CN111663193A - Method for improving strength of cellulose fiber and cellulose fiber prepared by method - Google Patents
Method for improving strength of cellulose fiber and cellulose fiber prepared by method Download PDFInfo
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- CN111663193A CN111663193A CN202010455625.2A CN202010455625A CN111663193A CN 111663193 A CN111663193 A CN 111663193A CN 202010455625 A CN202010455625 A CN 202010455625A CN 111663193 A CN111663193 A CN 111663193A
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- epichlorohydrin resin
- modified polyamide
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- polyamide epichlorohydrin
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- 238000000034 method Methods 0.000 title claims abstract description 90
- 229920003043 Cellulose fiber Polymers 0.000 title abstract description 57
- 239000004952 Polyamide Substances 0.000 claims abstract description 122
- 229920002647 polyamide Polymers 0.000 claims abstract description 122
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229920005989 resin Polymers 0.000 claims abstract description 96
- 239000011347 resin Substances 0.000 claims abstract description 96
- 238000009987 spinning Methods 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 41
- 239000011550 stock solution Substances 0.000 claims abstract description 38
- 229920000297 Rayon Polymers 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000001965 increasing effect Effects 0.000 claims abstract description 15
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 10
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 238000002715 modification method Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 abstract description 65
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract description 56
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract description 53
- 239000008112 carboxymethyl-cellulose Substances 0.000 abstract description 53
- 230000008569 process Effects 0.000 abstract description 52
- 238000004132 cross linking Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 11
- 239000001913 cellulose Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000004627 regenerated cellulose Substances 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 aldehyde compound Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- 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
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
- D06M15/09—Cellulose ethers
-
- 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
- D06M15/59—Polyamides; Polyimides
-
- 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
- D06M2200/35—Abrasion, pilling or fibrillation resistance
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a method for improving the strength of cellulose fiber, which comprises the steps of preparing a spinning solution; preparing a spinning stock solution, namely blending modified polyamide epichlorohydrin resin and carboxymethyl cellulose (CMC) with a viscose stock solution; the polyamide epichlorohydrin is modified by using the melamine or the benzoguanamine, so that the distance between molecular chains is increased, the rigidity of the prepared high-strength cellulose fiber is reduced, and the breaking elongation of the high-strength cellulose fiber is not much different from that of the conventional cellulose fiber; by adding the modified polyamide epichlorohydrin resin and the CMC with high substitution degree in the spinning forming and post-treatment processes, the influence caused by loss of modified substances in the spinning forming and post-treatment processes is avoided, and the subsequent crosslinking effect in the fiber is ensured; the prepared fiber has dry breaking strength of 2.77-3.05 cN/dtex and wet breaking strength of 1.69-1.95 c/dtex.
Description
Technical Field
The invention relates to a method for improving the strength of cellulose fibers and cellulose fibers prepared by the method, in particular to a method for preparing high-strength cellulose fibers by using cellulose pulp, wet strength agent modified polyamide epichlorohydrin resin (PAE resin) and sodium carboxymethylcellulose (CMC) as main raw materials and fibers thereof, belonging to the technical field of textile.
Background
Due to good hygroscopicity, comfortable wearing and excellent spinnability, the cellulose fiber has wide application, is often blended and interwoven with cotton, wool or various synthetic fibers, and is used for various clothes and decorative textiles. However, the common cellulose fiber has relatively low strength, is swollen by water in a wet state, has obvious strength reduction, poor dimensional stability and abrasion resistance and influences the wearability of the fabric. Therefore, the method for improving the performance of the cellulose fiber by process modification and other methods is an important direction for the development of the cellulose fiber, and a new variety of the cellulose fiber with high strength, high modulus, good size stability and excellent wear resistance is prepared.
Chinese patent CN201811436865.7 discloses a preparation method of high-orientation high-toughness regenerated cellulose fiber and the high-orientation high-toughness regenerated cellulose fiber. The patent technology firstly mixes regenerated cellulose solution with cross-linking agent to obtain mixed solution of regenerated cellulose and cross-linking agent; the cross-linking agent is selected from epoxy compound and/or aldehyde compound, including epichlorohydrin and epoxy chlorobutane or glutaraldehyde and succinaldehyde. The aldehyde substance is used, which easily causes environmental pollution, worsens the working environment and limits the production.
