CN115717330A - 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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- CN115717330A CN115717330A CN202211399690.3A CN202211399690A CN115717330A CN 115717330 A CN115717330 A CN 115717330A CN 202211399690 A CN202211399690 A CN 202211399690A CN 115717330 A CN115717330 A CN 115717330A
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 233
- 239000004952 Polyamide Substances 0.000 title claims abstract description 229
- 239000000835 fiber Substances 0.000 title claims abstract description 226
- 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 83
- 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 79
- 238000004140 cleaning Methods 0.000 claims abstract description 47
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 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
- 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
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- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 description 29
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
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- 150000001336 alkenes Chemical class 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000000269 nucleophilic effect Effects 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
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- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229920006052 Chinlon® Polymers 0.000 description 1
- QIZDQFOVGFDBKW-DHBOJHSNSA-N Pseudotropine Natural products OC1C[C@@H]2[N+](C)[C@H](C1)CC2 QIZDQFOVGFDBKW-DHBOJHSNSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
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- 239000013543 active substance Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
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- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 229920006130 high-performance polyamide Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- CYHOMWAPJJPNMW-JIGDXULJSA-N tropine Chemical compound C1[C@@H](O)C[C@H]2CC[C@@H]1N2C CYHOMWAPJJPNMW-JIGDXULJSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of methacrylic anhydride modified polyamide fiber, which comprises the following steps: step 1: polyamide fiber water washing pretreatment; step 2: polyamide fiber hydrolysis: and step 3: preparation of methacrylic anhydride modified polyamide fiber: mixing the amino-containing polyamide fiber 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 0.5h-1h, dropping methacrylic anhydride after cooling, and reacting for 0.5h-2.5h under the magnetic stirring; and (3) filtering after the reaction is finished, pouring the filtrate, cleaning the filter residue, and drying to finally obtain the double-bond methacrylic anhydride modified polyamide fiber. The method solves the problem of how to utilize methacrylic anhydride to modify polyamide fiber, so that the polyamide fiber has excellent surface activity and the preparation cost is reduced.
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
The polyamide fiber is commonly called chinlon in China, has excellent mechanical property, wear resistance and chemical corrosion resistance, and is widely applied to the fields of clothing, home textiles and industry. With the continuous improvement of the life quality of people, the demand of 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 sweat releasing, antibiosis, ultraviolet resistance and the like for improving the wearability will rapidly increase; secondly, the excellent performance of the polyamide fiber is utilized, and special functions such as high temperature resistance, flame retardance, high strength and modulus and the like are endowed through modification, so that the application of the high-function and high-performance polyamide fiber in the increasing national economy and national defense construction is increasing continuously. In addition, conductive fibers have emerged as a new fiber variety and are used in large quantities. The fiber has excellent performances such as good conductivity, antistatic property and durability. However, the surface of polyamide fibers is generally smooth and has weak interfacial bonding with the matrix. Secondly, 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, so that the surface activity of the fiber is improved.
Oliveria et al use double barrier dielectric plasma (DBD) to modify polyamide fibers, and increase surface roughness and improve wettability of polyamide fibers after plasma treatment. However, the plasma treatment technology is too costly to be popularized, and is generally dedicated to a special research institute or a research institute. Therefore, this method is difficult to popularize. Rietzler et al use CaCl 2 /H 2 The O/EtOH system surface modifies polyamide fibers, the treated polyamide fibers having greater diameter and surface roughness for advanced materials for storing and releasing 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 bonded in a non-covalent bond mode, and the bonding force after modification is not very strong. Yang Yanning et al adopt silane coupling agent KH-550 to perform surface treatment on polyamide fiber, and the interface bonding property of the treated fiber and resin is increased, and the mechanical property of the composite material is further improved. Lin Jeng-Shyong and Yuan Haigen and the like are used for increasing the interfacial bonding capacity of aramid fiber and epoxy resin, and are soaked and treated after sodium salt is dissolved by dimethyl sulfoxide, so that Na on the surface of the fiber + Chemical groups on the surface of aramid fibersThe activity is greatly improved, and the interface bonding capability of the composite material is further improved. After the aramid fiber is grafted by bromoacetic acid in Lin and compounded with epoxy resin, the interlayer peeling strength of the composite material is found to reach 28.45MPa, and is improved by 12%.
