CN114457591B - Antigen fibrillated cellulose fiber and preparation method thereof - Google Patents
Antigen fibrillated cellulose fiber and preparation method thereof Download PDFInfo
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- CN114457591B CN114457591B CN202210285111.6A CN202210285111A CN114457591B CN 114457591 B CN114457591 B CN 114457591B CN 202210285111 A CN202210285111 A CN 202210285111A CN 114457591 B CN114457591 B CN 114457591B
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 70
- 239000000427 antigen Substances 0.000 title claims abstract description 44
- 102000036639 antigens Human genes 0.000 title claims abstract description 44
- 108091007433 antigens Proteins 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009987 spinning Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 230000001112 coagulating effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000011550 stock solution Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000000890 antigenic effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 206010061592 cardiac fibrillation Diseases 0.000 abstract description 14
- 230000002600 fibrillogenic effect Effects 0.000 abstract description 13
- 229920002678 cellulose Polymers 0.000 abstract description 12
- 239000001913 cellulose Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 229920000433 Lyocell Polymers 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000835 fiber Substances 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 230000015271 coagulation Effects 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 239000004627 regenerated cellulose Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- -1 biology Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses an antigen fibrillated cellulose fiber and a preparation method thereof. The cellulose fiber with antigen fibrillation is prepared by adding the glycidyl ether type epoxy resin without an aldehyde crosslinking agent in the cellulose fiber spinning or post-treatment process and crosslinking the cellulose with the glycidyl ether type epoxy resin under proper content, proportion and reaction conditions, so that the problem that the cellulose fiber is easy to fibrillate is solved, and the processability and wearing comfort of the cellulose fiber are improved.
Description
Technical Field
The invention belongs to the technical field of fiber manufacturing, and particularly relates to an antigen fibrillated cellulose fiber and a preparation method thereof.
Background
With the development and progress of science and technology, the gradual exhaustion of traditional energy sources and the increasing awareness of human environmental protection, the development and utilization of novel green, renewable and environment-friendly materials are a necessary trend of polymer development. Due to the non-renewable nature of raw materials based on the traditional petroleum and coal industries, there is an urgent need to develop new materials from renewable resources through green processes to meet the social demands. Cellulose is one of the most abundant raw materials in nature, provides properties widely required by people, including biocompatibility, relative stability to most chemical products and the like, so that the development and utilization of the cellulose material has wide development prospect in the fields of food, textile, biology, medicine and the like.
Because the Lyocell product is 100 percent of cellulose, the Lyocell can be completely biodegraded into inorganic matters CO2 and H2O in a short time, the fiber is participated in the material circulation of the ecological system again, is environment-friendly and pollution-free, and is praised as a novel green fiber in the 21 st century. Lyocell is regenerated cellulose fiber spun by dry-wet method by taking pulp as a raw material and N-methylmorpholine-N-oxide (NMMO) as a solvent, compared with viscose fiber, the Lyocell fiber has the advantages of small raw material consumption, simple production process and short flow, the dissolution of the fiber and the NMMO is a pure physical process, the whole production flow is in a water system, no byproducts are generated, the recovery rate of the solvent NMMO is up to 99.5%, and the cellulose product can be naturally degraded, has no pollution to the environment and is completely green and environment-friendly.
Of all regenerated cellulose fibers, lyocell fibers have the highest degree of fibrillation. After the Lyocell fiber and the fabric thereof are subjected to the friction action of mechanical external force in a wet state, fine fibrils split along the fiber axial direction are separated on the surface of the fibrils, so that hairiness is easily generated on the surfaces of the fibers and the fabric thereof, and the product application of the Lyocell fiber is severely limited.
