CN115717330B - Methacrylic anhydride modified polyamide fiber and preparation method thereof - Google Patents
Methacrylic anhydride modified polyamide fiber and preparation method thereof Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 220
- 229920002647 polyamide Polymers 0.000 title claims abstract description 220
- 239000000835 fiber Substances 0.000 title claims abstract description 207
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000004140 cleaning Methods 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000007853 buffer solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 50
- 229910021641 deionized water Inorganic materials 0.000 claims description 50
- 239000012046 mixed solvent Substances 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- -1 filtering Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 description 28
- 239000004744 fabric Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of methacrylic anhydride modified polyamide fiber, which specifically comprises the following steps: step 1: washing and pre-treating polyamide fibers; step 2: polyamide fiber hydrolysis: step 3: preparation of methacrylic anhydride modified polyamide fiber: mixing the polyamide fiber containing amino groups obtained in the step 2 with a phosphoric acid buffer solution with the pH value of 7-8 under the water bath condition, magnetically stirring for 0.5-1 h, dropwise adding methacrylic anhydride after cooling, and reacting for 0.5-2.5 h under magnetic stirring; filtering after the reaction is finished, pouring out filtrate, cleaning filter residues, and drying to obtain the methacrylic anhydride modified polyamide fiber containing double bonds. The method solves the problem of how to modify the polyamide fiber by using the methacrylic anhydride, so that the polyamide fiber has excellent surface activity and simultaneously reduces the preparation cost.
Description
Technical Field
The invention belongs to the technical field of polyamide fiber surface modification, and particularly relates to a methacrylic anhydride modified polyamide fiber and a preparation method of the methacrylic anhydride modified polyamide fiber.
Background
Polyamide fibers are commonly called chinlon in China, have excellent mechanical properties, wear resistance and chemical corrosion resistance, and are widely applied to the fields of clothing, home textiles and industry. With the continuous improvement of the life quality of people, the demand for polyamide fiber products with high sensibility such as fine denier, superfine denier and special-shaped cross section and high functionality such as moisture absorption and perspiration, antibiosis, ultraviolet resistance and the like for improving the wearability is rapidly growing; secondly, by utilizing the excellent properties of the polyamide fibers, special functions such as high temperature resistance, flame retardance, high strength and high modulus are endowed by modification, and the application of the polyamide fibers with high functions and high performance in increasingly growing national economy and national defense construction is continuously increasing. In addition, conductive fibers are emerging as a new fiber variety and are used in a large number of applications. The fiber has excellent properties such as good conductivity, antistatic property, durability and the like. However, the surface of the polyamide fiber is generally smooth, and the interface bonding force with the matrix is weak. Secondly, the polyamide is used as an inert material, the surface of the fiber has no active group which can directly participate in the reaction, and researchers often modify the surface of the polyamide fiber to enable the surface of the fiber to have the active group and improve the surface activity of the fiber.
Oliveria et al employ dual barrier dielectric plasmaThe modification research of the sub-body (DBD) on the polyamide fiber increases the surface roughness after plasma treatment and improves the wettability of the polyamide fiber. However, the cost of the plasma treatment technology is too high, and the special research is generally performed by a special institute or a research institute, which cannot be popularized. Therefore, this method is difficult to popularize. CaCl for Rietzler et al 2 /H 2 The O/EtOH system surface modifies polyamide fibers with larger diameters and surface roughness for advanced materials for storage and release of active substances. However, the inorganic salt solution and the organic liquid affect the breaking strength of the polyamide fiber, the fiber and the matrix are combined in a non-covalent bond mode, and the bonding force after modification is not very strong. Yang Yanning et al surface treat polyamide fiber with silane coupling agent KH-550, and the interface bonding performance between the treated fiber and resin is improved, and the mechanical properties of the composite material are further improved. Lin Jeng-Skyong and Yuan Haigen, etc. to increase interfacial adhesion capability of aramid fiber and epoxy resin, after dissolving sodium salt with dimethyl sulfoxide, fiber is soaked, so that the surface of fiber is Na + The radical activity of the surface of the aramid fiber is greatly improved, and the interfacial bonding capability of the composite material is further improved. After the Lin is grafted with the bromoacetic acid and is compounded with the epoxy resin, the interlayer peeling strength of the composite material reaches 28.45MPa, and the improvement is 12%.