In the above polyamide fiber modification mode, the surface of the polyamide fiber is etched to a great extent, the breaking strength of the composite material is affected, and the preparation cost is too high. In addition, as an inert material, the polyamide fiber has few active groups which can participate in the reaction on the surface, and is difficult to modify.
Disclosure of Invention
The invention aims 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 interface compatibility of different matrixes and the polyamide fiber.
The second purpose of the invention is to provide a methacrylic anhydride modified polyamide fiber which has excellent surface activity and enhances the interface compatibility of different matrixes and polyamide fibers.
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: polyamide fiber water washing pretreatment;
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 water washing in the step 1 for reaction at room temperature; filtering after the reaction is finished, pouring the filtrate, cleaning the filter residue, and drying to finally obtain the polyamide fiber containing amino;
and step 3: preparation of methacrylic anhydride modified polyamide fiber:
mixing the amino-containing polyamide fiber obtained in the step 2 with a phosphoric acid buffer solution with the pH value of 7-8 under the condition of water bath, magnetically stirring for 0.5-1 h, dropping methacrylic anhydride after cooling, and reacting for 0.5-2.5 h under the magnetic stirring; and (3) filtering after the reaction is finished, pouring the filtrate, cleaning the filter residue, and drying to finally obtain the double-bond methacrylic anhydride modified polyamide fiber.
The present invention is also characterized in that,
the specific implementation steps of the step 1 are as follows:
the polyamide fiber is taken as a raw material, deionized water is added, ultrasonic cleaning is carried out for 0.5h-1h at room temperature, and drying is carried out at 60 ℃ -100 ℃ for standby after cleaning.
In step 1, the amount of deionized water is 5000-6000% of the dry weight of the polyamide.
In the step 2, in the mixed solvent, the using amount of concentrated sulfuric acid with the mass concentration of 98 percent is 15 to 20 percent of the dry weight of the polyamide fiber; the amount of the used deionized water is 5000-6000% of the dry weight of the polyamide fiber in the step 1; the reaction time is 4-5 h at room temperature.
In the step 2, the filter residue cleaning process comprises the following steps: ultrasonically cleaning the filter residue for 0.5-1 h at room temperature by using deionized water, filtering, and cleaning when the pH value of the filtrate is neutral.
In step 2, the drying temperature is as follows: 60-100 ℃.
In step 3, the temperature of the water bath is 70-80 ℃; the rotation speed of the two magnetic stirring steps is 3-10 rpm.
In the step 3, dropping methacrylic anhydride after the temperature is reduced to 30-60 ℃, wherein the dropping rate of the methacrylic anhydride is controlled to be 1-1.5 mL/min; methacrylic anhydride is used in an amount of 50% to 800% by dry weight of the aminated polyamide fiber in step 2.
In the step 3, the filter residue cleaning process comprises the following steps: ultrasonically cleaning the filter residue for 0.5-1 h at room temperature by using deionized water, and filtering, wherein the using amount 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 the method.
The invention has the beneficial effects that:
1. the invention has low manufacturing cost and simple and feasible preparation method, and utilizes chemical modification to graft carbon-carbon double bonds into the molecular chain of the polyamide fiber. The surface activity of the polyamide fiber is improved, the interface compatibility of different matrixes and the polyamide fiber is enhanced, and meanwhile, the surface of the modified polyamide fiber is roughened to generate more active functional groups such as amino and carboxyl, 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.
2. The method of the invention introduces carbon-carbon double bonds into the polyamide fibers, and titrates the percentage content of the carbon-carbon double bonds in the polyamide fibers by an iodometry method, wherein the content of the double bonds can reach 2.50-6.50% of the dry weight of the polyamide fibers.