The polyamide epichlorohydrin resin (PAE) is the most common wet strength agent in the papermaking field, and has the characteristics of high efficiency, wide application range and the like. In addition to increasing the wet strength properties of paper, PAE can also increase the dry strength to various degrees. Sodium carboxymethylcellulose (CMC) is a water-soluble cellulose derivative which is used more at present, is often used as a water retention agent in coating, and can also be used for improving the dry strength of paper. The contents of the above-mentioned systems are disclosed in the published papers "PAE/CMC two-dimensional enhancement system research" (Li Jian et al), "CS/CMC two-dimensional enhancement system preparation and application" (Cao Xiao Yao et al), "CMC/CTAB two-dimensional paper enhancement system action and mechanism research" (Chenlin et al), "PAE/CMC two-dimensional enhancement system application research in old corrugated paper pulp" (Pailajuan et al), patent CN201210445338.9 (a paper-making enhancement method), CN201510668362.2 (a production method of medical packaging paper with high antibacterial property), and so on.
By analysis, the application is limited to papermaking and has not been studied in other aspects. Because of the great difference between papermaking and fiber forming, the main points are as follows:
1. different characteristics of the final product
The fiber obtained by papermaking is a two-dimensional sheet structure substance, while the cellulose fiber is a substance with a thin and long structure with a certain length-diameter ratio, which determines the difference of the cellulose fiber and the cellulose fiber in the forming process, so that the cellulose fiber is more refined in the forming process, and the auxiliary agent has higher requirements in the application process.
2. Different technological process and technological conditions
The main flow in the papermaking process comprises the working procedures of cooking, washing, bleaching and the like, and most of the working procedures are carried out under the alkaline condition; the process flow of the cellulose fiber comprises the working procedures of dipping, squeezing, crushing, sulfonating, dissolving, spinning and the like, wherein the former phase is mainly carried out under alkaline conditions, and the spinning is carried out in acid bath acidity, so that the prior polyamide epichlorohydrin resin and CMC can be greatly different when used for papermaking and the cellulose fiber.
In the early stage test, the applicant finds that the polyamide epichlorohydrin resin can increase the rigidity of the fiber and reduce the elongation at break while improving the strength of the cellulose in the preparation process of the cellulose fiber; the polyamide epichlorohydrin resin and the CMC are easy to run off in the spinning forming and post-treatment processes, so that the crosslinking effect of the polyamide epichlorohydrin resin and the CMC in fibers is poor, and the strength of cellulose fibers is difficult to improve.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for improving the strength of cellulose fibers, which takes cellulose pulp, modified polyamide epichlorohydrin resin and high-substitution-degree CMC as raw materials, and improves the processes of shaping such as preliminary and simultaneous preforming of three components in a coagulating bath, further shaping in a second bath, oil bath treatment and the like by adjusting the composition of the coagulating bath and the post-treatment process, so that the retention amount of the modified polyamide epichlorohydrin resin is increased, high-temperature curing is performed in the drying process, and the bonding effect of the CMC is combined to further play a role in enhancing, so that the high-strength cellulose fibers are obtained, and the following technical problems are solved:
(1) the crosslinking and bonding effects of the modified polyamide epichlorohydrin resin and the CMC in the fiber are ensured, and the strength of the cellulose fiber is improved;
(2) the strength of the fiber is improved, the density of cross-linking points in the fiber is reduced, the rigidity of the fiber is reduced, and the influence on the elongation at break is small.
Another technical problem to be solved by the present invention is to provide a high-strength cellulose fiber prepared by the method.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method of increasing the strength of cellulosic fibers, the method comprising preparing a dope; the preparation of the spinning stock solution comprises the step of blending the modified polyamide epichlorohydrin resin, the CMC and the viscose stock solution.
The following is a further improvement of the above technical solution:
the preparation method comprises the following steps:
(1) cellulose pulp is used as raw material and is soaked, squeezed, crushed, aged and yellowThe step of dissolving and dissolving is carried out to prepare a viscose stock solution, wherein the alpha cellulose accounts for 8.2-9.0%, the sodium hydroxide accounts for 4.5-5.1%, the viscosity accounts for 45-55 s, and the ripening degree is 16-22 mL (10% NH)4Cl）；
(2) Adding the prepared modified polyamide epichlorohydrin resin and CMC into a viscose stock solution, blending, and fully mixing to obtain a spinning stock solution, or adding the modified polyamide epichlorohydrin resin and CMC into the viscose stock solution according to a proportion by using a pre-spinning injection device to obtain the spinning stock solution;
preferably, the ratio of the modified polyamide epichlorohydrin resin, the CMC and the alpha cellulose in the viscose stoste in the step (2) is 3.5-7.0:1.0-2.5: 90.5-95.5.
