A wood pulp based degradable hydroentangled wiping material and method of making the same

Abstract

The present application relates to the technical field of water-jet wiping material, in particular to a wood pulp-based degradable water-jet wiping material and a preparation method thereof. The method comprises the following steps: step 1: (1) sequentially mixing, carding and laying the pretreated wood pulp fibers and carboxylated cellulose, and performing primary water-jet reinforcement to form a degradable base layer; (2) mixing the cellulose fibers and polylactic acid fibers, carding and laying them on the surface of the degradable base layer, and performing secondary water-jet reinforcement to obtain a degradable water-jet base material; step 2: dipping and rolling the degradable water-jet base material in MOF antibacterial fixing slurry twice, drying, further spraying modified dye liquid on the surface, drying, winding and cutting; thus obtaining a water-jet wiping material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-jet wiping materials, in particular to a wood pulp-based degradable water-jet wiping material and a preparation method thereof. BACKGROUND

[0002] As an indispensable product in people's life, water-jet wiping materials can achieve convenient and efficient cleaning. However, traditional wiping materials are mainly based on petroleum-based fibers, which have problems such as non-degradability, high resource consumption, and microplastic pollution. With the continuous improvement of global environmental standards, consumers pay more and more attention to green products, and degradable wiping materials have become a popular research direction in the industry at this stage.

[0003] At present, the research and development of degradable wiping materials on the international market are mainly led by European and American enterprises. For example, Aishengya and Kimberly-Clark have launched wood pulp-based water-jet materials, but most of the products are based on original pulp color, lack of color design, and are difficult to meet the aesthetic needs. Even a few products that try simple coloring also have obvious color fading after rubbing and water, and generally have problems such as insufficient color stability and poor color fastness. At the same time, in the fields of medical care, maternity and infant care, etc., the antibacterial performance of ordinary degradable wiping materials cannot meet the use standards, and even a few that meet the antibacterial standards are prone to loss of antibacterial agents due to poor combination with the substrate during rubbing and humid environment during use, resulting in a decrease in antibacterial performance. This limits the application field of degradable wiping materials.

[0004] Therefore, how to realize the dual improvement of color fastness and antibacterial performance on the basis of ensuring degradability has become the key to breaking through the application limitations of existing degradable wiping materials.

[0005] In summary, it is of great significance to solve the above problems and prepare a wood pulp-based degradable water-jet wiping material. SUMMARY

[0006] The present application aims to provide a wood pulp-based degradable water-jet wiping material and a preparation method thereof to solve the problems raised in the background.

[0007] In order to solve the above technical problems, the present application provides the following technical solutions:

[0008] A preparation method of a wood pulp-based degradable water-jet wiping material, comprising the following steps:

[0009] Step 1: (1) mixing, carding and laying the pretreated wood pulp fibers and carboxylated cellulose in sequence, and performing primary water-jet reinforcement to form a degradable base layer; (2) mixing the cellulose fibers and polylactic acid fibers, carding and laying them on the surface of the degradable base layer, and performing secondary water-jet reinforcement to obtain a degradable water-jet base material;

[0010] Step 2: The degradable water-jet base material is placed in the MOF antibacterial fixing paste for two-dip two-nip, dried, and further sprayed with modified dye solution, dried, wound and cut to obtain the water-jet wiping material.

[0011] In a further aspect, the pretreated wood pulp fibers are obtained by plasma treatment; the plasma treatment process parameters are: vacuum degree 750-850 Pa; atmosphere pure oxygen; pure oxygen flow rate 1.2-1.5 L / min; treatment time 120-130 s; power 70-80 W. The surface hydroxyl content of the wood pulp fibers treated by plasma is improved, and the wood pulp fibers are tightly combined with the carboxylated cellulose by enhancing the polar effect of hydrogen bond and van der Waals force, so as to optimize the water-jet entanglement effect.

[0012] More preferably, the raw materials of the degradable water-jet base material include the following components: 60-80 parts of pretreated wood pulp fibers, 15-20 parts of carboxylated cellulose, 12-15 parts of cellulose fibers, and 10-15 parts of polylactic acid fibers by mass fraction.