3. The method solves the problem of how to modify the polyamide fiber by using methacrylic anhydride, so that the polyamide fiber has excellent surface activity, reactive active sites are increased, and the preparation cost is reduced. Meanwhile, the conductive carbon fiber is prepared by adding conductive carbon black on the basis of the prepared methacrylic anhydride modified polyamide fiber composite material, and the conductive carbon fiber is widely applied to the fields of manufacturing engineering plastics and the like.
Drawings
FIG. 1 is an ATR-IR infrared spectrum of a methacrylic anhydride-modified polyamide fiber obtained in example 1 of the present invention;
FIG. 2 is an ATR-IR infrared spectrum of a methacrylic anhydride-modified polyamide fiber obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of methacrylic anhydride modified polyamide fiber, which comprises the following steps:
step 1: polyamide fiber water washing pretreatment:
the specific implementation steps of the step 1 are as follows:
adding deionized water into polyamide fiber as a raw material, ultrasonically cleaning for 0.5-1 h at room temperature, and drying at 60-100 ℃ after cleaning; the using amount of the deionized water is 5000-6000% of the dry weight of the 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 water washing in the step 1, and reacting for 4-5 h at room temperature; filtering after the reaction is finished, pouring the filtrate, reserving the filter residue, cleaning the filter residue, ultrasonically cleaning the filter residue for 0.5-1 h at room temperature, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residue at the temperature of 60-100 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the dosage of concentrated sulfuric acid with the mass concentration of 98 percent is 15 to 20 percent of the dry weight of the polyamide fiber; the amount of the used deionized water is 5000-6000% of the dry weight of the polyamide fiber in the step 1;
and step 3: preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding a phosphoric acid buffer solution with the pH value of 7-8 to immerse the polyamide fiber in the conical flask, and placing the polyamide fiber in a constant-temperature water bath kettle at the temperature of 70-80 ℃ to magnetically stir for 0.5-1 h at the rotation speed of 3-10 rpm; when the two are fully mixed, the temperature is reduced to 30-60 ℃, methacrylic anhydride is slowly dripped into the conical flask when the temperature is constant, and the dripping speed of the methacrylic anhydride is controlled to be 1mL/min-1.5mL/min; the dosage of the methacrylic anhydride is 50 to 800 percent of the dry weight of the aminated polyamide fiber in the step 2, the reaction is carried out for 0.5 to 2.5 hours under the magnetic stirring, and the rotating speed is 3 to 10rpm; and (2) filtering after the reaction is finished, pouring out filtrate, mixing filter residue with deionized water, wherein the amount of the deionized water is 5000-6000% of the dry weight of the amino-containing polyamide fiber in the step (2), performing ultrasonic treatment for 0.5-1 h, removing residual methacrylic anhydride on the fiber, and drying at the temperature of 60-100 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
The reaction principle of the methacrylic anhydride modified polyamide fiber is as follows:
the polyamide fiber is hydrolyzed under an acidic condition, so that amino and carboxyl are generated on the surface of the polyamide fiber, next, lone pair electrons on the amino and carbon groups on methacrylic anhydride are subjected to nucleophilic addition-elimination reaction, a part of water is removed, and amide bonds are generated, so that carbon-carbon double bonds can be grafted to 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 simultaneously, reaction active 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 composed of repeated amide groups (-NH) 2 ) And a carboxyl group (-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 radical of a polyamide fiber such as a hydrocarbon radical)
The polyamide fibers in the examples were dried before use.