Currently, the approach to solving the problem of the tendency of Lyocell fibres to fibrillate is mainly to crosslink the fibres or their fabrics. Wherein, the patent of the invention No. CN103306136A reports that an aldehyde cross-linking agent formed by combining oligomeric polybasic acid with the molecular weight of 400-1000 and C2-C6 polybasic acid reacts with cellulose fibers, and has obvious effect on the antigen fibrillation performance of the fibers; in the patent report of the invention No. CN95192563.6, in order to enhance the crosslinking effect, a crosslinking agent with three acrylamide groups, preferably 1,3, 5-triacrylamide hexahydro-1, 3, 5-triazine is adopted to react with the wet solution spinning cellulose fiber to reduce fibrillation; however, the crosslinking agents used in the above patents have problems of aldehyde pollution, complex synthesis, complex process and the like, respectively, so that the industrial production of the antigen fibrillated cellulose fibers is difficult.
In addition, a great deal of research has shown that prolonged contact or wear of formaldehyde-containing fabrics can have a great impact on human health. There are two main approaches to solving this problem: firstly, the formaldehyde pollution problem is solved from the root, and a novel environment-friendly cross-linking agent capable of replacing urea formaldehyde resin is found. And secondly, carrying out post-processing treatment on formaldehyde pollution, so that formaldehyde volatilized from fibers or fabrics can be rapidly reduced and stably maintained below a standard value. Therefore, the development process of the environment-friendly formaldehyde-free crosslinking technology has important research significance for the post-treatment modification of cellulose fibers.
Disclosure of Invention
In order to further solve the defects in the prior art, the invention aims to provide the antigen fibrillated cellulose fiber and the preparation method thereof, the preparation method is simple, the produced fiber has very excellent antigen fibrillating performance, and the fiber does not contain formaldehyde, glutaraldehyde and other aldehyde substances, so that the requirements of actual processing and application are met.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A method for preparing an antigen fibrillated cellulose fiber, characterized by: comprises the steps of,
(1) Preparing finishing liquid containing an aldehyde-free cross-linking agent, wherein the aldehyde-free cross-linking agent is glycidyl ether type epoxy resin;
(2) And (3) immersing the cellulose fibers in the finishing liquid, and washing and drying the immersed cellulose fibers after the completion of immersing to obtain the antigen fibrillated cellulose fibers.
Further, the finishing liquid is prepared by mixing the glycidyl ether type epoxy resin and water in a mass ratio of 1:1000-1:100, preferably 1:600-1:100, more preferably 1:200.
Further, the mass of the glycidyl ether type epoxy resin is 1 to 60%, preferably 1 to 40%, more preferably 20% of the mass of the cellulose fiber.
Further, the time for immersing the cellulose fibers in the finishing liquid is 2 s-10 min; preferably, 10s-5min; more preferably, 10s-3min.
Further, the crosslinking reaction of the cellulose fiber with the aldehyde-free crosslinking agent glycidyl ether type epoxy resin in the finishing liquid may be terminated with an acidic substance such as hydrochloric acid, nitric acid, phosphoric acid, acetic acid, etc., preferably a hydrochloric acid solution, at a concentration of 0.0035 to 0.1546mol/L, preferably 0.0050 to 0.1300mol/L, more preferably 0.1000mol/L.
Since the crosslinking reaction is carried out under alkaline conditions, an acidic substance is preferably used as a reaction terminator.
Optionally, the finishing liquid can be placed in a finishing liquid tank and directly applied to a continuous production line of cellulose fibers, and the specific method is as follows: in the production process, cellulose fibers generated by coagulation through a coagulating bath are soaked in a finishing liquid tank after being drawn and washed, and the antigen fibrillated cellulose fibers are prepared by washing and drying after the soaking is finished.
Alternatively, commercially available cellulose fibers may be placed in the finishing tank containing the finishing liquid to crosslink, thereby preparing the fibrillated cellulose fibers.
The invention provides another preparation method of antigen fibrillated cellulose fiber, which is characterized in that: comprises the steps of,
(1) Adding an aldehyde-free cross-linking agent into cellulose fiber spinning stock solution according to the weight ratio to prepare spinning solution, wherein the aldehyde-free cross-linking agent is glycidyl ether type epoxy resin;
(2) Spinning the spinning solution by a wet method or a dry spray wet method, coagulating by a coagulating bath, washing with water, and drying to obtain the antigen fibrillated cellulose fiber.