[0013] More preferably, the preparation process of the MOF antibacterial fixing paste is as follows:

[0014] S1-1: At 0-5℃, nitrogen is introduced, N-hydroxymethyl acrylamide, methyl acrylate and methanol are added to divinyltriamine, and the mixture is reacted at room temperature for 3-5h. After removing methanol, the mixture is reacted at 90-120℃ for 8-12h. Then, cinnamyl aldehyde and tetrahydrofuran are added, 0.5wt%-0.6wt% acetic acid is used to adjust the pH to 5.5-6.0, and the mixture is reacted at 80-90℃ for 4-6h to obtain a Schiff base-based hyperbranched polymer;

[0015] S1-2: Zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are mixed, washed and dried, then added to DMF (N,N-dimethylformamide), acetic acid and deionized water are added, and the mixture is stirred at 110-130℃ for 20-40min, then washed and dried to obtain UiO-66-I4;

[0016] S1-3: UiO-66-I4, Schiff base-based hyperbranched polymer and deionized water are dispersed, and citric acid is added to adjust the pH to 5.0-5.5 to obtain the MOF antibacterial fixing paste.

[0017] More preferably, the raw materials of the MOF antibacterial fixing paste include the following components: 3-5 parts of UiO-66-I4, 8-12 parts of Schiff base-based hyperbranched polymer, and 120-150 parts of deionized water by mass fraction; and the concentration of citric acid is 0.5wt%-1.5wt%.

[0018] More preferably, the molar ratio of zinc chloride to 2,3,5,6-tetraiodoterephthalic acid in the UiO-66-I4 is 1:0.5~1; the raw material of the Schiff base-based hyperbranched polymer comprises the following components: 1~2 parts of N-hydroxymethyl acrylamide, 2~3.5 parts of methyl acrylate, 2~3 parts of divinyltriamine, 2~2.5 parts of cinnamaldehyde by mass fraction.

[0019] More preferably, the spraying amount of the modified dye solution is 5~10g / cm 2 ; the preparation process of the modified dye solution is as follows:

[0020] S2-1: Take berberine and 2,4-dimethoxybenzylamine and add them to DMSO (dimethyl sulfoxide), stir at 110~130℃ for 6~8h, cool and wash, freeze-dry, add to methanol, add 10wt%~15wt% hydrochloric acid, stir at room temperature for 5~7h, wash the precipitate and dry to obtain amino berberine;

[0021] S2-2: Take dehydrated lactic acid and ethylene glycol and add them to toluene, polycondense at 120~160℃ for 2~4h, cool and dry, add to epichlorohydrin, TBAB (tetrabutylammonium bromide), sodium hydroxide and tetrahydrofuran under nitrogen atmosphere, react at 60~65℃ for 5~8h, neutralize, remove tetrahydrofuran and dry to obtain epoxy-terminated lactic acid oligomer; add amino berberine, epoxy-terminated lactic acid oligomer and triethylamine to DMF, react at 45~55℃ for 7~9h and dry to obtain modified berberine;

[0022] S2-3: Add modified berberine, penetrant and buffer to deionized water and mix to obtain a modified dye solution.

[0023] More preferably, the components of the modified dye solution are as follows in terms of mass percentage: 5~8% modified berberine, 0.4~0.6% penetrant, 0.2~0.8% buffer, and the rest is deionized water; the raw material of the amino berberine comprises the following components: 2~3 parts of berberine, 4~7 parts of 2,4-dimethoxybenzylamine and 0.5~1 part of 10wt%~15wt% hydrochloric acid by mass fraction; the raw material of the modified berberine comprises the following components: 8~12 parts of lactic acid, 1~2 parts of ethylene glycol, 3~6 parts of epichlorohydrin, 0.2~0.5 parts of TBAB, 0.2~0.5 parts of sodium hydroxide, 8~12 parts of amino berberine and 0.5~0.8 parts of triethylamine by mass fraction.

[0024] More preferably, the process parameters of the first water jet reinforcement are as follows: water jet pressure is 3.5~4.5MPa, water jet number is 1~2, water jet height is 35~40mm, and web curtain speed is 10~15m / min;

[0025] The process parameters of the secondary water jet reinforcement are as follows: water jet pressure is 5.5-6.5 MPa, water jet path number is 2-3, water jet height is 40-45 mm, and net curtain speed is 15-20 m / min.