In the modification mode of the polyamide fiber, the surface of the polyamide fiber is etched to a great extent, the fracture strength of the composite material is affected, and the preparation cost is too high. In addition, the polyamide fiber is used as an inert material, has few active groups with surface energy participating in the reaction, and is difficult to modify.
Disclosure of Invention
The first object of the invention is to provide a preparation method of methacrylic anhydride modified polyamide fiber, which introduces carbon-carbon double bonds into the surface of the polyamide fiber, improves the surface activity of the polyamide fiber and enhances the interfacial compatibility of different matrixes and the polyamide fiber.
The second object of the invention is to provide a methacrylic anhydride modified polyamide fiber which has excellent surface activity and enhances the interfacial compatibility between different matrixes and the polyamide fiber.
The first technical scheme adopted by the invention is that the preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
step 1: washing and pre-treating polyamide fibers;
step 2: polyamide fiber hydrolysis:
mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, and mixing the mixed solvent with the polyamide fiber pretreated by the water washing in the step 1 to react at room temperature; filtering after the reaction is finished, pouring out filtrate, cleaning filter residues, and drying to obtain the polyamide fiber containing amino;
step 3: preparation of methacrylic anhydride modified polyamide fiber:
mixing the polyamide fiber containing amino groups obtained in the step 2 with a phosphoric acid buffer solution with the pH value of 7-8 under the water bath condition, magnetically stirring for 0.5-1 h, dropwise adding methacrylic anhydride after cooling, and reacting for 0.5-2.5 h under magnetic stirring; filtering after the reaction is finished, pouring out filtrate, cleaning filter residues, and drying to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
The present invention is also characterized in that,
the specific implementation steps of the step 1 are as follows:
taking polyamide fiber as a raw material, adding deionized water, ultrasonically cleaning for 0.5-1 h at room temperature, and drying at 60-100 ℃ for later use after cleaning.
In the step 1, the dosage of deionized water is 5000% -6000% of the dry weight of polyamide.
In the step 2, the using amount of the concentrated sulfuric acid with the mass concentration of 98% in the mixed solvent is 15% -20% of the dry weight of the polyamide fiber; the dosage of the deionized water is 5000% -6000% of the dry weight of the polyamide fiber in the step 1; the reaction time is 4h-5h at room temperature.
In the step 2, the filter residue cleaning process is as follows: and ultrasonically cleaning filter residues for 0.5 to 1 hour at room temperature by using deionized water, filtering, and finishing the cleaning when the pH value of the filtrate is neutral.
In the step 2, the drying temperature is as follows: 60-100 ℃.
In the step 3, the water bath temperature is 70-80 ℃; the rotation rate of the two magnetic stirring is 3rpm-10rpm.
In the step 3, methacrylic anhydride is dropwise added after the temperature is reduced to 30-60 ℃, and the speed of dropwise adding methacrylic anhydride is controlled to be 1-1.5 mL/min; the amount of methacrylic anhydride is 50% -800% of the dry weight of the aminated polyamide fiber in step 2.
In the step 3, the filter residue cleaning process is as follows: ultrasonically cleaning filter residues for 0.5-1 h at room temperature by using deionized water, and filtering, wherein the dosage of the deionized water is 5000-6000% of the dry weight of the amino-containing polyamide fiber in the step 2; the drying temperature is as follows: 60-100 ℃.
The second technical scheme adopted by the invention is that the methacrylic anhydride modified polyamide fiber is prepared by adopting the method.
The beneficial effects of the invention are as follows:
1. the preparation method is low in manufacturing cost, simple and feasible, and the carbon-carbon double bond is grafted into the polyamide fiber molecular chain by chemical modification. The surface activity of the polyamide fiber is improved, the interfacial compatibility of different matrixes and the polyamide fiber is enhanced, and meanwhile, the modified polyamide fiber surface is roughened to generate more active functional groups such as amino groups and carboxyl groups, so that more polymerization active points are formed, and the possibility is provided for preparing the polyamide conductive fiber by depositing the conductive material on the polyamide fiber surface through chemical crosslinking.