Further, the weight ratio of the glycidyl ether type epoxy resin to the cellulose fiber spinning stock in the spinning solution is 1:1000-50:1000, preferably 10:1000-30:1000, and more preferably 20:1000-30:1000.
The invention also provides a preparation method of the antigen fibrillated cellulose fiber, which comprises the following steps:
(1) Adding a cross-linking agent glycidyl ether type epoxy resin into cellulose fiber coagulating bath to prepare coagulating bath solution;
(2) The cellulose fiber spinning solution is spun by wet method or dry spray wet method, is coagulated by the coagulating bath solution, and is washed and dried to prepare the antigen fibrillated cellulose fiber.
Further, the pH of the finishing liquid and the spinning solution is 8-11, preferably 10.
Further, when a crosslinking agent glycidyl ether type epoxy resin is added to a cellulose fiber coagulation bath to prepare a coagulation bath solution, and further an antigen fibrillated cellulose fiber is prepared, the pH of the coagulation bath solution is 8 to 11, preferably 10.
Further, the temperature of the finishing liquid and the spinning solution is 40 to 70 ℃, preferably 50 to 60 ℃, more preferably 60 ℃.
Further, when a crosslinking agent glycidyl ether type epoxy resin is added to a cellulose fiber coagulation bath to prepare a coagulation bath solution, and further an antigen-fibrillated cellulose fiber is prepared, the temperature of the coagulation bath solution is 40 to 70 ℃, preferably 50 to 60 ℃, more preferably 60 ℃.
Further, the pH values of the finishing liquid and the spinning solution are regulated by an alkaline substance, or an alkaline substance and an acidic substance, wherein the alkaline substance comprises sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate and the like, the acidic substance comprises hydrochloric acid, nitric acid and the like, preferably a sodium hydroxide NaOH solution, and the concentration of the acidic substance is 0.0245-0.2043 mol/L, preferably 0.05000-0.1500 mol/L, more preferably 0.0800-0.1050 mol/L.
Further, when a crosslinking agent glycidyl ether type epoxy resin is added to a coagulation bath of cellulose fibers to prepare a coagulation bath solution, and further an antigen-fibrillated cellulose fibers are prepared, the pH of the coagulation bath solution is adjusted by an alkaline substance, or an alkaline substance and an acidic substance, the alkaline substance comprises sodium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, sodium carbonate, etc., the acidic substance comprises hydrochloric acid, nitric acid, etc., preferably sodium hydroxide NaOH solution, the concentration of which is 0.0245 to 0.2043mol/L, preferably 0.5000 to 0.1500mol/L, more preferably 0.800 to 0.1050mol/L.
Further, the glycidyl ether type epoxy resin is an epoxy resin of a glycidyl ether structure, preferably an aliphatic polyol glycidyl ether containing a plurality of epoxy groups, such as polyethylene glycol diglycidyl ether.
Further, the epoxy index of the glycidyl ether type epoxy resin is 0.10 to 0.70.
The epoxy index of the glycidyl ether type epoxy resin is a parameter for characterizing the number of epoxy groups on the side chain thereof, and the higher the epoxy index is, the more the number of epoxy groups on the side chain of the glycidyl ether type epoxy resin is, and vice versa. In the case of cellulose fibers, since the glycidyl ether type epoxy resin plays an antigen-fibrillation role by virtue of the epoxy groups on the side chains thereof, if the epoxy index is too low, the crosslinking action is limited, and if the epoxy index is too high, the mechanical strength of the resin is large, but the resin is brittle, and the product is hard. The epoxy index of the glycidyl ether type epoxy resin selected in the present invention is thus 0.10 to 0.70, preferably 0.25 to 0.45, more preferably 0.35.