[0026] More preferably, the two-dip two-rolling process is as follows: the degradable water jet base material is placed in the MOF antibacterial fixing slurry, dipped for 12-18 h, taken out and extruded, which is the first dip and roll; after the first dip and roll, the material is placed in the MOF antibacterial fixing slurry again, ultrasonic treated for 30-60 min, taken out and extruded again, which is the second dip and roll.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] The present application uses wood pulp fiber, carboxylated cellulose and other degradable fibers as the base material to realize the degradability of the material; the MOF antibacterial fixing slurry is used for dip and roll and spray modification of the dye liquid to synergistically improve the antibacterial and fixing properties of the material.

[0029] The MOF antibacterial fixing slurry is composed of UiO-66-I4, Schiff base based hyperbranched polymer, citric acid and solvent. Under the action of citric acid, the hydroxyl groups on the surface of MOF dissociate and carry negative charges; the Schiff base based hyperbranched polymer is deprotonated to form -NH 3+ with positive charges under the action of citric acid; and the two are closely connected through electrostatic interaction.

[0030] The Schiff base based hyperbranched polymer in the MOF antibacterial fixing slurry acts as an adhesive, which is prepared by synthesizing amino hyperbranched polymer through melt polycondensation, and then condensing the terminal amino groups with aldehyde groups to form Schiff base groups. The hyperbranched structure and terminal Schiff base groups of the adhesive can effectively inhibit the agglomeration of MOF caused by the hydrophilic swelling of traditional chitosan adhesives through coordination bonding with UiO-66-I4 by steric hindrance; at the same time, the hydrophobicity provided by the iodine phenyl groups in tetraiodoterephthalic acid further inhibits the penetration of water molecules, ensuring the structural stability of the MOF antibacterial fixing slurry in the wet state, and achieving the synergistic improvement of antibacterial property and durability.

[0031] UiO-66-I4 in the MOF antibacterial fixing slurry acts as the core component for antibacterial and fixing enhancement, and forms a coordination bond with the tetraiodoterephthalic acid ligand through Zn²⁺ as the metal node, to form the MOF framework and provide antibacterial performance; the porous structure and high specific surface area of UiO-66-I4 can physically adsorb modified berberine in the modified dye liquid, and the zinc ions can coordinate with the epoxy groups in the modified dye liquid, to further improve the fixing performance.

[0032] Among them, the modified berberine in the modified dye solution is the core component of the dye solution, and the benzisoquinoline quaternary ammonium salt structure in the molecule provides antibacterial performance. The modified berberine is formed by demethylation of the methoxy group at C9 of berberine to form amino berberine, and then grafted with an epoxy-terminated lactic acid oligomer: on the one hand, the introduction of epoxy group and ether bond enhances the binding force with the fiber, and the lactic acid oligomer is similar to the polylactic acid fiber, which further improves the structural stability and fixing performance; on the other hand, the modified berberine is hydrolyzed by esterase, which further guides the material degradation. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] It should be noted that the following parts are mass parts, and there is no special restriction on the purchase of all raw materials involved in the present application. Exemplary includes: in the following examples, the wood pulp fiber is L30R, purchased from Chengdu Kanghuijing Technology Co., Ltd.; the carboxylated cellulose fiber has a CAS number of 9004-34-6, purchased from Maier Technology Co., Ltd.; the cellulose fiber is purchased from Saide Li (China) Fiber Co., Ltd.; the polylactic acid fiber is purchased from Yisheng New Material (Suzhou) Co., Ltd.; N-hydroxymethyl acrylamide has a CAS number of 924-42-5; methyl acrylate has a CAS number of 96-33-3; divinyltriamine has a CAS number of 111-40-0; cinnamaldehyde has a CAS number of 104-55-2; zinc chloride has a CAS number of 7646-85-7; 2,3,5,6-tetraiodo-p-xylylene terephthalic acid has a CAS number of 7606-84-0; citric acid has a CAS number of 77-92-9; berberine has a CAS number of 2086-83-1; 2,4-dimethoxybenzylamine has a CAS number of 20781-20-8; lactic acid has a CAS number of 50-21-5; ethylene glycol has a CAS number of 107-21-1; epichlorohydrin has a CAS number of 106-89-8; TBAB has a CAS number of 1643-19-2; triethylamine has a CAS number of 121-44-8; fatty alcohol polyoxyethylene ether has a CAS number of 68131-39-5; DMSO has a CAS number of 67-68-5; chitosan has a relative molecular mass of 50000 and a CAS number of 9012-76-4.