Preferably, the preparation and modification method of the modified polyamide epichlorohydrin resin in the step (2) comprises the following steps: preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to be 30-50%, cooling to 90-120 ℃, adding melamine or benzoguanamine, wherein the amount of melamine or benzoguanamine is 10-30% of that of the polyamide prepolymer, reacting for 30-90min, cooling the product to 50-80 ℃, and adjusting the pH value to 2.0-5.0 after reacting for 2.0-4.0 h under the condition that the pH value is 7.5-9.5 (the pH value of the system is ensured in the reaction process), adding epichlorohydrin into the system, wherein the amount of epichlorohydrin is 30-50% of that of the polyamide prepolymer, stopping the reaction to obtain a modified polyamide epichlorohydrin resin solution, adjusting the pH value of the modified polyamide epichlorohydrin resin solution to be neutral, and enabling the solid content of the modified polyamide epichlorohydrin resin solution to be 10-15%.
Preferably, the carboxymethyl cellulose (CMC) in the step (2) has a substitution degree of 1.0 to 1.5, and is added to the modified polyamide-epichlorohydrin resin solution prepared above during use.
(3) And (3) filtering, defoaming, spinning and forming and post-treating the spinning solution after post-dissolving and blending, or spinning and forming, post-treating and drying the spinning solution obtained by blending through a pre-spinning injection device to obtain the high-strength cellulose fibers.
Preferably, in the spinning forming process in the step (3), the coagulation bath composition is adjusted, and the coagulation bath composition contains 0.5-1.5% of modified polyamide epichlorohydrin resin in addition to 7.5-8.5% of sulfuric acid, 1.2-1.6% of zinc sulfate, and 22.5-26.0% of sodium sulfate.
Preferably, in the spinning forming process in the step (3), the two-bath composition is adjusted, and the modified polyamide epichlorohydrin resin contains 10-20 g/L of sulfuric acid and 1.0-3.0%.
Preferably, in the post-treatment process in the step (3), sodium hydroxide is adopted in a desulfurization bath with the concentration of 4.0-8.0 g/L except for the conventional viscose fiber post-treatment process, and the desulfurization bath not only achieves the purpose of removing sulfur elements in the fibers, but also can provide a proper pH value for the modified polyamide epichlorohydrin resin to promote the crosslinking and curing of the modified polyamide epichlorohydrin resin.
Preferably, in the post-treatment process in the step (3), the composition of the oil bath is adjusted, and the oil bath contains 3.0-6.0 g/L of oil agent, 0.5-1.0% of modified polyamide epichlorohydrin resin and 0.5-1.0% of CMC.
Preferably, in the drying step in the step (3), the drying temperature is 125-140 ℃, the drying time is 30-90min, and the wet strength agent is ensured to be crosslinked.
In the production process, the preparation process, the spinning process and the post-treatment process of the viscose dope can be properly adjusted according to the production requirement and the requirement on the product.
The main components of the fiber prepared by the invention comprise 3.25-6.67% of modified polyamide epichlorohydrin resin and 0.89-2.26% of carboxymethyl cellulose (CMC). The polyamide epichlorohydrin resin can form an interpenetrating copolymer network structure in a cellulose fiber matrix, so that the polyamide epichlorohydrin resin has a remarkable enhancing effect, the melamine or benzoguanamine is used for modifying the cellulose fiber matrix to further improve the performance of the cellulose fiber matrix, and the bonding effect of CMC is combined, so that the dry breaking strength of the fiber is 2.77-3.05 cN/dtex, the wet breaking strength is 1.69-1.95 c/dtex, the wet modulus is 0.40-0.65 cN/dtex, and the elongation at break is 15.1-18.3%.
The invention adopts the technical scheme with the beneficial effects that:
1. the polyamide epichlorohydrin is modified by using melamine or benzoguanamine, so that the distance between molecular chains is increased, the rigidity of the prepared high-strength cellulose fiber is reduced, and the breaking elongation of the high-strength cellulose fiber is not much different from that of the conventional cellulose fiber.