The crosslinking time and the crosslinking agent mass ratio can influence the cellulose fiber antigen fibrillation effect, when the crosslinking time is shorter or the crosslinking agent mass ratio is lower, the crosslinked network structure is easy to deform, holes are larger, the antigen fibrillation capacity is poorer, as the crosslinking time or the crosslinking agent mass ratio is increased, the crosslinking point density is increased, the holes are smaller, the antigen fibrillation performance is enhanced, the enhancement effect is obvious, but the network structure deformation capacity is poor, gelation is serious, the fiber mechanical property is reduced, the viscosity of spinning solution is increased, the processing is difficult, and the practical value is lost due to the overlong crosslinking time or excessive crosslinking agent. In order to ensure the properties of the fibrillated antigenic cellulose fibers, both the crosslinking time and the crosslinking agent mass ratio should be controlled within the limits defined in the present invention.
Optionally, the cellulose fiber is one or more of Lyocell fiber, viscose fiber, acetate fiber, cuprammonium fiber and other regenerated cellulose fibers.
The invention also provides the antigen fibrillated cellulose fiber obtained by the preparation method.
According to the invention, an aldehyde-free cross-linking agent glycidyl ether type epoxy resin is added into a cellulose fiber aftertreatment finishing liquid or spinning stock liquid or coagulation bath, epoxy groups at two ends of the glycidyl ether type epoxy resin are subjected to ring opening at 40-70 ℃ under alkaline conditions and nucleophilic substitution reaction on hydroxyl groups on cellulose to form a covalent cross-linking network, a chemical reaction formula is shown in figure 1, hydroxyl groups on the surface of cellulose N (N') react with epoxy groups at two ends of the glycerol ether type epoxy resin P to form cellulose Q containing a covalent cross-linking network structure, stable chemical bonds are formed between the aldehyde-free cross-linking agent and the cellulose in the covalent cross-linking network, the transverse binding force among fibrils is enhanced, the possibility that the fibrils are stripped from a fiber main body is reduced, and the cellulose fiber with excellent antigen fibrillation performance is obtained. In addition, as can be seen from fig. 1, the epoxy groups on the side chains of the glycidyl ether type epoxy resin form hydroxyl groups after ring opening, and the hydroxyl groups can form a compact hydrogen bond crosslinked network structure with the hydroxyl groups of cellulose, so that the cellulose fiber antigen fibrillation performance is enhanced.
The invention utilizes the glycidyl ether type epoxy resin modified cellulose fiber without aldehyde crosslinking agent, has obvious antigen fibrillation effect, can control the crosslinking degree of a crosslinking network by controlling the content of the crosslinking agent, and meets the requirements of actual processing and application. The method has simple and easy steps. The formaldehyde-free crosslinking agent is nontoxic, has low cost and no environmental pollution, can not release formaldehyde compounds in the production and storage processes and the process of taking the fiber or fabric treated by the formaldehyde-free crosslinking agent, has high durability, and has no phenomena of chlorine absorption, chlorine loss and yellowing.
Drawings
FIG. 1 is a chemical reaction formula of a nucleophilic substitution reaction of epoxy groups at both ends of a glycidyl ether type epoxy resin and hydroxyl groups on cellulose fibers.
FIG. 2 is a microscopic image of an uncrosslinked Lyocell fiber after 24h of ultrasonic vibration treatment.
Fig. 3 to 7 are microscopic images of Lyocell fibers crosslinked with polyethylene glycol diglycidyl ether for 10s,30s,50s,70s,90s, respectively, after 24 hours of ultrasonic vibration treatment in a post-treatment process.
FIG. 8 is a microscopic image of polyethylene glycol diglycidyl ether crosslinked Lyocell fibers in a spin dope after 24 hours of ultrasonic agitation.
Reference numerals
N (N'): cellulose; p: glycerol ether type epoxy resin; q cellulose containing covalently crosslinked network structure
Detailed Description
The invention is further described below with reference to examples.
