasma technique
CN103031708A (en) * 2012-07-12 2013-04-10 山东理工大学 Method for improving surface activity of aramid fiber
CN105917046A (en) * 2014-01-15 2016-08-31 纳幕尔杜邦公司 Grafted para-aramid fiber and method of making

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JPS62243622A (en) * 1986-04-16 1987-10-24 Asahi Chem Ind Co Ltd Production of modified aramid material
CN101580594A (en) * 2009-06-10 2009-11-18 沈阳航空工业学院 Method for modifying aramid fiber composite material interface by dielectric barrier discharge plasma technique
CN103031708A (en) * 2012-07-12 2013-04-10 山东理工大学 Method for improving surface activity of aramid fiber
CN105917046A (en) * 2014-01-15 2016-08-31 纳幕尔杜邦公司 Grafted para-aramid fiber and method of making

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