Example 1
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) Polyamide fiber water washing pretreatment:
taking 1 part of polyamide base fabric sample with the cut length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning for 0.5h at room temperature, and drying at 70 ℃ for later use after cleaning; the using amount of the deionized water is 5000 percent of the dry weight of the 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-based fabric sample pretreated by water washing in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring out the filtrate, reserving filter residues, cleaning the filter residues, ultrasonically cleaning the filter residues at room temperature for 0.5h, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residues at the temperature of 60 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the use amount of concentrated sulfuric acid with the mass concentration of 98 percent is 15 percent 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 the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH value of 7 to immerse the polyamide fiber in the conical flask, and placing the polyamide fiber in a constant-temperature water bath kettle at 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 ℃, and when the temperature is constant, 1.2mL of methacrylic anhydride is slowly dripped into the conical flask, and the dripping speed of the methacrylic anhydride is controlled at 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; and (3) filtering after the reaction is finished, pouring out filtrate, mixing filter residue with deionized water, wherein the amount of the deionized water is 5000% of the dry weight of the amino-containing polyamide fiber in the step (2), performing ultrasonic treatment for 0.5h, removing residual methacrylic anhydride on the fiber, and drying at 60 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
FIG. 1 shows ATR-IR spectra of polyamide fibers and methacrylic anhydrified polyamide fibers. In the infrared spectrum, 3300cm -1 The left and right broadband belongs to the stretching vibration absorption peak of-OH and-NH in polyamide fiber and modified polyamide fiber, and is 2800cm -1 -3000cm -1 The fiber has stretching vibration absorption peak of methyl and methylene, and the polyamide fiber is 1643cm -1 The absorption peak and the modified polyamide fiber are 1639cm -1 The absorption peak at (A) belongs to the stretching vibration absorption peak of both C = O (amide I band), and the polyamide fiber is at 1537cm -1 The absorption peak and the modified polyamide fiber are at 1532cm -1 The absorption peaks at (A) belong to both C-H bending vibration and C-N stretching vibration in the C-N-H group (amide II band). At the same time change1643cm after sex -1 The absorption peak at (A) is shifted to 1639cm -1 ，1537cm -1 The absorption peak at (A) is shifted to 1532cm -1 Since the wave number of the peak is small and the frequency is low in accordance with the relationship between the wave number and the frequency, the lower the energy of the peak is, the influence of the structural change of the polyamide fiber is caused by the red shift of the two absorption peaks. This is probably due to the partial hydrolysis of the polyamide fibres to form amino and carboxyl groups. At 1325cm -1 And 1255cm -1 The two absorption peaks at (A) are respectively C-O stretching vibration of carboxylic acid and O-H in-plane bending vibration of C-O-H group. The stretching vibration energy of N-H in the amino is slightly higher than that of C-O of carboxylic acid. The reactivity of the amino group is higher than that of the carboxylic acid, and a theoretical basis is provided for the subsequent reaction of the methacrylic anhydride and the amino group. Comparing the peak shapes of the two types of fibers, the modified polyamide fiber is 1732cm -1 A new peak appears, which is a C = C stretching vibration absorption peak of the olefin, and which is a nucleophilic addition-elimination reaction of methacrylic anhydride with an amino group on the polyamide fiber, resulting in a blue shift of the absorption peak position of the double bond due to the generation of a conjugated structure between the C = O bond and the C = C bond. At 1107cm -1 、950cm -1 A new peak appears, this absorption peak being the out-of-plane bending vibration peak of C = C olefins. 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 to the surface of the polyamide fiber, the surface activity of the polyamide fiber is improved, the interface compatibility of different matrixes and the polyamide fiber is enhanced, meanwhile, the surface of the modified polyamide fiber is roughened to generate more active functional groups such as amino and carboxyl, 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 the double bond introduced into the methacrylic anhydride-modified polyamide fiber obtained in example 1 was 3.53% by dry weight of the polyamide.