2. In the method, carbon-carbon double bonds are introduced into the polyamide fiber, and the percentage content of the carbon-carbon double bonds in the polyamide fiber is titrated by an iodometry method, wherein the content of the double bonds can reach 2.50-6.50% of the dry weight of the polyamide fiber.
3. The method solves the problem of how to modify the polyamide fiber by using the methacrylic anhydride, so that the polyamide fiber has excellent surface activity, and meanwhile, the reactive sites are increased, and the preparation cost is reduced. Meanwhile, the conductive carbon black is added on the basis of the prepared methacrylic anhydride modified polyamide fiber composite material to prepare the conductive carbon fiber, and the conductive carbon fiber has wide application in the fields of manufacturing engineering plastics and the like.
Drawings
FIG. 1 is an ATR-IR infrared spectrum of methacrylic anhydride-modified polyamide fiber obtained in example 1 of the present invention;
FIG. 2 is an ATR-IR infrared spectrum of methacrylic anhydride-modified polyamide fiber obtained in example 2 of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention provides a preparation method of methacrylic anhydride modified polyamide fiber, which specifically comprises the following steps:
step 1: and (3) water washing pretreatment of polyamide fibers:
the specific implementation steps of the step 1 are as follows:
taking polyamide fibers as raw materials, adding deionized water, ultrasonically cleaning for 0.5-1 h at room temperature, and drying at 60-100 ℃ for later use after cleaning; the dosage of deionized water is 5000% -6000% of the dry weight of polyamide;
step 2: polyamide fiber hydrolysis:
mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fiber pretreated by washing in the step 1, and reacting for 4-5 h at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 0.5h-1h, filtering, after the filter residues are completely cleaned when the pH value of the filtrate is neutral, drying the cleaned filter residues at 60-100 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the using amount of the concentrated sulfuric acid with the mass concentration of 98 percent is 15 to 20 percent of the dry weight of the polyamide fiber; the dosage of the deionized water is 5000% -6000% of the dry weight of the polyamide fiber in the step 1;
step 3: preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding a phosphoric acid buffer solution with the pH value of 7-8 to submerge the polyamide fiber in the conical flask, and magnetically stirring the polyamide fiber in a constant-temperature water bath kettle with the temperature of 70-80 ℃ for 0.5-1 h, wherein the rotation speed is 3-10 rpm; when the two are fully mixed, the temperature is reduced to 30-60 ℃, methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1-1.5 mL/min; the dosage of the methacrylic anhydride is 50% -800% of the dry weight of the aminated polyamide fiber in the step 2, the reaction is carried out for 0.5h-2.5h under the magnetic stirring, and the rotation speed is 3rpm-10rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 5000-6000% of the dry weight of the polyamide fiber containing amino in the step 2, the ultrasonic treatment time is 0.5-1 h, removing the residual methacrylic anhydride on the fiber, and drying at 60-100 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
The reaction principle of the methacrylic anhydride modified polyamide fiber is as follows:
the polyamide fiber can be hydrolyzed under the acidic condition, so that amino and carboxyl are generated on the surface of the polyamide fiber, then the lone pair electrons on the amino can generate nucleophilic addition-elimination reaction with the carbon groups on the methacrylic anhydride, and a part of water is removed to generate an amide bond, so that the carbon-carbon double bond can be grafted onto the polyamide fiber, the surface activity of the polyamide fiber is improved, the interfacial compatibility of different matrixes and the polyamide fiber is enhanced, and meanwhile, the reactive sites are increased, so that the surface active groups of the modified polyamide fiber are greatly improved.
The molecular chain of the polyamide fiber is formed by repeating amide groups (-NH) 2 ) And carboxyl (-COOH). The molecular formula is as follows: [ NH-R-CO ]] X
The reaction equation for the hydrolysis of polyamide fibers in step (2) is as follows:
the reaction equation of the methacrylic anhydride modified polyamide fiber in the step (3) is as follows:
(R, R' is a hydrocarbon group or the like in the polyamide fiber)
The polyamide fibers in the examples all require a drying treatment prior to use.