2. By adding the modified polyamide epichlorohydrin resin and the CMC with high substitution degree in the spinning forming and post-treatment processes, the influence caused by loss of modified substances in the spinning forming and post-treatment processes is avoided, and the subsequent crosslinking effect in the fiber is ensured.
3. The high-strength cellulose fiber not only has a series of advantages of the cellulose fiber, but also has the added modified polyamide epichlorohydrin resin, CMC and cellulose matrix existing in the form of interpenetrating copolymer network, and the modified substance is used as an organic matter, so that the compatibility with the polymer matrix can be improved, and the phenomenon of phase separation is avoided. Therefore, the wet strength and modulus of the fiber are remarkably improved compared with those of common cellulose fibers, the dry breaking strength of the prepared fiber is 2.77-3.05 cN/dtex, the wet breaking strength is 1.69-1.95 cN/dtex, the wet modulus is 0.40-0.65 cN/dtex, the elongation at break is 15.1-18.3%, the fiber shrinkage is 1.1-1.6%, and the fuzzing and pilling grade of the prepared fabric is 4-5, so that the fiber has good mechanical properties and textile processability.
4. The preparation method provided by the invention has a simple process, can be completed on the basis of the existing cellulose fiber production process and equipment, and the strength and modulus of the prepared fiber are greatly improved compared with those of common cellulose fibers, so that a new thought and method are provided for the functional development of regenerated cellulose fibers, and the preparation method has a good development prospect.
The present invention will be described in detail with reference to examples.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: a high strength cellulose fiber having a gauge of 1.67dtex 38mm and a method for making the same comprising the steps of:
(1) preparation of viscose stock solution
Cellulose pulp is used as raw material, throughSoaking, squeezing, pulverizing, aging, yellowing, and dissolving to obtain viscose stock solution containing alpha cellulose 8.2%, sodium hydroxide 4.5%, viscosity 45s, and ripening degree 16mL (10% NH)4Cl）。
(2) Preparation of the spinning dope
Adding the prepared modified polyamide epichlorohydrin resin and CMC into the viscose stock solution, mixing, wherein the mass ratio of the modified polyamide epichlorohydrin resin to the CMC to the alpha cellulose in the viscose stock solution is 3.5:1.0:95.5, and fully mixing to obtain the spinning stock solution.
The modification method of the modified polyamide epichlorohydrin resin comprises the following steps:
preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to be 30%, cooling to 90 ℃, adding melamine with the amount of 10% of the amount of the polyamide prepolymer, reacting for 30min, cooling the product to 50 ℃, and adding epichlorohydrin into the system under the condition that the pH value of the system is ensured in the reaction process is 7.5, wherein the amount of the epichlorohydrin is 30% of the amount of the polyamide prepolymer, reacting for 2.0 hours, adjusting the pH value to 5.0 to terminate the reaction to obtain a modified polyamide epichlorohydrin resin solution, and adjusting the pH value of the modified polyamide epichlorohydrin resin solution to be neutral, wherein the solid content is 10%.
The substitution degree of the sodium carboxymethylcellulose (CMC) is 1.0, and the sodium carboxymethylcellulose (CMC) is added into the modified polyamide epichlorohydrin resin solution prepared in the using process.
(3) Spinning formation
The spinning forming process contains 1.5 percent of modified polyamide epichlorohydrin resin besides 7.5 percent of sulfuric acid, 1.2 percent of zinc sulfate and 22.5 percent of sodium sulfate;
the two-bath composition contained 3.0% of a modified polyamide epichlorohydrin resin in addition to 10g/L of sulfuric acid.
(4) Post-treatment
The post-treatment process adopts sodium hydroxide with the concentration of 4.0g/L for the desulfurization bath. The oil bath in the post-treatment process contains 3.0g/L of oil agent, 1.0 percent of modified polyamide epichlorohydrin resin and 1.0 percent of CMC.
(5) Drying by baking
The drying temperature is 140 ℃, and the drying time is 30min, so that the wet strength agent is ensured to be crosslinked.
The high-strength cellulose fiber prepared by the process contains 3.25% of modified polyamide epichlorohydrin resin, 0.89% of CMC, 2.77cN/dtex of dry breaking strength, 1.69cN/dtex of wet breaking strength, 0.4cN/dtex of wet modulus, 18.3% of elongation at break and 1.6% of fiber shrinkage, and the pilling grade of the prepared fabric is 4.
