CN111514660A - Aminated titanium oxide modified polyimide fiber filter material and preparation method thereof - Google Patents

Aminated titanium oxide modified polyimide fiber filter material and preparation method thereof Download PDF

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CN111514660A
CN111514660A CN202010372436.9A CN202010372436A CN111514660A CN 111514660 A CN111514660 A CN 111514660A CN 202010372436 A CN202010372436 A CN 202010372436A CN 111514660 A CN111514660 A CN 111514660A
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titanium oxide
aminated
modified polyimide
nano titanium
polyimide fiber
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王文爽
沈文齐
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Bengbu Taixin Material Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
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    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

The invention discloses an aminated titanium oxide modified polyimide fiber filter material, which comprises the following components in percentage by weight: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the copolymerization reaction system comprises the following raw materials in percentage by mass: 1.5-2.5% of aminated nano titanium oxide, 10-15% of 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and p-phenylenediamine, 1-1.5% of isoquinoline and the balance of N-methylpyrrolidone; the preparation method of the aminated nano titanium oxide comprises the following steps: dissolving titanium tetrachloride and gamma-aminoethyl aminopropyl trimethoxysilane in a 50% ethanol solution, dropwise adding a 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 6-12 h, dropwise adding N, N, N' -trimethylethylenediamine, standing and aging for 3-6 h, filtering, washing and drying. The invention realizes the modification effect of the nano titanium oxide on polyimide from a molecular layer for the first time, and the prepared filter material has high stability, good mechanical property, durability and weather resistance, and can not generate the phenomena of falling off and peeling off of the nano titanium oxide.