Example 1
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) And (3) water washing pretreatment of polyamide fibers:
taking 1 part of polyamide cloth sample with cutting length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning at room temperature for 0.5h, and drying at 70 ℃ for later use after cleaning; the dosage of deionized water is 5000% of the dry weight of polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fabric sample subjected to the water washing pretreatment in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 0.5h, filtering, cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residues at 60 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the amount of the concentrated sulfuric acid with the mass concentration of 98% is 15% of the dry weight of the polyamide fiber; the amount of deionized water used is 5000% of the dry weight of the polyamide fiber in step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with pH of 7 to submerge the polyamide fiber in the conical flask, and putting the conical flask into a constant-temperature water bath kettle with the temperature of 70 ℃ to magnetically stir for 0.5h, wherein the rotation speed is 3rpm; when the two are fully mixed, the temperature is reduced to 50 ℃, 1.2mL of methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 5000% of the dry weight of the polyamide fiber containing amino in the step 2, the ultrasonic treatment time is 0.5h, removing the residual methacrylic anhydride on the fiber, and drying at 60 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
FIG. 1 is an ATR-IR spectrum of a polyamide fiber, a methacrylated polyamide fiber. In infrared spectrogram, at 3300cm -1 The left and right broadband belongs to the stretching vibration absorption peak of-OH, -NH in the polyamide fiber and the modified polyamide fiber, and is 2800cm -1 -3000cm -1 The positions are the stretching vibration absorption peaks of methyl and methylene, and the polyamide fiber is 1643cm -1 Absorption peak at 1639cm and modified polyamide fiber -1 The absorption peak at which belongs to the telescopic vibration absorption peak of both C=O (amide I band), and the polyamide fiber is 1537cm -1 Absorption peak at 1532cm and modified polyamide fiber -1 The absorption peak at this point belongs to both the C-H bending vibration and the C-N stretching vibration in the C-N-H group (amide II band). 1643cm after simultaneous modification -1 The absorption peak at the position is shifted to 1639cm -1 ，1537cm -1 The absorption peak at the location shifted to 1532cm -1 Since the wave number of the peak becomes smaller and the frequency becomes lower according to the relation between the wave number and the frequency, the lower the energy of the peak is, the red shift of the two absorption peaks is affected by the structural change of the polyamide fiber. This is probably due to the partial hydrolysis of the polyamide fibres to amino and carboxyl groups. At 1325cm -1 And 1255cm -1 The two absorption peaks at this point are C-O stretching vibration of carboxylic acid and in-plane bending vibration of O-H in the C-O-H group, respectively. The N-H telescopic vibration energy in the amino group is slightly higher than that of the carboxylic acid C-O. The reactivity of amino is higher than that of carboxylic acid, which provides theoretical basis for subsequent methacrylic anhydride and amino generation reaction. As can be seen by comparing the peak shapes of the two, the modified polyamide fiber is at 1732cm -1 A new peak appears, the absorption peak is C=C telescopic vibration absorption peak of olefin, the peak is nucleophilic addition of methacrylic anhydride and amino groups on polyamide fiberElimination reaction, resulting in blue shift of the absorption peak position of the double bond due to the conjugated structure generated between the c=o bond and the c=c bond. At 1107cm -1 、950cm -1 A new peak appears, which is the out-of-plane bending vibration peak of c=c olefin. Therefore, the methacrylic anhydride successfully modifies the polyamide fiber, unsaturated carbon-carbon double bonds are successfully grafted on the polyamide fiber, the carbon-carbon double bonds are introduced into the surface of the polyamide fiber, the surface activity of the polyamide fiber is improved, the interfacial compatibility between different matrixes and the polyamide fiber is enhanced, and meanwhile, the modified polyamide fiber surface is roughened to generate more active functional groups such as amino groups and carboxyl groups, so that more polymerization active points are formed, and the possibility is provided for preparing the polyamide conductive fiber by depositing a conductive material on the surface of the polyamide fiber through chemical crosslinking.
The content of introduced double bonds in the methacrylic anhydride-modified polyamide fiber obtained in example 1 was 3.53% of the dry weight of the polyamide.