[0035] In the following examples, the following is particularly stated:

[0036] (1) The raw materials of the modified dye liquid, each component accounts for 6.5% of the mass percentage: modified berberine, 0.5% of the penetrant, 0.5% of the buffer, and the rest is deionized water; wherein the spraying amount of the modified dye liquid is 8g / cm 2 . Among them, the penetrant is a fatty alcohol polyoxyethylene ether; the buffer is a phosphate-citric acid system, and the pH is 5.5;

[0037] (2) The plasma treatment process parameters are: vacuum degree is 800Pa; atmosphere is pure oxygen; pure oxygen flow rate is 1.3L / min; treatment time is 125s; power is 75W; the process parameters of the first water jet reinforcement are: water jet pressure is 4MPa, water jet number is 1, water jet height is 38mm, and net curtain speed is 13m / min; the process parameters of the second water jet reinforcement are: water jet pressure is 6MPa, water jet number is 2, water jet height is 43mm, and net curtain speed is 18m / min.

[0038] Example 1: A preparation method of a wood pulp-based degradable water jet wiping material, comprising the following steps:

[0039] Step 1: S1-1: At 1℃, nitrogen is introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol are added to 2.5 parts of divinyltriamine, and the reaction is carried out at room temperature for 4h, after removing the methanol, the reaction is carried out at 105℃ for 10h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, and 0.55wt% acetic acid are added to adjust the pH to 5.8, and the reaction is carried out at 85℃ for 5h to obtain a Schiff base-based hyperbranched polymer; S1-2: zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are mixed according to a molar ratio of 1:0.8, ball-milled, washed, and dried, then added to DMF, acetic acid and deionized water are added, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base-based hyperbranched polymer, and 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2 to obtain a MOF antibacterial fixing slurry;

[0040] Step 2: S2-1: Take 2.5 parts of berberine, 5.5 parts of 2,4-dimethoxybenzylamine into DMSO, stir at 120℃ for 7h, cool and wash, freeze-dry, then add to methanol, add 0.8 parts of 12wt% hydrochloric acid, stir at room temperature for 6h, wash the precipitate and dry to obtain amino berberine; S2-2: Take 10 parts of dehydrated lactic acid, 1.5 parts of ethylene glycol into toluene, polycondense at 140℃ for 3h, cool and dry, then add to 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, tetrahydrofuran, react at 62℃ for 6.5h, neutralize, remove tetrahydrofuran and dry to obtain epoxy-terminated lactic acid oligomer; add 10 parts of amino berberine, epoxy-terminated lactic acid oligomer, 0.6 parts of triethylamine into DMF, react at 50℃ for 8h, dry to obtain modified berberine; S2-3: add modified berberine, penetrant, buffer to deionized water, mix to obtain modified dye solution;

[0041] Step 3: S3-1: take wood pulp fibers for plasma treatment to obtain pretreated wood pulp fibers; S3-2: take 60 parts of pretreated wood pulp fibers, 15 parts of carboxylated cellulose, sequentially open and mix, card and lay on the surface of the degradable base layer, once water jet reinforcement to form a degradable water jet base material; S3-3: take 12 parts of cellulose fibers, 10 parts of polylactic acid fibers, open and mix, card and lay on the surface of the degradable base layer, twice water jet reinforcement to obtain a degradable water jet base material;

[0042] Step 4: place the degradable water jet base material in the MOF antibacterial fixing slurry, immerse for 16h, take out and extrude for the first dip; after the first dip, place it again in the MOF antibacterial fixing slurry, ultrasonic treatment for 45min, take out and extrude for the second time, dry; further spray the modified dye solution on the surface, dry, roll, cut to obtain a water jet wiping material.