Example 2: a high strength cellulose fiber having a gauge of 1.67dtex 38mm and a method for making the same comprising the steps of:
(1) preparation of viscose stock solution
Cellulose pulp is used as a raw material, and is subjected to the steps of dipping, squeezing, crushing, ageing, yellowing and dissolving to prepare a viscose stock solution, wherein the alpha cellulose accounts for 8.35 percent, the sodium hydroxide accounts for 4.68 percent, the viscosity is 48s, and the maturity is 18.6mL (10 percent NH)4Cl）。
(2) Preparation of the spinning dope
Adding the prepared modified polyamide epichlorohydrin resin and CMC into the viscose stock solution, mixing, wherein the mass ratio of the modified polyamide epichlorohydrin resin to the CMC to the alpha cellulose in the viscose stock solution is 4.2:1.6:94.2, and fully mixing to obtain the spinning stock solution.
The preparation and modification method of the modified polyamide epichlorohydrin resin comprises the following steps: preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to 36%, cooling to 96 ℃, adding melamine with the amount of 15.6% of the amount of the polyamide prepolymer, reacting for 44min, cooling the product to 58 ℃, adding epichlorohydrin into the system under the condition that the pH value of the system is ensured in the reaction process is 8.0, adjusting the pH value to 4.5 after reacting for 2.5 hours, so that a modified polyamide epichlorohydrin resin solution is obtained after the reaction is terminated, and adjusting the pH value of the modified polyamide epichlorohydrin resin solution to be neutral, wherein the solid content is 12.5%.
The substitution degree of the sodium carboxymethylcellulose (CMC) is 1.1, and the sodium carboxymethylcellulose (CMC) is added into the modified polyamide epichlorohydrin resin solution prepared in the using process.
(3) Spinning formation
The spinning forming process contains 1.3 percent of modified polyamide epichlorohydrin resin besides 7.8 percent of sulfuric acid, 1.31 percent of zinc sulfate and 23.6 percent of sodium sulfate. The two-bath composition contained 2.5% of a modified polyamide epichlorohydrin resin in addition to 12.5g/L of sulfuric acid.
(4) Post-treatment
The post-treatment process adopts sodium hydroxide with the concentration of 4.9g/L for the desulfurization bath. The oil bath in the post-treatment process contains 0.72 percent of modified polyamide epichlorohydrin resin and 0.81 percent of CMC besides 3.8g/L of oil agent.
(5) Drying by baking
The drying temperature is 135 ℃, and the drying time is 45min, so that the wet strength agent is ensured to be crosslinked.
The high-strength cellulose fiber prepared by the process contains 3.91 percent of modified polyamide epichlorohydrin resin, 1.48 percent of CMC, 2.82cN/dtex of dry breaking strength, 1.75cN/dtex of wet breaking strength, 0.47cN/dtex of wet modulus, 17.2 percent of elongation at break and 1.5 percent of fiber shrinkage, and the manufactured fabric has a fuzzing and pilling grade of 4.
Example 3: a high strength cellulose fiber having a gauge of 1.56dtex 38mm and a method for making the same comprising the steps of:
(1) preparation of viscose stock solution
Cellulose pulp is used as a raw material, and is subjected to the steps of dipping, squeezing, crushing, ageing, yellowing and dissolving to prepare a viscose stock solution, wherein the alpha cellulose accounts for 8.67 percent, the sodium hydroxide accounts for 4.83 percent, the viscosity is 51s, and the maturity is 19.8mL (10 percent NH)4Cl）。
(2) Preparation of the spinning dope
Adding the prepared modified polyamide epichlorohydrin resin and CMC into the viscose stock solution through injection before spinning, wherein the mass ratio of the modified polyamide epichlorohydrin resin to the CMC to the alpha cellulose in the viscose stock solution is 5.1:1.9:93.0, and fully mixing to obtain the spinning stock solution.
The preparation and modification method of the modified polyamide epichlorohydrin resin comprises the following steps: preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to be 41%, cooling to 105 ℃, adding benzoguanamine with the dosage of 21.7% of the polyamide prepolymer, after reacting for 58min, cooling the product to 66.5 ℃, adding epichlorohydrin into the system under the condition that the pH value of the system is ensured in the reaction process is 8.5, adjusting the pH value to be 3.5 after reacting for 3.0 hours, stopping the reaction to obtain a modified polyamide epichlorohydrin resin solution, and adjusting the pH value of the modified polyamide epichlorohydrin resin to be neutral, wherein the solid content is 13.0%.