Example 2
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) Polyamide fiber water washing pretreatment:
taking 1 part of polyamide base fabric sample with the cut length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning for 0.5h at room temperature, and drying at 70 ℃ for later use after cleaning; the using amount of the deionized water is 5000 percent of the dry weight of the 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-based fabric sample pretreated by water washing in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring the filtrate, reserving the filter residue, cleaning the filter residue, ultrasonically cleaning the filter residue at room temperature for 0.5h, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residue at 100 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the use amount of concentrated sulfuric acid with the mass concentration of 98 percent is 15 percent 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 the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH value of 7.4 to immerse the polyamide fiber in the conical flask, placing the polyamide fiber in a constant-temperature water bath kettle at the temperature of 70 ℃, and magnetically stirring for 0.5h at the rotation speed of 3rpm; when the two are fully mixed and the temperature is reduced to 30 ℃, slowly dripping 1.2mL of methacrylic anhydride into the conical flask when the temperature is constant, and controlling the dripping speed of the methacrylic anhydride to be 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; and (3) filtering after the reaction is finished, pouring out the filtrate, mixing the filter residue with deionized water, wherein the use amount of the deionized water is 5000% of the dry weight of the amino-containing polyamide fiber in the step (2), performing ultrasonic treatment for 2 hours, removing the residual methacrylic anhydride on the fiber, and drying at 70 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
FIG. 2 shows ATR-IR spectra of polyamide fibers and methacrylic anhydrified polyamide fibers. In the infrared spectrum, 3300cm -1 Left and right wide frequency bands belonging to the groupThe expansion vibration absorption peak of-OH and-NH in the amide fiber and the modified polyamide fiber is 2800cm -1 -3000cm -1 The absorption peak of the elastic vibration is methyl and methylene, and the polyamide fiber is 1639cm -1 The absorption peak of the fiber and the modified polyamide fiber are 1643cm -1 The absorption peak at (A) belongs to the stretching vibration absorption peak of both C = O (amide I band), and the polyamide fiber is at 1532cm -1 The absorption peak and the modified polyamide fiber are at 1537cm -1 The absorption peaks at (A) belong to both C-H bending vibration and C-N stretching vibration in the C-N-H group (amide II band). 1643cm after simultaneous modification -1 The absorption peak of (A) is shifted to 1639cm -1 ，1537cm -1 The absorption peak at (A) is shifted to 1532cm -1 Since the wave number of the peak is small and the frequency is low in accordance with the relationship between the wave number and the frequency, the lower the energy of the peak is, the influence of the structural change of the polyamide fiber is caused by the red shift of the two absorption peaks. This is probably due to the partial hydrolysis of the polyamide fibres to form amino and carboxyl groups. At 1325cm -1 And 1255cm -1 The two absorption peaks at (A) are respectively C-O stretching vibration of carboxylic acid and O-H in-plane bending vibration of C-O-H group. The stretching vibration energy of N-H in the amino is slightly higher than that of C-O of carboxylic acid. The reactivity of the amino group is higher than that of the carboxylic acid, and a theoretical basis is provided for the subsequent reaction of the methacrylic anhydride and the amino group. Comparing the peak shapes of the two types of fibers, the modified polyamide fiber is found to be at 1723cm -1 A new peak appears, which is a C = C stretching vibration absorption peak of the olefin, and which is a nucleophilic addition-elimination reaction of methacrylic anhydride with an amino group on the polyamide fiber, resulting in a blue shift of the absorption peak position of the double bond due to the generation of a conjugated structure between the C = O bond and the C = C bond. At 1122cm -1 、948cm -1 A new peak appears, this absorption peak being the out-of-plane bending vibration peak of C = C olefins. Therefore, the methacrylic anhydride successfully modifies the polyamide fiber, and unsaturated carbon-carbon double bonds are successfully grafted on the polyamide fiber.
The content of the double bond introduced into the methacrylic anhydride-modified polyamide fiber obtained in example 2 was 5.52% by dry weight of the polyamide.
Example 3
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) Polyamide fiber water washing pretreatment:
taking 1 part of polyamide base fabric sample with the cut length of 20mm multiplied by 20mm, adding the sample into a beaker, adding deionized water, ultrasonically cleaning for 0.5h at room temperature, and drying at 70 ℃ for later use after cleaning; the using amount of the deionized water is 5000% of the dry weight of the 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-based fabric sample pretreated by water washing in the step 1, and reacting for 4 hours at room temperature; filtering after the reaction is finished, pouring the filtrate, reserving the filter residue, cleaning the filter residue, ultrasonically cleaning the filter residue at room temperature for 0.5h, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residue at the temperature of 60 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the use amount of concentrated sulfuric acid with the mass concentration of 98 percent is 15 percent of the dry weight of the polyamide fiber; the amount of the deionized water used is 5000 percent of the dry weight of the polyamide fiber in the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH value of 8 to immerse the polyamide fiber in the conical flask, and placing the polyamide fiber in a constant-temperature water bath kettle at 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 dripped into the conical flask when the temperature is constant, and the dripping speed of the methacrylic anhydride is controlled at 1mL/min; reacting for 0.5h under magnetic stirring, wherein the rotation speed is 3rpm; and (3) filtering after the reaction is finished, pouring out filtrate, mixing filter residue with deionized water, wherein the amount of the deionized water is 5000% of the dry weight of the amino-containing polyamide fiber in the step (2), performing ultrasonic treatment for 0.5h, removing residual methacrylic anhydride on the fiber, and drying at 80 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
The content of the double bond introduced into the methacrylic anhydride-modified polyamide fiber obtained in example 3 was 3.64% by dry weight of the polyamide.
