CN113426310B - Non-woven fabric base material for high-stiffness tubular membrane and preparation method thereof - Google Patents
Non-woven fabric base material for high-stiffness tubular membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a non-woven fabric base material for a high-stiffness tubular membrane and a preparation method thereof. The method selects dimer acid, octadecanedioic acid and decanediamine as monomers to prepare a polyamide matrix through polycondensation; then respectively preparing hydroxylated nano silicon dioxide and gamma-glycidyl ether oxypropyl trimethoxy silane modified montmorillonite, and carrying out hydrothermal reaction on the two to obtain a composite inorganic filler; then, the polyamide matrix and the composite inorganic filler are subjected to crosslinking and full mixing, and then melt blending extrusion granulation, injection molding and irradiation crosslinking are sequentially carried out to obtain the hot melt adhesive; and finally, arranging the high-hardness hot melt adhesive between the two layers of non-woven fabrics in a fiber glue spraying manner, and carrying out hot-press bonding to obtain the non-woven fabric substrate for the high-stiffness tubular membrane. Through the mode, the hardness of the hot melt adhesive can be effectively improved, and the non-woven fabric base material with high stiffness, good strength and high bursting strength is obtained, so that the application requirement of the high-stiffness tubular film can be met.
Description
Technical Field
The invention relates to the technical field of non-woven fabric base materials for tubular membranes, in particular to a non-woven fabric base material for a high-stiffness tubular membrane and a preparation method thereof.
Background
The tubular membrane is used as a form of membrane component, and is suitable for membrane separation technologies such as ultrafiltration, microfiltration, nanofiltration and reverse osmosis. The tubular membrane has the advantages of wide flow channel, difficult pollution, easy cleaning, low requirement on the pretreatment precision of feed liquid and the like, so the tubular membrane is widely applied to the fields of landfill leachate treatment, industrial wastewater treatment, special material separation and the like. The existing tubular membrane mainly comprises a support tube and a filter membrane, wherein the support tube can be a metal tube, a non-woven fabric tube or other tubes; among them, the support tube made of the non-woven fabric has the advantages of high compressive strength, good water permeability, simple production process, low cost, etc., and thus is widely used as a support material for tubular membranes.
In the production process of the tubular membrane taking the non-woven fabric base material as the supporting material, the non-woven fabric base material is usually rolled into a supporting tube with required length, then the membrane casting solution is uniformly coated on the inner wall of the supporting tube, then the supporting tube is put into the coagulating liquid to form a uniform membrane, and finally the membrane component is cast through post-treatment. During this production process, the properties of the nonwoven fabric substrate used will directly affect the properties of the tubular film ultimately produced. However, the conventional nonwoven fabric substrate is generally a single nonwoven fabric, and the material is soft, the stiffness is poor, the strength is low, and further the stiffness of the produced tubular film is insufficient, and the tubular film is difficult to use as a high pressure resistant tubular film.
For example, patent publication No. CN111485453A provides a method for producing a nonwoven fabric for supporting a separation membrane. The synthetic fibers are dispersed into fiber pulp by adding water and pulping, so that the fiber pulp is uniformly dispersed in water, the fibers are pumped to a papermaking net by a flow system for forming, and wet paper sheets are formed after dehydration; and evaporating, dehydrating and drying the wet paper, performing thermal bonding through hot pressing, and finally curing through a cooling roller to obtain the non-woven fabric with excellent mechanical strength and film peeling strength. However, although the above method can improve the mechanical strength of the nonwoven fabric to some extent, the improvement is mainly the tensile strength and the film peel strength of the nonwoven fabric, and the improvement of the stiffness of the nonwoven fabric is not significant, and it is difficult to use the nonwoven fabric as a support material for a high-stiffness tubular film.