The substitution degree of the sodium carboxymethylcellulose (CMC) is 1.2, and the sodium carboxymethylcellulose (CMC) is added into the modified polyamide epichlorohydrin resin solution prepared in the using process.
(3) Spinning formation
The spinning forming process contains 1.0 percent of modified polyamide epichlorohydrin resin besides 8.05 percent of sulfuric acid, 1.39 percent of zinc sulfate and 24.3 percent of sodium sulfate. The two-bath composition contained 2.0% of a modified polyamide epichlorohydrin resin in addition to 15.2g/L of sulfuric acid.
(4) Post-treatment
The oil bath in the post-treatment process contains 0.63 percent of modified polyamide epichlorohydrin resin and 0.65 percent of CMC besides 4.5g/L of oil agent. The post-treatment process adopts sodium hydroxide with the concentration of 6.1g/L for the desulfurization bath.
(5) Drying by baking
The drying temperature is 131 ℃, and the drying time is 65min, so that the wet strength agent is ensured to be crosslinked.
The high-strength cellulose fiber prepared by the process contains 4.82% of modified polyamide epichlorohydrin resin, 1.69% of CMC, 2.90cN/dtex of dry breaking strength, 1.81cN/dtex of wet breaking strength, 0.53cN/dtex of wet modulus, 16.6% of elongation at break and 1.4% of fiber shrinkage, and the pilling grade of the prepared fabric is 4.
Example 4: a high strength cellulose fiber having a gauge of 1.33dtex 38mm and a method for making the same comprising the steps of:
(1) preparation of viscose stock solution
Cellulose pulp is used as a raw material, and is subjected to the steps of dipping, squeezing, crushing, ageing, yellowing and dissolving to prepare a viscose stock solution, wherein the alpha cellulose accounts for 8.81 percent, the sodium hydroxide accounts for 4.93 percent, the viscosity is 53s, and the maturity is 20.5mL (10 percent NH)4Cl）。
(2) Preparation of the spinning dope
Adding the prepared modified polyamide epichlorohydrin resin and CMC into a viscose stock solution by a pre-spinning injection process, wherein the mass ratio of the modified polyamide epichlorohydrin resin to the CMC to alpha cellulose in the viscose stock solution is 6.2:2.2:91.6, and fully mixing to obtain a spinning stock solution.
The preparation and modification method of the modified polyamide epichlorohydrin resin comprises the following steps: preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to be 46%, cooling to 113 ℃, adding melamine with the amount of 25.3% of that of the polyamide prepolymer, reacting for 75min, cooling the product to 73 ℃, adding epoxy chloropropane with the amount of 47% of that of the polyamide prepolymer to the system under the condition of pH value of 9.0, reacting for 3.5 hours, adjusting the pH value to 2.5 to terminate the reaction to obtain a modified polyamide epoxy chloropropane resin solution, and adjusting the pH value of the modified polyamide epoxy chloropropane resin solution to be neutral, wherein the solid content is 14%.
The substitution degree of the sodium carboxymethylcellulose (CMC) is 1.3, and the sodium carboxymethylcellulose (CMC) is added into the modified polyamide epichlorohydrin resin solution prepared in the using process.
(3) Spinning formation
The spinning forming process contains 0.8 percent of modified polyamide epichlorohydrin resin besides 8.38 percent of sulfuric acid, 1.51 percent of zinc sulfate and 25.2 percent of sodium sulfate. The two-bath composition contained 1.5% of a modified polyamide epichlorohydrin resin in addition to 17.8g/L of sulfuric acid.
(4) Post-treatment
The post-treatment process adopts sodium hydroxide with the concentration of 7.5g/L for the desulfurization bath. The oil bath in the post-treatment process contains 0.58 percent of modified polyamide epichlorohydrin resin and 0.62 percent of CMC besides 5.6g/L of oil agent.
(5) Drying by baking
The drying temperature used was 128 ℃ and the drying time 81min to ensure crosslinking of the wet strength agent.
The high-strength cellulose fiber prepared by the process contains 5.91 percent of modified polyamide epichlorohydrin resin, 2.02 percent of CMC, 2.96cN/dtex of dry breaking strength, 1.87cN/dtex of wet breaking strength, 0.59cN/dtex of wet modulus, 15.9 percent of elongation at break and 1.3 percent of fiber shrinkage, and the pilling grade of the prepared fabric is 5.