Example 4
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) Polyamide fiber water washing pretreatment:
taking 1 part of polyamide base fabric sample with the cut 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 using amount of the deionized water is 6000 percent of the dry weight of the polyamide;
(2) Hydrolysis of polyamide fibres
Mixing concentrated sulfuric acid with the mass concentration of 98% and deionized water to obtain a mixed solvent, mixing the mixed solvent with the polyamide base cloth sample pretreated by water washing in the step 1, and reacting for 5 hours at room temperature; filtering after the reaction is finished, pouring the filtrate, reserving the filter residue, cleaning the filter residue, ultrasonically cleaning the filter residue for 1h at room temperature, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residue at 100 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the dosage of the concentrated sulfuric acid with the mass concentration of 98 percent is 20 percent of the dry weight of the polyamide fiber; the amount of deionized water used is 6000 percent of the dry weight of the polyamide fiber in the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH value of 7.6 to immerse the polyamide fiber in the conical flask, placing the polyamide fiber in a constant-temperature water bath kettle at the temperature of 80 ℃, and magnetically stirring for 1h at the rotation speed of 10rpm; when the two are fully mixed, the temperature is reduced to 60 ℃, and when the temperature is constant, 1.2mL of methacrylic anhydride is slowly dripped into the conical flask, and the dripping speed of the methacrylic anhydride is controlled at 1.5mL/min; reacting for 2.5 hours under magnetic stirring, wherein the rotation speed is 10rpm; and (3) filtering after the reaction is finished, pouring out filtrate, mixing filter residue with deionized water, wherein the dosage of the deionized water is 6000% of the dry weight of the amino-containing polyamide fiber in the step (2), performing ultrasonic treatment for 1h, removing residual methacrylic anhydride on the fiber, and drying at 100 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
The content of the double bond introduced into the methacrylic anhydride-modified polyamide fiber obtained in example 4 was 5.06% by dry weight of the polyamide.
Example 5
The preparation method of the methacrylic anhydride modified polyamide fiber comprises the following steps:
(1) Polyamide fiber water washing pretreatment:
taking 1 part of polyamide base fabric sample with the cut 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 using amount of the deionized water is 5500 percent of the dry weight of the 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-based fabric sample pretreated by water washing in the step 1, and reacting for 4.5 hours at room temperature; filtering after the reaction is finished, pouring the filtrate, reserving the filter residue, cleaning the filter residue, ultrasonically cleaning the filter residue for 1h at room temperature, filtering, finishing cleaning when the pH value of the filtrate is neutral, and drying the cleaned filter residue at 90 ℃ to obtain the amino-containing polyamide fiber;
in the mixed solvent: the dosage of concentrated sulfuric acid with the mass concentration of 98 percent is 18 percent of the dry weight of the polyamide fiber; the amount of deionized water used is 5500% of the dry weight of the polyamide fiber in the step 1;
(3) Preparation of methacrylic anhydride modified polyamide fiber
Putting the amino-containing polyamide fiber obtained in the step 2 into a conical flask, adding 50mL of phosphoric acid buffer solution with the pH value of 7.6 to immerse the polyamide fiber in the conical flask, placing the polyamide fiber in a constant-temperature water bath kettle at the temperature of 75 ℃, and magnetically stirring for 1h at the rotation speed of 5rpm; when the two are fully mixed, the temperature is reduced to 40 ℃, and when the temperature is constant, 1.2mL of methacrylic anhydride is slowly dripped into the conical flask, and the dripping speed of the methacrylic anhydride is controlled at 1.3mL/min; reacting for 2 hours under magnetic stirring, wherein the rotation speed is 5rpm; and (3) filtering after the reaction is finished, pouring out the filtrate, mixing the filter residue with deionized water, wherein the use amount of the deionized water is 5500% of the dry weight of the amino-containing polyamide fiber obtained in the step (2), performing ultrasonic treatment for 1 hour, removing the residual methacrylic anhydride on the fiber, and drying at 90 ℃ to obtain the double-bond methacrylic anhydride modified polyamide fiber.