In view of the above, there is a need to design an improved nonwoven fabric substrate for a high stiffness tubular film to solve the above problems.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a nonwoven fabric substrate for a high-stiffness tubular film and a method for preparing the same. Preparing a long-chain aliphatic polyamide matrix by selecting diacid and diamine with long chains as monomers, uniformly loading a composite inorganic filler formed by reacting hydroxylated nano silicon dioxide and modified montmorillonite in the polyamide matrix, and performing irradiation crosslinking under the action of a crosslinking agent to obtain a high-hardness hot melt adhesive; the prepared high-hardness hot melt adhesive is arranged between two layers of non-woven fabrics in a fiber glue spraying mode, and the non-woven fabric base material with high stiffness, good strength and high bursting strength is formed after hot-pressing adhesion, so that the high-hardness hot melt adhesive is applied to preparation of a high-stiffness tubular film.
In order to achieve the above object, the present invention provides a method for preparing a non-woven fabric substrate for a high-stiffness tubular film, comprising the steps of:
s1, preparing a polyamide matrix through polycondensation by using predetermined amounts of dimer acid, octadecanedioic acid and decanediamine as monomers;
s2, preparing hydroxylated nano silicon dioxide and montmorillonite modified by gamma-glycidyl ether oxypropyl trimethoxy silane respectively; mixing the hydroxylated nano-silica and the modified montmorillonite according to a first preset mass ratio, and then carrying out hydrothermal reaction to obtain a composite inorganic filler;
s3, mixing the polyamide matrix obtained in the step S1, the composite inorganic filler obtained in the step S2 and a cross-linking agent according to a second preset mass ratio, and then sequentially carrying out melt blending, extrusion granulation, injection molding and irradiation cross-linking to obtain a hot melt adhesive;
s4, spraying the hot melt adhesive obtained in the step S3 on the upper surface of the first layer of non-woven fabric in a fiber glue spraying mode, then overlapping the second layer of non-woven fabric on the upper surface of the first layer of non-woven fabric sprayed with the hot melt adhesive, and obtaining the non-woven fabric substrate for the high-stiffness tubular membrane after hot pressing treatment.
As a further improvement of the present invention, in step S1, the preparation process of the polyamide matrix comprises the following steps:
mixing dimer acid and octadecanedioic acid according to the molar ratio of 1 (1-3), adding catalyst phosphoric acid, heating to 120-140 ℃, adding decamethylene diamine, and fully reacting to obtain a polyamide matrix; the molar ratio of amino in the decamethylene diamine to carboxyl in the dimer acid and octadecanedioic acid is 1 (0.9-1.1).
As a further improvement of the present invention, in step S2, the preparation method of the hydroxylated nano-silica comprises the following steps:
adding nano-silica with the average particle size of 30-100 nm into an aqueous solution of hydrogen peroxide according to the mass-to-volume ratio of 1g (3-10) mL, performing ultrasonic dispersion, performing oil bath reflux at 100-110 ℃ for 1-3 h, cooling, and then sequentially performing centrifugation, washing and drying to obtain hydroxylated nano-silica.
As a further improvement of the invention, in step S2, the first preset mass ratio is 1 (3-5); the reaction temperature of the hydrothermal reaction is 130-150 ℃, and the reaction time is 8-10 h.
As a further improvement of the invention, in step S3, the second predetermined mass ratio is 100 (4-8) to (1-5).
As a further improvement of the present invention, in step S3, the crosslinking agent is triallyl cyanurate; the irradiation dose of the electron beam for irradiation crosslinking is 30-50 kGy.
In a further improvement of the present invention, in step S4, the fiber spray method is to spray the hot melt adhesive as fiber adhesive filaments with a diameter of 1-5 μm, and the spraying amount of the hot melt adhesive is 2-10 g/m2。
As a further improvement of the present invention, in step S4, the first layer nonwoven fabric and the second layer nonwoven fabric are both polyester nonwoven fabrics prepared by a paper making method; the temperature of the hot pressing treatment is 180-200 ℃.
In order to achieve the purpose, the invention also provides a non-woven fabric base material for the high-stiffness tubular membrane, which is prepared according to any one of the technical schemes and comprises two layers of non-woven fabrics and a hot melt adhesive arranged between the two layers of non-woven fabrics and used for bonding the two layers of non-woven fabrics.
As a further improvement of the invention, the hardness of the hot melt adhesive is 60-70 HD; the non-woven fabric base material for the high-stiffness tubular film has stiffness of 4.5-6.5 mN.m, bursting strength of 350-420 kPa and tensile strength of 8.5-11 kN/m.