Description

Aminated titanium oxide modified polyimide fiber filter material and preparation method thereof
Technical Field
The invention belongs to the technical field of polyimide preparation, and particularly relates to an aminated titanium oxide modified polyimide fiber filter material and a preparation method thereof.
Background
Polyimide is a polymer containing imide rings (-CO-N-CO-) on the main chain, has high temperature resistance of more than 400 ℃, long-term use temperature range of-200-300 ℃, excellent thermal stability and mechanical strength, corrosion resistance and high insulativity, a dielectric constant of 4.0 at 103 Hz and dielectric loss of only 0.004-0.007, belongs to F to H, is one of organic polymer materials with the best comprehensive performance, and is widely applied to the fields of aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, lasers and the like.
With the increasing severity of the environmental pollution caused by high-temperature flue gas such as industrial flue gas, combustion coal, automobile exhaust, biomass combustion, metallurgy, etc., the high-temperature filtration and dust removal technology has become a research hotspot in the industrial and academic industries. At present, high-temperature flue gas filter materials mainly take high-temperature resistant polymer fibers such as polyimide, polyphenylene sulfide, aromatic polyamide, polysulfonamide, polytetrafluoroethylene and the like as raw materials, and mainly filter and separate fine particles in high-temperature flue gas, but industrial high-temperature flue gas often contains SOx、NOx、H2S, HCN, etc., and various photocatalyst/polyimide composite materials have been developed to further degrade the toxic and harmful gases.
The existing polyimide/titanium dioxide composite material is mainly utilizedThe nano titanium oxide is prepared by mixing and reacting the nano titanium oxide, diamine and dianhydride, but the nano titanium oxide does not participate in polymerization reaction, but is compounded with the polyimide fiber in a physical blending mode, the combination firmness is not high, and the nano titanium oxide is easy to fall off from the surface of the polyimide fiber, for example, the patent of application number CN201710857569.3 discloses the polyimide/titanium dioxide hybrid fiber, and nano TiO is utilized24,4' -diaminodiphenyl ether and pyromellitic dianhydride are mixed and reacted to prepare the polyimide/titanium dioxide hybrid fiber, but the nano TiO is2Is a physical doping mode. In addition, the method is only suitable for the synthesized polyimide fiber, is not suitable for diamine monomers and dianhydride monomers which do not undergo condensation polymerization, has limitations on synthesis process and application, is also physical deposition essentially, does not have chemical crosslinking effect on polyimide and titanium oxide, has poor durability and wear resistance, can cause the titanium oxide deposited on the surface to fall off after long-term use, and can cause the nano particles to easily perform in-situ blocking on the pore diameter of the fiber membrane in the direct deposition process so as to greatly reduce the filtration efficiency of the fiber membrane, for example, the patent with the application number of CN201610050579.1 discloses a preparation method of the polyimide fiber membrane with the surface coated with a titanium dioxide nano layer, the polyamide acid fiber membrane is treated by a titanium compound, for example, patent with application number of CN201710132514.6, discloses a polyimide/titanium dioxide composite fiber and a preparation method and application thereof, wherein a titanyl sulfate solution is used for impregnating the polyimide fiber, ammonia water is added for in-situ precipitation, and the polyimide/titanium dioxide composite fiber is obtained after heat treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an aminated titanium oxide modified polyimide fiber filter material and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
an aminated titanium oxide modified polyimide fiber filter material: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the copolymerization reaction system comprises the following raw materials in percentage by mass:
Figure BDA0002478643700000031
the preparation method of the aminated nano titanium oxide comprises the following steps: dissolving titanium tetrachloride and gamma-aminoethyl aminopropyltrimethoxysilane in a 50% ethanol solution, dropwise adding a 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 6-12 h, dropwise adding N, N, N' -trimethylethylenediamine, standing and aging for 3-6 h, filtering, washing and drying to obtain aminated nano titanium oxide; the using proportion of titanium tetrachloride, gamma-aminoethyl aminopropyltrimethoxysilane, N, N, N' -trimethylethylenediamine, 2mol/L NaOH solution and 50% ethanol solution is (10-20) mmol: (4-7.5) mmol: (1-1.5) mmol: (20-40) mL: 100 mL.
Preferably, the molar ratio of the 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride to the p-phenylenediamine is 1: (0.85-0.9).
A preparation method of a modified polyimide fiber filter material comprises the following steps:
s1: preparing modified polyimide: dissolving 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and p-phenylenediamine in an N-methylpyrrolidone solvent, adding isoquinoline, heating to 120-180 ℃, uniformly dividing the functionalized nano titanium oxide for 3 times, adding the mixture into a reaction system, stirring and polymerizing for 12-24 hours, and synthesizing a modified polyimide solution;
s2: electrostatic spinning: and diluting the modified polyimide solution to a solid content of 5-10%, and performing electrostatic spinning under a voltage of 15-20 kV to prepare the titanium oxide cross-linked modified polyimide fiber non-woven fabric.
The invention has the beneficial effects that:
1. according to the invention, the aminated nano titanium oxide is prepared by a hydrothermal method of gamma-aminoethyl aminopropyltrimethoxysilane, N, N, N' -trimethylethylenediamine and titanium tetrachloride for the first time, and then the amidation reaction between amino and carboxyl is utilized to carry out condensation copolymerization with dianhydride monomers and diamine monomers, so that the nano titanium oxide is grafted or crosslinked onto a polyimide molecular chain.
2. The polyimide fiber non-woven fabric prepared by the method has high specific surface area which can reach 804.9m2More than g, wherein the surface area of the micropores with the pore diameter of less than 1nm can reach 172.6m2More than g, the filter efficiency of the high-temperature flue gas is effectively improved, and meanwhile, toxic and harmful substances in the high-temperature flue gas can be efficiently degraded.
Drawings