The antigen fibrillation performance and the mechanical property of the antigen fibrillated cellulose fiber are respectively tested by adopting an ultrasonic oscillation treatment method and an electronic single fiber brute force instrument.
Example 1
(1) Preparation of finishing liquid:
1g of polyethylene glycol diglycidyl ether with an epoxy index of 0.35 is dissolved in 200g of water to prepare a finishing liquid, the finishing liquid is heated to 60 ℃, and the PH value of the finishing liquid is regulated to 10 by NaOH solution regulator with a concentration of 0.1035 mol/L;
(2) Preparation of antigen fibrillated Lyocell fibers:
Five groups of Lyocell fibers, each weighing 5g, were immersed in the finishing liquor for 10s,30s,50s,70s,90s, respectively (stop reaction with 0.1000mol/L HCl solution). And after taking out, rolling the finishing liquid in the fibers, repeatedly washing with water, and drying in an oven at 60 ℃ to obtain 5 groups of antigen fibrillated Lyocell fibers.
The mechanical properties are shown in Table 1.
TABLE 1
| Sample of | Breaking strength (cN/dtex) | Elongation at break (%) |
| Uncrosslinked Lyocell fibers | 4.58 | 6.83 |
| Lyocell fibers crosslinked for 10s | 4.48 | 7.09 |
| Lyocell fibers crosslinked for 30s | 4.40 | 7.22 |
| Lyocell fibers crosslinked for 50s | 5.05 | 6.61 |
| Lyocell fibers crosslinked for 70s | 4.94 | 7.22 |
| Lyocell fibers crosslinked for 90s | 4.94 | 6.61 |
As can be seen from Table 1, the strength at break and the elongation at break of the antigen fibrillated Lyocell fiber prepared in example 1 of the present invention are not significantly reduced compared with those of the uncrosslinked Lyocell fiber, indicating that the mechanical properties of the antigen fibrillated Lyocell fiber are not reduced by the addition of the crosslinking agent.
Fig. 2 shows a microscopic image of an uncrosslinked Lyocell fiber after 24h of ultrasonic oscillation treatment. Fig. 3 to 7 show microscopic images of Lyocell fibers crosslinked with polyethylene glycol diglycidyl ether for 24 hours after ultrasonic vibration treatment for 10s,30s,50s,70s,90s, respectively. It can be seen that many fibrils are peeled off from the surface of the uncrosslinked Lyocell fibers, the fibers have a hairy appearance, and a fibrillation phenomenon is generated, and as the crosslinking time increases, the reduction of the fluff on the surface of the fibers is obvious, and when the crosslinking time is more than 30 seconds, the surface of the fibers is free of the fluff, and the antigen fibrillation effect is obvious.
Example 2
(1) Preparation of the spinning solution:
Adding 30g of polyethylene glycol diglycidyl ether (epoxy index 0.35) into 1000g of Lyocell fiber spinning stock solution at normal temperature to prepare spinning solution, and adjusting the pH value of the spinning solution to 10 by using a NaOH solution with the concentration of 0.1035mol/L as an adjusting agent;
(2) Preparation of antigen fibrillated Lyocell fibers:
And (3) mechanically stirring the spinning solution prepared in the step (1) uniformly at the temperature of 60 ℃, defoaming and standing under vacuum, spinning and extruding the spinning solution into a coagulating bath by a wet method or a dry-spray wet method, washing with water, and drying to obtain the antigen fibrillated Lyocell fiber. The mechanical properties are shown in Table 2.
TABLE 2
| Sample of | Breaking strength (cN/dtex) | Elongation at break (%) |
| Uncrosslinked Lyocell fibers | 4.58 | 6.83 |
| Crosslinked Lyocell fibers | 4.55 | 7.11 |
As can be seen from Table 2, the polyethylene glycol diglycidyl ether crosslinked Lyocell fiber prepared in example 2 of the present invention has no significant decrease in breaking strength and elongation at break compared with the uncrosslinked Lyocell fiber, indicating that the mechanical properties of the fibrillated Lyocell fiber are not diminished by the addition of the crosslinking agent.