The invention has the beneficial effects that:
(1) according to the preparation method of the non-woven fabric base material for the high-stiffness tubular membrane, diacid and diamine with long chains are selected as monomers, so that an aliphatic polyamide matrix with long chains is prepared; and the composite inorganic filler formed by the reaction of the hydroxylated nano-silica and the modified montmorillonite is uniformly loaded in the polyamide matrix, and then radiation crosslinking is carried out under the action of a crosslinking agent, so that the high-hardness hot melt adhesive is prepared. On the basis, the prepared high-hardness hot melt adhesive is arranged between two layers of non-woven fabrics in a fiber glue spraying mode, and the non-woven fabric base material with high stiffness, good strength and high bursting strength is prepared after hot-pressing bonding.
(2) According to the invention, octadecanedioic acid and decanediamine with longer carbon chains are selected as polymerization monomers, so that on one hand, the prepared polyamide matrix contains longer carbon chains to reduce the melting point of the polyamide matrix, facilitate the subsequent hot pressing process, and improve the mechanical properties of the polyamide matrix such as hardness and tensile strength so as to prepare the hot melt adhesive with high hardness; on the other hand, when the polyamide matrix with longer carbon chains is subjected to irradiation crosslinking under the action of the crosslinking agent, a tightly crosslinked three-dimensional network structure is more easily formed, the hardness and the tensile strength of the finally prepared hot melt adhesive are further improved, and a foundation is provided for effectively improving the mechanical property of the non-woven fabric substrate.
(3) According to the invention, the nano silicon dioxide is hydroxylated, so that the surface of the nano silicon dioxide is provided with a large number of hydroxyl groups; meanwhile, the gamma-glycidyl ether oxypropyltrimethoxysilane is used for modifying the montmorillonite, so that the montmorillonite is hydrophobic and oleophilic, the compatibility of the montmorillonite with a polyamide matrix is improved, and the montmorillonite is fully dispersed in the polyamide matrix; and epoxy groups carried in the montmorillonite modified by the gamma-glycidyl ether oxypropyl trimethoxysilane can react with hydroxyl groups on the surface of the hydroxylated nano-silica, so that the epoxy groups and the hydroxylated nano-silica are effectively combined to form the composite inorganic filler, and the composite inorganic filler is uniformly loaded in a polyamide matrix through a melt blending process. On the basis, the irradiation crosslinking can further promote the close combination of the composite inorganic filler and the polyamide matrix, so that the finally prepared hot melt adhesive has excellent mechanical properties such as high hardness, high strength and the like, and the requirements of practical application are met.
(4) The hot melt adhesive prepared by the invention has higher hardness and strength, can be arranged between two layers of non-woven fabrics in a fiber glue spraying manner, and not only can the hot melt adhesive be loaded on the surfaces of the non-woven fabrics by ultrafine fiber glue wires in the fiber glue spraying manner, so that the prepared non-woven fabric base material has better air permeability, but also the consumption of the hot melt adhesive can be effectively reduced under the condition of ensuring the bonding strength and the stiffness of the non-woven fabric base material. The non-woven fabric base material for the high-stiffness tubular film prepared by the preparation method provided by the invention has the advantages of high stiffness, high bursting strength and high tensile strength, and can completely meet the requirements of practical application.
Drawings
Fig. 1 is a schematic structural diagram of a nonwoven fabric substrate for a high-stiffness tubular film according to the present invention.