Example 2
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) And (3) water washing pretreatment of polyamide fibers:
taking 1 part of polyamide cloth sample with cutting length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning at room temperature for 0.5h, and drying at 70 ℃ for later use after cleaning; the dosage of deionized water is 5000% of the dry weight of polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fabric sample subjected to the water washing pretreatment in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 0.5h, filtering, cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residues at 100 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the amount of the concentrated sulfuric acid with the mass concentration of 98% is 15% of the dry weight of the polyamide fiber; the amount of deionized water used is 5000% of the dry weight of the polyamide fiber in step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH of 7.4 to submerge the polyamide fiber in the conical flask, and putting the conical flask into a constant-temperature water bath kettle with the temperature of 70 ℃ to magnetically stir for 0.5h, wherein the rotation speed is 3rpm; when the two are fully mixed, the temperature is reduced to 30 ℃, 1.2mL of methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 5000% of the dry weight of the polyamide fiber containing amino in the step 2, carrying out ultrasonic treatment for 2 hours, removing the residual methacrylic anhydride on the fiber, and drying at 70 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
FIG. 2 is an ATR-IR spectrum of polyamide fibers, methacrylated polyamide fibers. In infrared spectrogram, at 3300cm -1 The left and right broadband belongs to the stretching vibration absorption peak of-OH, -NH in the polyamide fiber and the modified polyamide fiber, and is 2800cm -1 -3000cm -1 The positions are the stretching vibration absorption peaks of methyl and methylene, and the polyamide fiber is 1639cm -1 Absorption peak at 1643cm and modified polyamide fiber -1 The absorption peak at the position belongs to the telescopic vibration absorption peak of C=O (amide I band) of the polyamide fiber and the polyamide fiber is 1532cm -1 Absorption peak at 1537cm and modified polyamide fiber -1 The absorption peak at this point belongs to both the C-H bending vibration and the C-N stretching vibration in the C-N-H group (amide II band). 1643cm after simultaneous modification -1 The absorption peak at the position is shifted to 1639cm -1 ，1537cm -1 The absorption peak at the location shifted to 1532cm -1 Since the wave number of the peak becomes smaller and the frequency becomes lower according to the relation between the wave number and the frequency, the lower the energy of the peak is, the red shift of the two absorption peaks is affected by the structural change of the polyamide fiber. This is probably due to the partial hydrolysis of the polyamide fibres to amino and carboxyl groups. At 1325cm -1 And 1255cm -1 The two absorption peaks at this point are C-O stretching vibration of carboxylic acid and in-plane bending vibration of O-H in the C-O-H group, respectively. The N-H telescopic vibration energy in the amino group is slightly higher than that of the carboxylic acid C-O. The reactivity of amino is higher than that of carboxylic acid, which provides theoretical basis for subsequent methacrylic anhydride and amino generation reaction. As a result of comparing the peak shapes of the two, it can be seen that the modified polyamide fiber is at 1723cm -1 A new peak appears, which is a c=c stretching vibration absorption peak of an olefin, which is a nucleophilic addition-elimination reaction of methacrylic anhydride with amino groups on polyamide fibers, and a blue shift occurs in the absorption peak position of a double bond due to a conjugated structure generated between c=o bonds and c=c bonds. At 1122cm -1 、948cm -1 A new peak appears, which is the out-of-plane bending vibration peak of c=c olefin. Thus, the successful modification of the polyamide fiber by methacrylic anhydride is demonstrated, and unsaturated carbon-carbon double bonds are successfully grafted on the polyamide fiber.
The content of introduced double bonds in the methacrylic anhydride-modified polyamide fiber obtained in example 2 was 5.52% of the dry weight of the polyamide.
Example 3
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) And (3) water washing pretreatment of polyamide fibers:
taking 1 part of polyamide cloth sample with cutting length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning at room temperature for 0.5h, and drying at 70 ℃ for later use after cleaning; the dosage of deionized water is 5000% of the dry weight of polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fabric sample subjected to the water washing pretreatment in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 0.5h, filtering, cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residues at 60 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the amount of the concentrated sulfuric acid with the mass concentration of 98% is 15% of the dry weight of the polyamide fiber; the amount of deionized water used is 5000% of the dry weight of the polyamide fiber in step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with pH of 8 to submerge the polyamide fiber in the conical flask, and putting the conical flask into a constant-temperature water bath kettle with the temperature of 70 ℃ to magnetically stir for 0.5h, wherein the rotation speed is 3rpm; when the two are fully mixed, the temperature is reduced to 50 ℃, 0.9mL of methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 5000% of the dry weight of the polyamide fiber containing amino in the step 2, the ultrasonic treatment time is 0.5h, removing the residual methacrylic anhydride on the fiber, and drying at 80 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
The content of introduced double bonds in the methacrylic anhydride modified polyamide fiber obtained in example 3 was 3.64% of the dry weight of the polyamide.