Fig. 2 shows a microscopic image of uncrosslinked Lyocell fibers after 24 hours of sonication, and fig. 8 shows a microscopic image of antigen fibrillated Lyocell fibers after 24 hours of sonication. It can be seen that the surface of the antigen-fibrillated Lyocell fiber prepared in example 2 of the present invention is almost free of lint, and the antigen-fibrillating effect is remarkable, compared with the uncrosslinked Lyocell fiber.
Claims (8)
1. A method for preparing an antigen fibrillated cellulose fiber, characterized by: comprises the steps of,
(1) Preparing finishing liquid containing an aldehyde-free cross-linking agent, wherein the aldehyde-free cross-linking agent is glycidyl ether type epoxy resin;
(2) Immersing cellulose fibers in the finishing liquid, washing with water and drying after the immersing is finished, so as to prepare antigen cellulose fibers;
wherein the pH value of the finishing liquid is 8-11, the temperature of the finishing liquid is 40-70 ℃, and the epoxy index of the glycidyl ether type epoxy resin is 0.10-0.70.
2. The method for producing an antigen fibrillated cellulose fiber according to claim 1, characterized in that: the finishing liquid is prepared by mixing the formaldehyde-free cross-linking agent glycidyl ether type epoxy resin and water according to the mass ratio of 1:1000-1:100.
3. The method for producing an antigen fibrillated cellulose fiber according to claim 1, characterized in that: the mass of the formaldehyde-free cross-linking agent is 1-60% of the mass of the cellulose fiber.
4. The method for producing an antigen fibrillated cellulose fiber according to claim 1, characterized in that: the time for immersing the cellulose fiber in the finishing liquid is 2 s-10 min.
5. The method for producing an antigen fibrillated cellulose fiber according to claim 1, characterized in that: the crosslinking reaction of the cellulose fiber and the glycidyl ether type epoxy resin in the finishing liquid is terminated by at least one acidic substance selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
6. A method for preparing an antigen fibrillated cellulose fiber, characterized by: comprises the steps of,
(1) Adding an aldehyde-free cross-linking agent into cellulose fiber spinning stock solution according to the weight ratio to prepare spinning solution, wherein the aldehyde-free cross-linking agent is glycidyl ether type epoxy resin;
(2) Spinning the spinning solution by a wet method or a dry spray wet method, solidifying by a coagulating bath, and then washing and drying to obtain the antigen fibrillated cellulose fiber;
wherein the pH of the spinning solution is 8-11, the temperature of the spinning solution is 40-70 ℃, and the epoxy index of the glycidyl ether type epoxy resin is 0.10-0.70.
7. The method for producing an antigen fibrillated cellulose fiber according to claim 6, characterized in that: the weight ratio of the glycidyl ether type epoxy resin in the spinning solution to the cellulose fiber spinning solution is 1:1000-50:1000.
8. An antigen fibrillated cellulose fiber characterized by: the fibrillated antigenic cellulose fiber obtained by the preparation method according to any one of claims 1 and 6.
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| JPH09158050A (en) * | 1995-10-04 | 1997-06-17 | Kanebo Ltd | Antipilling solvent-spun cellulosic fiber, its fiber structure and its production |
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| JPH10158921A (en) * | 1996-11-19 | 1998-06-16 | Kanebo Ltd | Anti-pilling solvent-spun cellulosic fiber, its fiber structure and production |
| JPH10212671A (en) * | 1997-01-28 | 1998-08-11 | Kanebo Ltd | Cellulosic fiber and crosslinking modification of structural material of the same |
| EP3594247A4 (en) * | 2017-03-07 | 2020-12-02 | Kao Corporation | Method for producing modified cellulose fibers |
| CN112410908B (en) * | 2020-11-17 | 2021-04-27 | 青岛尼希米生物科技有限公司 | Protein modified cellulose composite fiber and preparation method and application thereof |
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