Reference numerals
1-a first layer of non-woven fabric; 2-hot melt adhesive; 3-second layer of non-woven fabric.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a non-woven fabric base material for a high-stiffness tubular membrane, which comprises the following steps:
s1, preparing a polyamide matrix through polycondensation by using predetermined amounts of dimer acid, octadecanedioic acid and decanediamine as monomers;
s2, preparing hydroxylated nano silicon dioxide and montmorillonite modified by gamma-glycidyl ether oxypropyl trimethoxy silane respectively; mixing the hydroxylated nano-silica and the modified montmorillonite according to a first preset mass ratio, and then carrying out hydrothermal reaction to obtain a composite inorganic filler;
s3, mixing the polyamide matrix obtained in the step S1, the composite inorganic filler obtained in the step S2 and a cross-linking agent according to a second preset mass ratio, and then sequentially carrying out melt blending, extrusion granulation, injection molding and irradiation cross-linking to obtain a hot melt adhesive;
s4, spraying the hot melt adhesive obtained in the step S3 on the upper surface of the first layer of non-woven fabric in a fiber glue spraying mode, then overlapping the second layer of non-woven fabric on the upper surface of the first layer of non-woven fabric sprayed with the hot melt adhesive, and obtaining the non-woven fabric substrate for the high-stiffness tubular membrane after hot pressing treatment.
In step S1, the preparation process of the polyamide matrix includes the following steps:
mixing dimer acid and octadecanedioic acid according to the molar ratio of 1 (1-3), adding catalyst phosphoric acid, heating to 120-140 ℃, adding decamethylene diamine, and fully reacting to obtain a polyamide matrix; the molar ratio of amino in the decamethylene diamine to carboxyl in the dimer acid and octadecanedioic acid is 1 (0.9-1.1).
In step S2, the preparation method of the hydroxylated nano-silica includes the steps of:
adding nano-silica with the average particle size of 30-100 nm into an aqueous solution of hydrogen peroxide according to the mass-to-volume ratio of 1g (3-10) mL, performing ultrasonic dispersion, performing oil bath reflux at 100-110 ℃ for 1-3 h, cooling, and then sequentially performing centrifugation, washing and drying to obtain hydroxylated nano-silica.
The first preset mass ratio is 1 (3-5); the reaction temperature of the hydrothermal reaction is 130-150 ℃, and the reaction time is 8-10 h.
In step S3, the second predetermined mass ratio is 100 (4-8): 1-5; the cross-linking agent is triallyl cyanurate; the irradiation dose of the electron beam for irradiation crosslinking is 30-50 kGy.
In step S4, the hot melt adhesive is sprayed out by the fiber glue spraying mode through fiber glue wires with the diameter of 1-5 μm, and the spraying amount of the hot melt adhesive is 2-10 g/m2(ii) a The first layer of non-woven fabric and the second layer of non-woven fabric are both polyester non-woven fabrics prepared by a papermaking method; the temperature of the hot pressing treatment is 180-200 ℃.
The invention also provides a non-woven fabric substrate for the high-stiffness tubular membrane, which is prepared according to the technical scheme and comprises two layers of non-woven fabrics and hot melt adhesive arranged between the two layers of non-woven fabrics and used for bonding the two layers of non-woven fabrics.
The hardness of the hot melt adhesive is 60-70 HD; the non-woven fabric base material for the high-stiffness tubular film has stiffness of 4.5-6.5 mN.m, bursting strength of 350-420 kPa and tensile strength of 8.5-11 kN/m.
The nonwoven fabric substrate for a high-stiffness tubular film and the method for producing the same according to the present invention will be described with reference to specific examples.
Example 1
The embodiment provides a preparation method of a non-woven fabric base material for a high-stiffness tubular membrane, which comprises the following steps:
s1 preparation of Polyamide matrix
Mixing dimer acid and octadecanedioic acid according to a molar ratio of 1:2, adding the mixture into a three-neck flask, adding phosphoric acid serving as a catalyst, heating the mixture to 130 ℃ under the protection of nitrogen, and then dropwise adding decanediamine to ensure that the molar ratio of amino in the decanediamine to carboxyl in the dimer acid and octadecanedioic acid is 1:1 so as to ensure full reaction. After adding decamethylenediamine, pre-polycondensation is carried out for 1h at 130 ℃, then the temperature is raised to 240 ℃ for reaction for 3h, then the pressure is gradually reduced for polycondensation for 1h, finally the mixture is continuously stirred for 0.5h under normal pressure, and the polyamide matrix is obtained after cooling.