FIG. 1 is a flow chart of a preparation method of an aminated titanium oxide modified polyimide fiber filter material.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
A preparation method of an aminated titanium oxide modified polyimide fiber filter material comprises the following steps: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the method specifically comprises the following steps:
s1: preparing aminated nano titanium oxide: dissolving 25mmol of titanium tetrachloride and 10mmol of gamma-aminoethyl aminopropyltrimethoxysilane in 250mL of 50% ethanol solution, dropwise adding 50mL of 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 6 hours, dropwise adding 2.5mmol of N, N, N' -trimethylethylenediamine, standing and aging for 3 hours, filtering, washing and drying to obtain aminated nano titanium oxide;
s2: preparing modified polyimide: 7.715g of 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 2.285g of p-phenylenediamine (the molar ratio of the two is 1: 0.85) are dissolved in 87.5g of N-methylpyrrolidone solvent, 1g of isoquinoline is added, the temperature is raised to 60 ℃, 1.5g of functionalized nano titanium oxide is evenly divided for 3 times and added into a reaction system, stirring and polymerization are carried out for 4 hours, the temperature is continuously raised to 180 ℃, and imidization is carried out for 10 hours, so as to synthesize a modified polyimide solution;
s2: electrostatic spinning: and diluting the modified polyimide solution to 5% of solid content, and performing electrostatic spinning at 15kV voltage to prepare the titanium oxide cross-linked modified polyimide fiber non-woven fabric.
Example 2
A preparation method of an aminated titanium oxide modified polyimide fiber filter material comprises the following steps: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the method specifically comprises the following steps:
s1: preparing aminated nano titanium oxide: dissolving 37.5mmol of titanium tetrachloride and 19.5mmol of gamma-aminoethyl aminopropyltrimethoxysilane in 250mL of 50% ethanol solution, dropwise adding 75mL of 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 10h, dropwise adding 4.4mmol of N, N, N' -trimethylethylenediamine, standing and aging for 5h, filtering, washing and drying to obtain aminated nano titanium oxide;
s2: preparing modified polyimide: 9.644g of 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 2.856g of p-phenylenediamine (the molar ratio of the two is 1: 0.85) are dissolved in 84.25g of N-methylpyrrolidone solvent, 1.25g of isoquinoline is added, the temperature is raised to 80 ℃, 2.0g of functionalized nano titanium oxide is evenly divided for 3 times and added into a reaction system, stirring and polymerization are carried out for 6 hours, the temperature is continuously raised to 200 ℃, and imidization is carried out for 15 hours, so as to synthesize a modified polyimide solution;
s2: electrostatic spinning: and diluting the modified polyimide solution to a solid content of 7.5%, and performing electrostatic spinning at a voltage of 18kV to prepare the titanium oxide cross-linked modified polyimide fiber non-woven fabric.
Example 3
A preparation method of an aminated titanium oxide modified polyimide fiber filter material comprises the following steps: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the method specifically comprises the following steps:
s1: preparing aminated nano titanium oxide: dissolving 50mmol of titanium tetrachloride and 18.75mmol of gamma-aminoethyl aminopropyltrimethoxysilane in 250mL of 50% ethanol solution, dropwise adding 100mL of 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 12 hours, dropwise adding 3.75mmol of N, N, N' -trimethylethylenediamine, standing and aging for 6 hours, filtering, washing and drying to obtain aminated nano titanium oxide;
s2: preparing modified polyimide: 11.573g of 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and 3.427g of p-phenylenediamine (the molar ratio of the two is 1: 0.85) are dissolved in 81g of N-methylpyrrolidone solvent, 1.5g of isoquinoline is added, the temperature is raised to 100 ℃, 2.5g of functionalized nano titanium oxide is evenly divided for 3 times and added into a reaction system, stirring and polymerization are carried out for 8 hours, the temperature is continuously raised to 200 ℃ for imidization for 18 hours, and a modified polyimide solution is synthesized;
s2: electrostatic spinning: and diluting the modified polyimide solution to a solid content of 10%, and performing electrostatic spinning at a voltage of 20kV to prepare the titanium oxide cross-linked modified polyimide fiber non-woven fabric.
Comparative example 1: the preparation method is the same as that of example 1, except that: the non-aminated nano titanium oxide is directly mixed with 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and p-phenylenediamine to prepare the composite polyimide fiber non-woven fabric.
The titanium oxide/polyimide fiber nonwoven fabrics prepared in examples 1 to 3 and comparative example 1 were subjected to a structural stability test: the titanium oxide/polyimide fiber nonwoven fabrics prepared in examples 1 to 3 and comparative example 1 were measured for initial mass M1, treated at 6-stage wind speed for 12 hours, and then tested for mass M2, and the weight loss ratio was calculated as 100% × (M1-M2)/M1, with the test results shown in Table 1:
table 1:
example 1 Example 2 Example 3 Comparative example 1
Weight loss rate/%) 0.5％ 0.4％ 0.5％ 12.4％
Other performance metrics are shown in table 2:
table 2:
example 1 Example 2 Example 3 Comparative example 1
Specific surface area/m2/g 804.9 880.5 861.7 566.4
Micropore specific surface area/m with aperture less than 1nm2/g 172.6 197.8 194.4 83.1
Tensile strength/GPa 0.28 0.31 0.34 0.15
Tensile modulus/GPa 2.65 2.92 3.26 1.39
In embodiments 1 to 3, the aminated nano titanium oxide is prepared by a hydrothermal method using γ -aminoethyl aminopropyltrimethoxysilane, N' -trimethylethylenediamine and titanium tetrachloride for the first time, and then the amidation reaction between amino groups and carboxyl groups is utilized to perform condensation copolymerization with dianhydride monomers and diamine monomers, so that the nano titanium oxide is grafted or crosslinked on a polyimide molecular chain.
The polyimide fiber non-woven fabrics prepared in the embodiments 1 to 3 have high specific surface area which can reach 804.9m2More than g, wherein the surface area of the micropores with the pore diameter of less than 1nm can reach 172.6m2More than g, effectively improves the filtering efficiency of the high-temperature flue gas, and can efficiently degrade the toxicity in the high-temperature flue gasAnd (4) harmful substances.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (3)