Example 4
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) And (3) water washing pretreatment of polyamide fibers:
taking 1 part of polyamide cloth sample with cutting length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning for 1h at room temperature, and drying at 100 ℃ for later use after cleaning; the dosage of deionized water is 6000% of the dry weight of polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fabric sample subjected to the water washing pretreatment in the step 1, and reacting for 5 hours at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 1h, filtering, after the filter residues are completely cleaned when the pH value of the filtrate is neutral, drying the cleaned filter residues at the temperature of 100 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the amount of the concentrated sulfuric acid with the mass concentration of 98% is 20% of the dry weight of the polyamide fiber; the dosage of deionized water is 6000% of the dry weight of the polyamide fiber in the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH of 7.6 to submerge the polyamide fiber in the conical flask, and putting the conical flask into a constant-temperature water bath kettle with the temperature of 80 ℃ to magnetically stir for 1h, wherein the rotation speed is 10rpm; when the two are fully mixed, the temperature is reduced to 60 ℃, 1.2mL of methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1.5mL/min; reacting for 2.5h under magnetic stirring, wherein the rotation speed is 10rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 6000% of the dry weight of the polyamide fiber containing amino in the step 2, carrying out ultrasonic treatment for 1h, removing the residual methacrylic anhydride on the fiber, and drying at 100 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
The content of introduced double bonds in the methacrylic anhydride modified polyamide fiber obtained in example 4 was 5.06% of the dry weight of the polyamide.
Example 5
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) And (3) water washing pretreatment of polyamide fibers:
taking 1 part of polyamide cloth sample with cutting length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning for 1h at room temperature, and drying at 100 ℃ for later use after cleaning; the dosage of deionized water is 5500% of the dry weight of polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide fabric sample subjected to the water washing pretreatment in the step 1, and reacting for 4.5 hours at room temperature; filtering after the reaction is finished, pouring out filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 1h, filtering, after the filter residues are completely cleaned when the pH value of the filtrate is neutral, drying the cleaned filter residues at 90 ℃ to obtain the amino-containing polyamide fiber;
mixed solvent: the amount of the concentrated sulfuric acid with the mass concentration of 98% is 18% of the dry weight of the polyamide fiber; the amount of deionized water used was 5500% of the dry weight of the polyamide fiber of step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the polyamide fiber containing amino groups obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH of 7.6 to submerge the polyamide fiber in the conical flask, and putting the conical flask into a constant-temperature water bath kettle with the temperature of 75 ℃ to magnetically stir for 1h, wherein the rotation speed is 5rpm; when the two are fully mixed, the temperature is reduced to 40 ℃, 1.2mL of methacrylic anhydride is slowly added dropwise into the conical flask when the temperature is constant, and the speed of the methacrylic anhydride dropwise is controlled to be 1.3mL/min; reacting for 2h under magnetic stirring, wherein the rotation speed is 5rpm; filtering after the reaction is finished, pouring out filtrate, mixing filter residues with deionized water, wherein the dosage of the deionized water is 5500% of the dry weight of the polyamide fiber containing amino in the step 2, carrying out ultrasonic treatment for 1h, removing the residual methacrylic anhydride on the fiber, and drying at 90 ℃ to obtain the methacrylic anhydride modified polyamide fiber containing double bonds.
The methacrylic anhydride manufacturer used in examples 1-5 was 94% by Shanghai Michelia Biochemical technology Co., ltd, and contained 0.2% topanol stabilizer. The polyamide fiber manufacturer is Wanhua chemical group Co., ltd, the molecular weight is 15000-23000, the specification is superfine fiber synthetic leather base cloth of indefinite island, and the fiber diameter is 1.4mm.