S2 preparation of composite inorganic filler
Nano silicon dioxide with the average particle size of 50nm is prepared according to the mass-volume ratio of 1g: adding 5mL of the mixture into an aqueous solution of hydrogen peroxide (the volume fraction of the hydrogen peroxide is 30%), fully dispersing under the action of ultrasound, performing oil bath reflux for 2 hours at 105 ℃, cooling, and then sequentially performing centrifugation, washing and drying to obtain the hydroxylated nano silicon dioxide.
Then montmorillonite with the average particle size of 5 mu m is mixed according to the mass volume ratio of 1g: adding 50mL of ethanol aqueous solution (the volume fraction of ethanol is 50%), fully dispersing under the action of ultrasound, adding silane coupling agent gamma-glycidyl ether oxypropyl trimethoxy silane (KH-560) until the dosage of KH-560 accounts for 15% of the weight of the montmorillonite, fully stirring for 4h at 80 ℃, cooling, and then sequentially centrifuging, washing and drying to obtain the modified montmorillonite.
Mixing hydroxylated nano silicon dioxide and modified montmorillonite according to the mass ratio of 1:4, ultrasonically dispersing in water, and then placing in a high-pressure reaction kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is set to be 140 ℃, and the reaction time is set to be 9 hours. And after the reaction is completed, cooling, filtering and drying to obtain the composite inorganic filler.
S3 preparation of hot melt adhesive
Mixing the polyamide matrix obtained in the step S1, the composite inorganic filler obtained in the step S2 and the crosslinking agent triallyl cyanurate according to the mass ratio of 100:6:3, placing the mixture in a double-screw extruder, performing melt mixing, extruding and granulating at the extrusion temperature of 240 ℃, and then placing the granulated particles in an injection molding machine for injection molding at the injection molding temperature of 250 ℃; and finally, carrying out irradiation crosslinking on the injection molded sample by using an electron beam accelerator in a nitrogen atmosphere, wherein the irradiation dose is 40kGy, and obtaining the hot melt adhesive 2 after irradiation crosslinking.
S4 preparation of non-woven fabric base material for high-stiffness tubular membrane
Adopting a fiber glue spraying mode to spray glue on the hot melt glue 2 obtained in the step S3 with fiber glue threads with the diameter of 3 mu m according to the ratio of 5g/m2The spraying amount of the adhesive is uniformly sprayed on the upper surface of the first layer of non-woven fabric 1, then the second layer of non-woven fabric 3 is superposed on the upper surface of the first layer of non-woven fabric 1 sprayed with the hot melt adhesive 2, and hot pressing treatment is carried out at 190 ℃ to fully bond the first layer of non-woven fabric 1 and the second layer of non-woven fabric 3, so that the non-woven fabric substrate for the high-stiffness tubular membrane is obtained.
Wherein the first layer of non-woven fabric and the second layer of non-woven fabric are both prepared by a papermaking method and have the gram weight of 100g/m2The preparation method of the polyester non-woven fabric comprises the following steps:
mixing polyester fibers and bonding fibers according to a mass ratio of 65:35, placing the mixture into a pulping machine, and adding water for pulping to obtain fiber pulp; and adding water into the fiber slurry, uniformly stirring, fully diluting the fiber slurry into fiber suspension, making the fiber suspension into a net by using a paper making machine, and drying at 80 ℃ to obtain the polyester non-woven fabric.
The structural schematic diagram of the non-woven fabric substrate for the high-stiffness tubular film prepared in the above manner is shown in fig. 1, and the non-woven fabric substrate comprises a first layer of non-woven fabric 1, a second layer of non-woven fabric 3 and a hot melt adhesive 2 arranged between the first layer of non-woven fabric 1 and the second layer of non-woven fabric 3.
In order to examine the actual improvement effect of the preparation method provided in this example on the mechanical properties of the nonwoven fabric substrate, the hardness of the hot melt adhesive obtained in step S3 and the stiffness, bursting strength, and tensile strength of the nonwoven fabric substrate for the high-stiffness tubular film obtained in step S4 were measured, and the results are shown in table 1.
TABLE 1 Performance parameters of the hot melt adhesive and nonwoven substrates prepared in example 1
As can be seen from Table 1, the hot melt adhesive prepared by the embodiment has higher hardness, and the non-woven fabric substrate prepared on the basis has higher stiffness, bursting strength and tensile strength, can completely meet the application requirements in a high-stiffness tubular film, and has better application prospect and higher application value.