1. An aminated titanium oxide modified polyimide fiber filter material is characterized in that: the polyamide fiber is prepared by copolymerizing aminated nano titanium oxide, dianhydride monomer and diamine monomer, and then performing electrostatic spinning to obtain polyimide fiber non-woven fabric; the copolymerization reaction system comprises the following raw materials in percentage by mass:
Figure FDA0002478643690000011
the preparation method of the aminated nano titanium oxide comprises the following steps: dissolving titanium tetrachloride and gamma-aminoethyl aminopropyltrimethoxysilane in a 50% ethanol solution, dropwise adding a 2mol/L NaOH solution, uniformly stirring, carrying out hydrothermal reaction at 150 ℃ for 6-12 h, dropwise adding N, N, N' -trimethylethylenediamine, standing and aging for 3-6 h, filtering, washing and drying to obtain aminated nano titanium oxide; the using proportion of titanium tetrachloride, gamma-aminoethyl aminopropyltrimethoxysilane, N, N, N' -trimethylethylenediamine, 2mol/L NaOH solution and 50% ethanol solution is (10-20) mmol: (4-7.5) mmol: (1-1.5) mmol: (20-40) mL: 100 mL.
2. The aminated titania-modified polyimide fiber filter material of claim 1, wherein the molar ratio of 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride to p-phenylenediamine is 1: (0.85-0.9).
3. The preparation method of the modified polyimide fiber filter material as claimed in any one of claims 1 to 2, comprising the following steps:
s1: preparing modified polyimide: dissolving 2,3 ', 4,4' -diphenyl ether tetracarboxylic dianhydride and p-phenylenediamine in an N-methylpyrrolidone solvent, adding isoquinoline, heating to 60-100 ℃, uniformly dividing the functionalized nano titanium oxide for 3 times, adding the mixture into a reaction system, stirring and polymerizing for 4-8 hours, continuously heating to 180-200 ℃, and imidizing for 10-18 hours to synthesize a modified polyimide solution;
s2: electrostatic spinning: and diluting the modified polyimide solution to a solid content of 5-10%, and performing electrostatic spinning under a voltage of 15-20 kV to prepare the titanium oxide cross-linked modified polyimide fiber non-woven fabric.
CN202010372436.9A 2020-05-06 2020-05-06 Aminated titanium oxide modified polyimide fiber filter material and preparation method thereof Withdrawn CN111514660A (en)

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