[0043] Example 2: a preparation method of a wood pulp-based degradable water jet wiping material, comprising the following steps:

[0044] Step 1: S1-1: nitrogen was bubbled at 1℃, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, methanol were added into 2.5 parts of divinyltriamine, reacted at room temperature for 4h, after removing methanol, reacted at 105℃ for 10h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, 0.55wt% acetic acid were added to adjust pH to 5.8, reacted at 85℃ for 5h, to obtain a Schiff base based hyperbranched polymer; S1-2: zinc chloride, 2,3,5,6-tetraiodoterephthalic acid were mixed by ball milling, washed and dried, then added into DMF, acetic acid and deionized water were added, stirred at 120℃ for 30min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base based hyperbranched polymer, 135 parts of deionized water were dispersed, 1wt% citric acid was added to adjust pH to 5.2, to obtain a MOF antibacterial fixing sizing material;

[0045] Step 2: S2-1: 2.5 parts of berberine, 5.5 parts of 2,4-dimethoxybenzylamine were added into DMSO, stirred at 120℃ for 7h, washed and cooled, then freeze-dried and added into methanol, 0.8 parts of 12wt% hydrochloric acid was added, stirred at room temperature for 6h, the precipitate was washed and dried to obtain amino berberine; S2-2: 10 parts of dehydrated lactic acid, 1.5 parts of ethylene glycol were added into toluene, polycondensed at 140℃ for 3h, after cooling and drying, added into 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, tetrahydrofuran, reacted at 62℃ for 6.5h, neutralized, removed tetrahydrofuran and dried to obtain an epoxy-terminated lactic acid oligomer; 10 parts of amino berberine, epoxy-terminated lactic acid oligomer, 0.6 parts of triethylamine were added into DMF, reacted at 50℃ for 8h, dried to obtain a modified berberine; S2-3: the modified berberine, penetrant, buffer were added into deionized water, mixed to obtain a modified dye solution;

[0046] Step 3: S3-1: wood pulp fibers were subjected to plasma treatment to obtain pretreated wood pulp fibers; S3-2: 70 parts of pretreated wood pulp fibers, 18 parts of carboxylated cellulose were sequentially subjected to opening and mixing, carding and laying, once water jet reinforcement to form a degradable base layer; S3-3: 13 parts of cellulose fibers, 12 parts of polylactic acid fibers were opened and mixed, and laid on the surface of the degradable base layer by carding, and then subjected to secondary water jet reinforcement to obtain a degradable water jet base material;

[0047] Step 4: the degradable water jet base material was placed in the MOF antibacterial fixing sizing material, soaked for 16h, taken out and extruded for once dipping; after once dipping, it was placed in the MOF antibacterial fixing sizing material again, subjected to ultrasonic treatment for 45min, taken out and extruded for twice dipping, and dried; the surface was further sprayed with the modified dye solution, dried, wound, cut and obtained a water jet wiping material.

[0048] Example 3: A method for preparing a wood pulp-based degradable hydroentangled wiping material, comprising the following steps:

[0049] Step 1: S1-1: Under the condition of 1 ℃, nitrogen was introduced, 1.5 parts of N- hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol were added into 2.5 parts of divinyltriamine, and reacted at room temperature for 4 h. After removing the methanol, it was reacted at 105 ℃ for 10 h. Then 2.3 parts of cinnamyl aldehyde and tetrahydrofuran were added, and 0.55 wt% acetic acid was used to adjust the pH to 5.8. It was reacted at 85 ℃ for 5 h to obtain a Schiff base-based hyperbranched polymer. S1-2: Zinc chloride and 2,3,5,6-tetraiodoterephthalic acid were mixed according to a molar ratio of 1:0.8, ball-milled, washed, and dried. Then it was added into DMF, and acetic acid and deionized water were added. It was stirred at 120 ℃ for 30 min, washed, and dried to obtain UiO-66-I4. S1-3: 4 parts of UiO-66-I4, 10 parts of the Schiff base-based hyperbranched polymer, and 135 parts of deionized water were dispersed, and 1 wt% citric acid was added to adjust the pH to 5.2 to obtain a MOF antibacterial fixing slurry;