Examples 2 to 13 and comparative examples 1 to 5
Examples 2 to 13 and comparative examples 1 to 5 each provide a method for producing a nonwoven fabric substrate for a high-stiffness tubular film.
The difference between examples 2-13 and example 1 is that the process parameters of the preparation process are adjusted, the process parameters corresponding to each example are shown in table 2, and the remaining steps and parameters are the same as those of the examples, and are not described herein again.
Further, comparative example 1 is different from example 1 only in that an equivalent amount of the poly diacid is substituted for the octadecanedioic acid and an equivalent amount of the ethylene diamine is substituted for the decamethylene diamine in step S1; comparative example 2 and comparative example 3 are different only in that single hydroxylated nano silica and modified montmorillonite are used as inorganic fillers in step S2, respectively; the difference of the comparative example 4 is that unmodified nano-silica and montmorillonite with equal mass are respectively used for replacing hydroxylated nano-silica and modified montmorillonite to obtain purely mixed inorganic filler; comparative example 5 differs only in that no crosslinking agent was added in step S3 and no irradiation crosslinking was performed. The rest steps of each proportion are the same as those in embodiment 1, and are not described again.
TABLE 2 Process parameters for examples 2 to 13
The hardness of the hot melt adhesives prepared in examples 2 to 13 and comparative examples 1 to 5, and the stiffness, bursting strength, and tensile strength of the nonwoven fabric base material for high-stiffness tubular films were measured, and the results are shown in table 3.
TABLE 3 Performance parameters for examples 2-13 and comparative examples 1-5
It can be seen from table 2 and table 3 that, when the non-woven fabric substrate for the high-stiffness tubular film is prepared, the properties of the prepared hot melt adhesive and the non-woven fabric substrate can be regulated and controlled by adjusting corresponding process parameters. According to the test data of the embodiments 2 to 13, the process parameters are adjusted within a certain range, the hardness of the hot melt adhesive can be adjusted and controlled between 60 HD and 70HD, the stiffness of the prepared non-woven fabric substrate is controlled to be 4.5 mN.m to 6.5 mN.m, the bursting strength is controlled to be 350 kPa to 420kPa, and the tensile strength is controlled to be 8.5 kN/m to 11kN/m, so that all performance parameters of the non-woven fabric substrate can meet the application requirements of the high-stiffness tubular film.
In addition, the performances of the hot melt adhesive and the non-woven fabric substrate prepared in the comparative examples 1 to 5 are obviously inferior to those of the examples, which shows that the mechanical properties of the hot melt adhesive and the non-woven fabric substrate can be effectively improved by selecting the types of the polymerization monomers, correspondingly modifying the nano silicon dioxide and the montmorillonite and setting the irradiation crosslinking, and all the steps are absent. Based on the method, the non-woven fabric substrate for the high-stiffness tubular membrane is prepared by selecting diacid and diamine with long chains as monomers to prepare a long-chain aliphatic polyamide matrix, uniformly loading a composite inorganic filler formed by reacting hydroxylated nano silicon dioxide and modified montmorillonite in the polyamide matrix, and performing irradiation crosslinking under the action of a crosslinking agent to prepare the high-hardness hot melt adhesive; on the basis, the prepared high-hardness hot melt adhesive is arranged between two layers of non-woven fabrics in a fiber glue spraying mode, and then hot pressing treatment is carried out to enable the non-woven fabrics to be effectively bonded, so that the non-woven fabric base material with high stiffness, good strength and high bursting strength can be obtained, and the non-woven fabric base material is applied to a high-stiffness tubular membrane to meet the requirements of practical application.