Example 5: a high strength cellulose fiber having a gauge of 1.33dtex 38mm and a method for making the same comprising the steps of:
(1) preparation of viscose stock solution
Cellulose pulp is used as a raw material, and is subjected to the steps of dipping, squeezing, crushing, ageing, yellowing and dissolving to prepare a viscose stock solution, wherein 9.0 percent of alpha cellulose, 5.1 percent of sodium hydroxide, 55s of viscosity and 22mL (10 percent of NH) of maturity4Cl）。
(2) Preparation of the spinning dope
Adding the prepared modified polyamide epichlorohydrin resin and CMC into the viscose stock solution, mixing, wherein the mass ratio of the modified polyamide epichlorohydrin resin to the CMC to the alpha cellulose in the viscose stock solution is 7.0:2.5:90.5, and fully mixing to obtain the spinning stock solution.
The preparation and modification method of the modified polyamide epichlorohydrin resin comprises the following steps: preparing an intermediate polyamide prepolymer solution according to known knowledge, adjusting the solid content of the polyamide prepolymer to be 50%, cooling to 120 ℃, adding benzoguanamine with the dosage of 30% of the polyamide prepolymer, reacting for 90min, cooling the product to 80 ℃, adding epoxy chloropropane with the dosage of 50% of the polyamide prepolymer to the system under the condition of pH. value of 9.5, reacting for 4.0 h, adjusting the pH value to 2.0 to terminate the reaction to obtain the modified polyamide epoxy chloropropane resin, and adjusting the pH value of the modified polyamide epoxy chloropropane resin solution to be neutral, wherein the solid content is 15%.
The substitution degree of the sodium carboxymethylcellulose (CMC) is 1.5, and the sodium carboxymethylcellulose (CMC) is added into the modified polyamide epichlorohydrin resin solution prepared in the using process.
(3) Spinning formation
The spinning forming process contains 0.5 percent of modified polyamide epichlorohydrin resin besides 8.5 percent of sulfuric acid, 1.6 percent of zinc sulfate and 26.0 percent of sodium sulfate. The two-bath composition contained 1.0% of a modified polyamide epichlorohydrin resin in addition to 20g/L of sulfuric acid.
(4) Post-treatment
The post-treatment process adopts sodium hydroxide with the concentration of 8.0g/L for the desulfurization bath. The oil bath in the post-treatment process contains 0.5 percent of modified polyamide epichlorohydrin resin and 0.5 percent of CMC besides 6.0g/L of oil agent.
(5) Drying by baking
The drying temperature is 125 ℃, and the drying time is 90min, so that the wet strength agent is ensured to be crosslinked.
The high-strength cellulose fiber prepared by the process has the modified polyamide epichlorohydrin resin content of 6.67 percent, the CMC content of 2.26 percent, the dry breaking strength of 3.05cN/dtex, the wet breaking strength of 1.95cN/dtex, the wet modulus of 0.65cN/dtex, the elongation at break of 15.1 percent and the fiber shrinkage of 1.1 percent, and the pilling grade of the prepared fabric is 5 grade.
Comparative example 1
On the basis of example 5, modified polyamide epichlorohydrin resin and CMC are not added in the whole production process, modified polyamide epichlorohydrin resin or CMC is not contained in the coagulating bath, the two baths and the oil bath, and the prepared conventional cellulose fiber with the same specification has the dry breaking strength of 2.45cN/dtex, the wet breaking strength of 1.33cN/dtex, the wet modulus of 0.26cN/dtex, the elongation at break of 19.1 percent and the fiber shrinkage of 2.9 percent, and the pilling grade of the made fabric is 2 grade. Therefore, the physical and mechanical properties, the dimensional stability and the fluffing and pilling grade of the made fabrics of the cellulose fibers can be obviously improved by utilizing the technology.