[0050] Step 2: S2-1: 2.5 parts of berberine and 5.5 parts of 2,4-dimethoxybenzylamine were added into DMSO, and stirred at 120 ℃ for 7 h. After cooling and washing, it was freeze-dried and added into methanol. 0.8 parts of 12 wt% hydrochloric acid was added, and stirred at room temperature for 6 h. The precipitate was washed and dried to obtain amino berberine. S2-2: 10 parts of dehydrated lactic acid and 1.5 parts of ethylene glycol were added into toluene, and polycondensed at 140 ℃ for 3 h. After cooling and drying, it was added into 4.5 parts of epichlorohydrin, 0.3 parts of TBAB, 0.3 parts of sodium hydroxide, and tetrahydrofuran under nitrogen atmosphere, and reacted at 62 ℃ for 6.5 h. After neutralization and removal of tetrahydrofuran, it was dried to obtain an epoxy-terminated lactic acid oligomer. 10 parts of amino berberine, the epoxy-terminated lactic acid oligomer, and 0.6 parts of triethylamine were added into DMF, and reacted at 50 ℃ for 8 h. After drying, a modified berberine was obtained. S2-3: The modified berberine, a penetrating agent, and a buffer were added into deionized water, mixed, and a modified dye solution was obtained;

[0051] Step 3: S3-1: Wood pulp fibers were subjected to plasma treatment to obtain pretreated wood pulp fibers. S3-2: 80 parts of the pretreated wood pulp fibers and 20 parts of carboxylated cellulose were sequentially subjected to opening and mixing, carding and laying, and once hydroentanglement to form a degradable base layer. S3-3: 15 parts of cellulose fibers and 15 parts of polylactic acid fibers were opened and mixed, and laid on the surface of the degradable base layer. After secondary hydroentanglement, a degradable hydroentangled base material was obtained.

[0052] Step 4: The degradable water-jet base material is placed in the MOF antibacterial fixing paste for 16 h, taken out and extruded, which is the first dip; after the first dip, it is placed in the MOF antibacterial fixing paste again, ultrasonically treated for 45 min, taken out and extruded again, which is the second dip, and dried; its surface is further sprayed with modified dye solution, dried, wound and cut, to obtain a water-jet wiping material.

[0053] Comparative Example 1: Based on Example 2, 2, 3, 5, 6-tetraiodoterephthalic acid is adjusted to terephthalic acid, and the rest of the process remains unchanged, which is adjusted to:

[0054] Step 1: S1-1: At 1℃, nitrogen is introduced, 1.5 parts of N-hydroxymethyl acrylamide, 2.6 parts of methyl acrylate, and methanol are added to 2.5 parts of divinyltriamine, reacted at room temperature for 4 h, after removing the methanol, reacted at 105℃ for 10 h; then 2.3 parts of cinnamyl aldehyde, tetrahydrofuran, and 0.55wt% acetic acid are added to adjust the pH to 5.8, and reacted at 85℃ for 5 h to obtain a Schiff base-based hyperbranched polymer; S1-2: zinc chloride and terephthalic acid are mixed in a molar ratio of 1:0.8, ball-milled, washed and dried, added to DMF, added with acetic acid and deionized water, stirred at 120℃ for 30 min, washed and dried to obtain UiO-66-I4; S1-3: 4 parts of UiO-66-I4, 10 parts of Schiff base-based hyperbranched polymer, and 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2, to obtain a MOF antibacterial fixing paste.

[0055] Comparative Example 2: Based on Example 2, the Schiff base-based hyperbranched polymer is adjusted to chitosan, and the rest of the process remains unchanged, which is adjusted to:

[0056] Step 1: S1-1: Zinc chloride and 2, 3, 5, 6-tetraiodoterephthalic acid are mixed in a molar ratio of 1:0.8, ball-milled, washed and dried, added to DMF, added with acetic acid and deionized water, stirred at 120℃ for 30 min, washed and dried to obtain UiO-66-I4; S1-2: 4 parts of UiO-66-I4, 10 parts of chitosan, and 135 parts of deionized water are dispersed, 1wt% citric acid is added to adjust the pH to 5.2, to obtain a MOF antibacterial fixing paste.

[0057] Comparative Example 3: Based on Example 2, N-hydroxymethyl acrylamide and cinnamyl aldehyde are not added, and the rest of the process remains unchanged, which is adjusted to:

[0058] Step 1: S1-1: At 1℃, nitrogen gas is introduced, and 3.5 parts of methyl acrylate and methanol are added to 2.5 parts of divinyltriamine. The mixture is reacted at room temperature for 4 hours. After removing the methanol, the mixture is reacted at 105℃ for 10 hours to obtain a hyperbranched polymer. S1-2: Zinc chloride and 2,3,5,6-tetraiodoterephthalic acid are mixed and ball-milled at a molar ratio of 1:0.8, washed and dried, and added to DMF. Acetic acid and deionized water are added, and the mixture is stirred at 120℃ for 30 minutes. After washing and drying, UiO-66-I4 is obtained. S1-3: 4 parts of UiO-66-I4, 9 parts of hyperbranched polymer and 135 parts of deionized water are dispersed, and 1 wt% citric acid is added to adjust the pH to 5.2 to obtain MOF antibacterial color-fixing paste.