In conclusion, the invention provides a non-woven fabric base material for a high-stiffness tubular membrane and a preparation method thereof. The method selects dimer acid, octadecanedioic acid and decanediamine as monomers to prepare a polyamide matrix through polycondensation; then respectively preparing hydroxylated nano silicon dioxide and gamma-glycidyl ether oxypropyl trimethoxy silane modified montmorillonite, and carrying out hydrothermal reaction on the two to obtain a composite inorganic filler; then, the polyamide matrix and the composite inorganic filler are subjected to crosslinking and full mixing, and then melt blending extrusion granulation, injection molding and irradiation crosslinking are sequentially carried out to obtain the hot melt adhesive; and finally, arranging the high-hardness hot melt adhesive between the two layers of non-woven fabrics in a fiber glue spraying manner, and carrying out hot-press bonding to obtain the non-woven fabric substrate for the high-stiffness tubular membrane. Through the mode, the hardness of the hot melt adhesive can be effectively improved, and the non-woven fabric base material with high stiffness, good strength and high bursting strength is obtained, so that the application requirement of the high-stiffness tubular film can be met.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a non-woven fabric base material for a high-stiffness tubular film is characterized by comprising the following steps:
s1, preparing a polyamide matrix through polycondensation by using predetermined amounts of dimer acid, octadecanedioic acid and decanediamine as monomers;
s2, preparing hydroxylated nano silicon dioxide and montmorillonite modified by gamma-glycidyl ether oxypropyl trimethoxy silane respectively; mixing the hydroxylated nano-silica and the modified montmorillonite according to a first preset mass ratio, and then carrying out hydrothermal reaction to obtain a composite inorganic filler;
s3, mixing the polyamide matrix obtained in the step S1, the composite inorganic filler obtained in the step S2 and a cross-linking agent according to a second preset mass ratio, and then sequentially carrying out melt blending, extrusion granulation, injection molding and irradiation cross-linking to obtain a hot melt adhesive;
s4, spraying the hot melt adhesive obtained in the step S3 on the upper surface of the first layer of non-woven fabric in a fiber glue spraying mode, then overlapping the second layer of non-woven fabric on the upper surface of the first layer of non-woven fabric sprayed with the hot melt adhesive, and obtaining the non-woven fabric substrate for the high-stiffness tubular membrane after hot pressing treatment.
2. The method for producing a nonwoven fabric substrate for a high-stiffness tubular film according to claim 1, characterized in that: in step S1, the preparation process of the polyamide matrix includes the following steps:
mixing dimer acid and octadecanedioic acid according to the molar ratio of 1 (1-3), adding catalyst phosphoric acid, heating to 120-140 ℃, adding decamethylene diamine, and fully reacting to obtain a polyamide matrix; the molar ratio of amino in the decamethylene diamine to carboxyl in the dimer acid and octadecanedioic acid is 1 (0.9-1.1).
3. The method for producing a nonwoven fabric substrate for a high-stiffness tubular film according to claim 1, characterized in that: in step S2, the preparation method of the hydroxylated nano-silica includes the steps of:
adding nano-silica with the average particle size of 30-100 nm into an aqueous solution of hydrogen peroxide according to the mass-to-volume ratio of 1g (3-10) mL, performing ultrasonic dispersion, performing oil bath reflux at 100-110 ℃ for 1-3 h, cooling, and then sequentially performing centrifugation, washing and drying to obtain hydroxylated nano-silica.
4. The method for producing a nonwoven fabric substrate for a high-stiffness tubular film according to claim 1, characterized in that: in step S2, the first preset mass ratio is 1 (3-5); the reaction temperature of the hydrothermal reaction is 130-150 ℃, and the reaction time is 8-10 h.
5. The method for producing a nonwoven fabric substrate for a high-stiffness tubular film according to claim 1, characterized in that: in step S3, the second predetermined mass ratio is 100 (4-8): 1-5.
6. The method for producing a nonwoven fabric substrate for a high-stiffness tubular film according to claim 1, characterized in that: in step S3, the crosslinking agent is triallyl cyanurate; the irradiation dose of the electron beam for irradiation crosslinking is 30-50 kGy.