Comparative example 2
On the basis of example 5, only modified polyamide epichlorohydrin resin (the mass ratio of the modified polyamide epichlorohydrin resin to the methylcellulose in the viscose stoste is 7.0: 93.0), and after fully mixing, a spinning stoste is obtained, a spinning forming process contains 0.5 percent of the modified polyamide epichlorohydrin resin besides 8.5 percent of sulfuric acid, 1.6 percent of zinc sulfate and 26.0 percent of sodium sulfate, a two-bath composition also contains 1.0 percent of the modified polyamide epichlorohydrin resin besides 20g/L of sulfuric acid, a post-treatment process desulfurization bath adopts sodium hydroxide, the concentration is 8.0g/L, an oil bath in the post-treatment process contains 0.5 percent of the modified polyamide epichlorohydrin resin besides 6.0g/L of an oil agent, and other processes are the same as in example 5), and the dry breaking strength of the prepared conventional cellulose fiber with the same specification is 2.92cN/dtex, the wet breaking strength is 1.83cN/dtex, the wet modulus is 0.56cN/dtex, the elongation at break is 11.3%, the fiber shrinkage is 1.2%, and the finished fabric has a 4-grade fluff and pilling grade. Therefore, the physical and mechanical properties, the dimensional stability and the fluffing and pilling grade of the made fabrics of the cellulose fibers can be obviously improved by utilizing the technology.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still make modifications to the technical solutions described in the foregoing embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method of increasing the strength of cellulosic fibers, characterized by: the method comprises preparing a spinning dope; the preparation of the spinning stock solution comprises the step of blending the modified polyamide epichlorohydrin resin, the CMC and the viscose stock solution.
2. A method of increasing the strength of cellulosic fibers according to claim 1, wherein: the mass ratio of the modified polyamide epichlorohydrin resin, the CMC and the alpha cellulose in the viscose stock solution is 3.5-7.0:1.0-2.5: 90.5-95.5.
3. A method of increasing the strength of cellulosic fibers according to claim 1, wherein: the method also comprises spinning and forming; and spinning and forming, wherein the coagulating bath comprises 0.5-1.5% of modified polyamide epichlorohydrin resin, and the second bath comprises 1.0-3.0% of modified polyamide epichlorohydrin resin.
4. A method of increasing the strength of cellulosic fibers according to claim 1, wherein: the method also comprises post-treatment, wherein the post-treatment comprises 0.5-1.0% of modified polyamide epichlorohydrin resin and 0.5-1.0% of CMC in an oil bath.
5. A method of increasing the strength of cellulosic fibers according to any of claims 1, 2 or 4, wherein: the degree of substitution of the CMC is 1.0 to 1.5.
6. A method of increasing the strength of cellulosic fibres, as claimed in any one of claims 1 to 4, in which: the modification method of the modified polyamide epichlorohydrin resin comprises the steps of adjusting the solid content of a polyamide prepolymer in a polyamide prepolymer solution to be 30% -50%, cooling to 90-120 ℃, adding melamine or benzoguanamine, wherein the amount of the melamine or benzoguanamine is 10% -30% of that of the polyamide prepolymer, reacting for 30-90min, cooling the product to 50-80 ℃, adding epichlorohydrin under the condition that the pH value is 7.5-9.5, the amount of the epichlorohydrin is 30% -50% of that of the polyamide prepolymer, reacting for 2.0-4.0 hours, adjusting the pH value to be 2.0-5.0, stopping the reaction, adjusting the pH value to be neutral, and enabling the solid content to be 10% -15%, thus obtaining the modified polyamide epichlorohydrin resin solution.
7. A method of increasing the strength of cellulosic fibers according to claim 1, wherein: the viscose stock solution comprises 8.2-9.0% of alpha cellulose, 4.5-5.1% of sodium hydroxide, 45-55 s of viscosity and 10% of NH4The aging degree under Cl is 16-22 mL.
8. A method of increasing the strength of cellulosic fibers according to claim 3, wherein: the coagulating bath also comprises 7.5-8.5% of sulfuric acid, 1.2-1.6% of zinc sulfate and 22.5-26.0% of sodium sulfate; the two baths also comprise 10-20 g/L sulfuric acid.
9. A method of increasing the strength of cellulosic fibers according to claim 4, wherein:
in the post-treatment, sodium hydroxide is adopted in a desulfurization bath, and the concentration is 4.0-8.0 g/L; the upper oil bath also comprises 3.0-6.0 g/L of oil solution; the method further comprises drying, wherein the drying temperature is 125-140 ℃, and the drying time is 30-90 min.
10. The cellulosic fiber produced by the method of increasing the strength of cellulosic fiber of claim 1, wherein: the fiber contains 3.25 to 6.67 percent of modified polyamide epichlorohydrin resin and 0.89 to 2.26 percent of CMC; the dry breaking strength is 2.77-3.05 cN/dtex, the fiber shrinkage is 1.1-1.6%, and the fuzzing and pilling grade of the made fabric is 4-5.
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