Claims (2)
1. The preparation method of the methacrylic anhydride modified polyamide fiber is characterized by comprising the following steps of:
step 1: washing and pre-treating polyamide fibers;
the specific implementation steps of the step 1 are as follows:
taking polyamide fibers as raw materials, adding deionized water, ultrasonically cleaning for 0.5-1 h at room temperature, and drying at 60-100 ℃ for later use after cleaning;
in the step 1, the dosage of deionized water is 5000% -6000% of the dry weight of polyamide;
step 2: polyamide fiber hydrolysis:
mixing concentrated sulfuric acid with the mass concentration of 98% with deionized water to obtain a mixed solvent, and mixing the mixed solvent with the polyamide fiber pretreated by the water washing in the step 1 to react at room temperature; filtering after the reaction is finished, pouring out filtrate, cleaning filter residues, and drying to obtain the polyamide fiber containing amino;
in the step 2, the using amount of the concentrated sulfuric acid with the mass concentration of 98% in the mixed solvent is 15% -20% of the dry weight of the polyamide fiber; the dosage of the deionized water is 5000% -6000% of the dry weight of the polyamide fiber in the step 1; the reaction time is 4h-5h at room temperature;
in the step 2, the filter residue cleaning process is as follows: ultrasonically cleaning filter residues for 0.5-1 h at room temperature by using deionized water, filtering, and finishing cleaning when the pH value of the filtrate is neutral;
in the step 2, the drying temperature is as follows: 60-100 ℃;
step 3: preparation of methacrylic anhydride modified polyamide fiber:
mixing the polyamide fiber containing amino groups obtained in the step 2 with a phosphoric acid buffer solution with the pH value of 7-8 under the water bath condition, magnetically stirring for 0.5-1 h, dropwise adding methacrylic anhydride after cooling, and reacting for 0.5-2.5 h under magnetic stirring; filtering after the reaction is finished, pouring out filtrate, cleaning filter residues, and drying to obtain methacrylic anhydride modified polyamide fibers containing double bonds;
in the step 3, the water bath temperature is 70-80 ℃; the rotation speed of the magnetic stirring for two times is 3rpm-10rpm;
in the step 3, methacrylic anhydride is dropwise added after the temperature is reduced to 30-60 ℃, and the speed of dropwise adding methacrylic anhydride is controlled to be 1-1.5 mL/min; the amount of methacrylic anhydride is 50% -800% of the dry weight of the aminated polyamide fiber in the step 2;
in the step 3, the filter residue cleaning process is as follows: ultrasonically cleaning filter residues for 0.5-1 h at room temperature by using deionized water, and filtering, wherein the dosage of the deionized water is 5000-6000% of the dry weight of the amino-containing polyamide fiber in the step 2; the drying temperature is as follows: 60-100 ℃.
2. Methacrylic anhydride modified polyamide fiber, characterized in that it is produced by the method according to claim 1.
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| WO2007036929A3 (en) * | 2005-09-29 | 2009-04-09 | Nilit Ltd | Modified polyamides, uses thereof and process for their preparation |
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| CN103710979A (en) * | 2013-12-03 | 2014-04-09 | 陕西科技大学 | Method for improving sanitation properties of polyamide superfine fiber synthetic leather base cloth |
| CN109183405A (en) * | 2018-08-24 | 2019-01-11 | 贵州大学 | A kind of processing method on nylon 66 fiber surface |
| CN114875666A (en) * | 2022-07-11 | 2022-08-09 | 江苏恒力化纤股份有限公司 | Preparation method of super-hydrophobic polyamide fiber product |
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| WO2007036929A3 (en) * | 2005-09-29 | 2009-04-09 | Nilit Ltd | Modified polyamides, uses thereof and process for their preparation |
| CN101407995A (en) * | 2008-11-20 | 2009-04-15 | 沈阳工业大学 | Aramid fiber surface modified method |
| CN103710979A (en) * | 2013-12-03 | 2014-04-09 | 陕西科技大学 | Method for improving sanitation properties of polyamide superfine fiber synthetic leather base cloth |
| CN109183405A (en) * | 2018-08-24 | 2019-01-11 | 贵州大学 | A kind of processing method on nylon 66 fiber surface |
| CN114875666A (en) * | 2022-07-11 | 2022-08-09 | 江苏恒力化纤股份有限公司 | Preparation method of super-hydrophobic polyamide fiber product |
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