7. The method for producing the nonwoven fabric substrate for a high-stiffness tubular film according to any one of claims 1 to 6, characterized in that: in step S4, the hot melt adhesive is sprayed out by the fiber glue spraying mode through fiber glue wires with the diameter of 1-5 μm, and the spraying amount of the hot melt adhesive is 2-10 g/m2。
8. The method for producing the nonwoven fabric substrate for a high-stiffness tubular film according to any one of claims 1 to 7, characterized in that: in step S4, the first layer of nonwoven fabric and the second layer of nonwoven fabric are both polyester nonwoven fabrics prepared by a paper making method; the temperature of the hot pressing treatment is 180-200 ℃.
9. The non-woven fabric substrate for the high-stiffness tubular membrane is characterized in that: the non-woven fabric substrate for the high-stiffness tubular film is prepared according to the preparation method of any one of claims 1 to 8, and comprises two layers of non-woven fabrics and hot melt adhesive arranged between the two layers of non-woven fabrics and used for bonding the two layers of non-woven fabrics.
10. The nonwoven fabric substrate for a high-stiffness tubular film according to claim 9, characterized in that: the hardness of the hot melt adhesive is 60-70 HD; the non-woven fabric base material for the high-stiffness tubular film has stiffness of 4.5-6.5 mN.m, bursting strength of 350-420 kPa and tensile strength of 8.5-11 kN/m.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10057149A1 (en) * | 2000-11-17 | 2002-05-23 | Kloeber Johannes | Diffusion-open roofing membrane |
| CN102675609A (en) * | 2012-06-07 | 2012-09-19 | 昆山天洋热熔胶有限公司 | Rapid crystallization type nanometer composite polyester hot melt adhesive and preparing process thereof |
| CN103184030A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
| CN103834346A (en) * | 2012-11-22 | 2014-06-04 | 上海理日化工新材料有限公司 | Dimer acid type polyamide hot-melt adhesive composition |
| CN104804659A (en) * | 2015-05-11 | 2015-07-29 | 上海天洋热熔粘接材料股份有限公司 | Hot melt rubber film for adhering metal and non-polar material and preparation method of hot melt rubber film |
| CN108753241A (en) * | 2018-06-25 | 2018-11-06 | 江苏科琪高分子材料研究院有限公司 | Silane modified polyether hot-melt adhesive composition and preparation method thereof |
| KR20200119511A (en) * | 2019-04-10 | 2020-10-20 | 나홍주 | Sound absorbing material and method for fabricating the same |
| CN112895653A (en) * | 2019-11-19 | 2021-06-04 | 上海天洋热熔粘接材料股份有限公司 | Cross-linked modified copolyamide hot melt adhesive net film and preparation and use methods thereof |
-
2021
- 2021-06-25 CN CN202110715898.0A patent/CN113426310B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10057149A1 (en) * | 2000-11-17 | 2002-05-23 | Kloeber Johannes | Diffusion-open roofing membrane |
| CN103184030A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Novel polyamide adhesive |
| CN102675609A (en) * | 2012-06-07 | 2012-09-19 | 昆山天洋热熔胶有限公司 | Rapid crystallization type nanometer composite polyester hot melt adhesive and preparing process thereof |
| CN103834346A (en) * | 2012-11-22 | 2014-06-04 | 上海理日化工新材料有限公司 | Dimer acid type polyamide hot-melt adhesive composition |
| CN104804659A (en) * | 2015-05-11 | 2015-07-29 | 上海天洋热熔粘接材料股份有限公司 | Hot melt rubber film for adhering metal and non-polar material and preparation method of hot melt rubber film |
| CN108753241A (en) * | 2018-06-25 | 2018-11-06 | 江苏科琪高分子材料研究院有限公司 | Silane modified polyether hot-melt adhesive composition and preparation method thereof |
| KR20200119511A (en) * | 2019-04-10 | 2020-10-20 | 나홍주 | Sound absorbing material and method for fabricating the same |
| CN112895653A (en) * | 2019-11-19 | 2021-06-04 | 上海天洋热熔粘接材料股份有限公司 | Cross-linked modified copolyamide hot melt adhesive net film and preparation and use methods thereof |
Non-Patent Citations (1)
| Title |
|---|
| 二聚酸型聚酰胺热熔胶的应用与改性研究进展;祝爱兰等;《中国胶粘剂》;20081230;第17卷(第12期);第53-57页 * |
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