The methacrylic anhydride manufacturer used in examples 1-5 was Shanghai Michelin Biochemical technology Ltd, 94% specification, containing 0.2% of the tropanol stabilizer. The polyamide fiber manufacturer is Wanhua chemical group limited company, the molecular weight of the polyamide fiber is 15000-23000, the polyamide fiber is the amorphous island superfine fiber synthetic leather base cloth, and the fiber diameter is 1.4mm.
Claims (10)
1. The preparation method of the methacrylic anhydride modified polyamide fiber is characterized by comprising the following steps:
step 1: polyamide fiber water washing pretreatment;
and 2, step: 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 water washing in the step 1 for reaction at room temperature; filtering after the reaction is finished, pouring the filtrate, cleaning the filter residue, and drying to finally obtain the polyamide fiber containing amino;
and step 3: preparation of methacrylic anhydride modified polyamide fiber:
mixing the amino-containing polyamide fiber obtained in the step 2 with a phosphoric acid buffer solution with the pH value of 7-8 under the condition of water bath, magnetically stirring for 0.5-1 h, dropping methacrylic anhydride after cooling, and reacting for 0.5-2.5 h under the magnetic stirring; and (3) filtering after the reaction is finished, pouring the filtrate, cleaning the filter residue, and drying to finally obtain the double-bond methacrylic anhydride modified polyamide fiber.
2. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein the step 1 is carried out by the following steps:
the polyamide fiber is taken as a raw material, deionized water is added, ultrasonic cleaning is carried out for 0.5-1 h at room temperature, and drying is carried out at 60-100 ℃ after cleaning is finished for standby.
3. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 2, wherein in the step 1, the amount of deionized water is 5000-6000% of the dry weight of the polyamide.
4. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein in the step 2, the amount of 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 using amount of the deionized water is 5000-6000% of the dry weight of the polyamide fiber in the step 1; the reaction time is 4-5 h at room temperature.
5. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein in the step 2, the process of cleaning the filter residue comprises: ultrasonically cleaning the filter residue for 0.5-1 h at room temperature by using deionized water, filtering, and cleaning when the pH value of the filtrate is neutral.
6. The method for preparing methacrylic anhydride-modified polyamide fiber according to claim 1, wherein in the step 2, the drying temperature is: 60-100 ℃.
7. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein in the step 3, the water bath temperature is 70 ℃ to 80 ℃; the rotation speed of the two magnetic stirring steps is 3-10 rpm.
8. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein in step 3, after the temperature is reduced to 30 ℃ to 60 ℃, methacrylic anhydride is added dropwise, and the rate of adding methacrylic anhydride dropwise is controlled to be 1mL/min to 1.5mL/min; methacrylic anhydride is used in an amount of 50% to 800% by dry weight of the aminated polyamide fiber in step 2.
9. The method for preparing methacrylic anhydride modified polyamide fiber according to claim 1, wherein in the step 3, the process of cleaning the filter residue comprises: ultrasonically cleaning the filter residue for 0.5-1 h at room temperature by using deionized water, and filtering, wherein the using amount 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 ℃.
10. Methacrylic anhydride modified polyamide fibre, characterized in that it is obtained by a process according to any one of claims 1 to 9.
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| WO2007036929A2 (en) * | 2005-09-29 | 2007-04-05 | Nilit Ltd. | Modified polyamides, uses thereof and process for their preparation |
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| 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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| WO2007036929A2 (en) * | 2005-09-29 | 2007-04-05 | 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 |
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