[0059] Comparative Example 4: Based on Example 2, the modified berberine was changed to berberine, while the rest of the process remained unchanged. The adjustment was as follows:

[0060] Step 2: Add berberine, penetrant, and buffer to deionized water, mix, and obtain modified dye solution.

[0061] Test Experiment 1: Antibacterial Performance Test: The spunlace wiping materials prepared in Examples 1-3 and Comparative Examples 1-4 were tested for antibacterial performance using the shaking method according to GB / T20944.3-2008. The products were washed 5 times and the antibacterial performance was tested again. The results are shown in Table 1.

[0062]

[0063] Test Experiment 2: Color fastness test: The spunlace rubbing materials prepared in Examples 1-3 and Comparative Examples 1-4 were tested for color fastness to dry (wet) rubbing and color fastness to water, respectively; the results are shown in Table 2.

[0064]

[0065] The results analysis shows that the scheme can realize the improvement of antibacterial and fixation performances according to the data analysis of Tables 1-2; the data of Comparative Example 1 shows that the 2,3,5,6-tetraiodo terephthalic acid is adjusted to terephthalic acid, losing the iodine-based antibacterial ability, greatly reducing the antibacterial property, and lacking the synergistic effect between iodine and dye, and reducing the fixation property; the data of Comparative Example 2 shows that the Schiff base-based hyperbranched polymer is adjusted to chitosan, which is easy to produce swelling and agglomeration, greatly reducing the structural stability, and reducing the fixation and antibacterial properties; the data of Comparative Example 3 shows that the N-hydroxymethyl acrylamide and cinnamaldehyde are not added, the hydrophilicity of the hyperbranched polymer is reduced, the Schiff base group cannot be formed, the antibacterial property is reduced, and the covalent cross-linking with the dye molecules cannot be formed, the interface bonding force is weak, and the fixation and antibacterial durability are greatly reduced; the data of Comparative Example 4 shows that the modified berberine is adjusted to berberine, which has poor dispersibility, reducing the fixation property, and the interface bonding force with the fiber is reduced, the structural stability is reduced, and the antibacterial and durability are reduced.

[0066] It is apparent for those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and thus can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. The foregoing embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the present application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A method for preparing a wood pulp-based biodegradable hydroentangled wiping material, characterized in that: Includes the following steps: Step 1: (1) Pretreated wood pulp fiber and carboxylated cellulose are opened, mixed, carded and laid on the web, and then hydroentangled and reinforced in one step to form a biodegradable base layer; (2) Cellulose fiber and polylactic acid fiber are opened and mixed, carded and laid on the surface of the biodegradable base layer, and then hydroentangled and reinforced in the second step to obtain a biodegradable hydroentangled base material. Step 2: Dip and rub the biodegradable spunlace base material in MOF antibacterial color-fixing paste twice, and dry it; further spray the surface with modified dye liquid, dry it, roll it up and cut it to obtain the spunlace wiping material. The preparation process of the MOF antibacterial color-fixing paste is as follows: S1-1: Nitrogen gas is introduced at 0~5℃, and N-hydroxymethylacrylamide, methyl acrylate and methanol are added to divinyltriamine. The reaction is carried out at room temperature for 3~5h. After removing methanol, the reaction is carried out at 90~120℃ for 8~12h. Then cinnamaldehyde and tetrahydrofuran are added, and the pH is adjusted to 5.5~6.0 with 0.5wt%~0.6wt% acetic acid. The reaction is carried out at 80~90℃ for 4~6h to obtain Schiff base hyperbranched polymer. S1-2: Zinc chloride and 2,3,5,6-tetraiodoterephthalic acid were mixed, ball-milled, washed and dried, added to DMF, acetic acid and deionized water were added, stirred at 110~130℃ for 20~40 min, washed and dried to obtain UiO-66-I4; S1-3: Disperse UiO-66-I4, Schiff base hyperbranched polymer, and deionized water, and add citric acid to adjust the pH to 5.0~5.5 to obtain MOF antibacterial color-fixing paste; The spraying amount of the modified dye solution is 5~10 g / cm³. 2 The preparation process of the modified dye solution is as follows: S2-1: Berberine and 2,4-dimethoxybenzylamine were added to DMSO and stirred at 110~130℃ for 6~8h. After cooling and washing, the mixture was freeze-dried and added to methanol. 10wt%~15wt% hydrochloric acid was added and stirred at room temperature for 5~7h. The precipitate was washed and dried to obtain aminoberberine. S2-2: Dehydrated lactic acid and ethylene glycol are added to toluene and polycondensed at 120-160℃ for 2-4 hours. After cooling and drying, under a nitrogen atmosphere, epichlorohydrin, TBAB, sodium hydroxide, and tetrahydrofuran are added and reacted at 60-65℃ for 5-8 hours. After neutralization and removal of tetrahydrofuran, the product is dried to obtain an epoxy-terminated lactic acid oligomer. Aminoberberine, the epoxy-terminated lactic acid oligomer, and triethylamine are added to DMF and reacted at 45-55℃ for 7-9 hours. After drying, modified berberine is obtained. S2-3: Add modified berberine, penetrant, and buffer to deionized water, mix, and obtain modified dye solution.

2. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 1, characterized in that: The raw materials of the biodegradable spunlace base material include the following components: by mass parts, 60-80 parts of pretreated wood pulp fiber, 15-20 parts of carboxylated cellulose, 12-15 parts of cellulose fiber, and 10-15 parts of polylactic acid fiber.

3. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 1, characterized in that: The raw materials of the MOF antibacterial color-fixing paste include the following components, by mass parts: 3-5 parts UiO-66-I4, 8-12 parts Schiff base hyperbranched polymer, and 120-150 parts deionized water; wherein the concentration of citric acid is 0.5wt%-1.5wt%.

4. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 3, characterized in that: The UiO-66-I4 comprises zinc chloride and 2,3,5,6-tetraiodoterephthalic acid in a molar ratio of 1:0.5~1; the raw material of the Schiff base hyperbranched polymer comprises the following components: by mass parts, 1~2 parts N-hydroxymethylacrylamide, 2~3.5 parts methyl acrylate, 2~3 parts divinyltriamine, and 2~2.5 parts cinnamaldehyde.

5. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 1, characterized in that: The modified dye solution comprises, by mass percentage: 5-8% modified berberine, 0.4-0.6% penetrant, 0.2-0.8% buffer, and the remainder is deionized water; the raw material of the aminoberberine includes the following components: by mass, 2-3 parts berberine, 4-7 parts 2,4-dimethoxybenzylamine, and 0.5-1 parts 10wt%-15wt% hydrochloric acid; The modified berberine raw materials include the following components by mass: 8-12 parts lactic acid, 1-2 parts ethylene glycol, 3-6 parts epichlorohydrin, 0.2-0.5 parts TBAB, 0.2-0.5 parts sodium hydroxide, 8-12 parts aminoberberine, and 0.5-0.8 parts triethylamine.

6. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 1, characterized in that: The process parameters for the first hydroentanglement reinforcement are: hydroentanglement pressure of 3.5~4.5MPa, number of hydroentanglement passes of 1~2, hydroentanglement height of 35~40mm, and conveyor speed of 10~15m / min. The process parameters for the secondary hydroentanglement reinforcement are as follows: hydroentanglement pressure is 5.5~6.5MPa, the number of hydroentanglement passes is 2~3, the hydroentanglement height is 40~45mm, and the conveyor belt speed is 15~20m / min.

7. The method for preparing a wood pulp-based biodegradable hydroentangled wiping material according to claim 1, characterized in that: The two-dip and two-roll process is as follows: the biodegradable spunlace base material is placed in MOF antibacterial color-fixing slurry and soaked for 12-18 hours, then taken out and squeezed, which is the first dip and roll; after the first dip and roll, it is placed in MOF antibacterial color-fixing slurry again, ultrasonically treated for 30-60 minutes, then taken out and squeezed a second time, which is the second dip and roll.

8. The spunlace wiping material prepared by the method for preparing a wood pulp-based biodegradable spunlace wiping material according to any one of claims 1 to 7.

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