CN116926715B - Preparation process of semi-degradable fiber - Google Patents
Preparation process of semi-degradable fiber Download PDFInfo
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- CN116926715B CN116926715B CN202310711422.9A CN202310711422A CN116926715B CN 116926715 B CN116926715 B CN 116926715B CN 202310711422 A CN202310711422 A CN 202310711422A CN 116926715 B CN116926715 B CN 116926715B
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- 239000000835 fiber Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 89
- 239000012792 core layer Substances 0.000 claims abstract description 55
- 239000002344 surface layer Substances 0.000 claims abstract description 51
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000004970 Chain extender Substances 0.000 claims description 31
- 239000003431 cross linking reagent Substances 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 21
- 229920001661 Chitosan Polymers 0.000 claims description 21
- 235000010413 sodium alginate Nutrition 0.000 claims description 21
- 229940005550 sodium alginate Drugs 0.000 claims description 21
- 239000000661 sodium alginate Substances 0.000 claims description 21
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 20
- 229920000742 Cotton Polymers 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001896 polybutyrate Polymers 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention discloses a preparation process of semi-degradable fiber, which relates to the technical field of fiber yarn preparation, and the prepared semi-degradable fiber comprises a core layer non-degradable polymer and a surface layer degradable polymer coated on a surface layer of the core layer non-degradable polymer, wherein an interpenetrating network polymer layer for increasing compatibility of the core layer non-degradable polymer and the surface layer degradable polymer is arranged between the core layer non-degradable polymer and the surface layer degradable polymer. According to the semi-degradable fiber, the non-degradable polymer of the core layer and the degradable polymer of the surface layer are bonded through the interpenetrating network polymer layer, so that the compatibility between the non-degradable polymer of the core layer and the degradable polymer of the surface layer is improved, and the toughness of the semi-degradable fiber is improved.
Description
Technical Field
The invention belongs to the technical field of fiber yarn preparation, and particularly relates to a preparation process of semi-degradable fibers.
Background
At present, most of fiber yarns are prepared by compounding non-degradable single materials such as Polyester (PET), polypropylene (PP) and the like, and the compounding method is to tightly bond the inside of the fiber yarns to form the fiber yarns with certain elasticity by a fiber yarn glue bonding or hot melting mode.
The above-mentioned filaments have the following disadvantages:
(1) The material has no degradation function and cannot meet the existing environmental protection requirements;
(2) If two polymers are adopted for compounding to prepare the fiber yarn, the performance of the polymers is different, the compatibility is poor, and the toughness of the fiber yarn is low.
Disclosure of Invention
The invention aims to provide a preparation process of semi-degradable fiber, which aims to solve the problems that the fiber yarn does not have degradability and the compatibility between two polymer materials is poor.
To achieve the above object, according to a first aspect of the present invention, there is provided a semi-degradable fiber, the semi-degradable fiber comprising a core non-degradable polymer and a surface layer degradable polymer coated on a surface layer of the core non-degradable polymer, wherein an interpenetrating network polymer layer for increasing compatibility between the core non-degradable polymer and the surface layer degradable polymer is disposed between the core non-degradable polymer and the surface layer degradable polymer.
In the prior art, most of the fibers are fibers prepared from non-degradable polymer materials or fibers prepared from polymer materials with similar properties, and the fibers are formed by melting or bonding single components or components with similar properties, so that the bonding effect is good, but the properties of two materials of the core non-degradable polymer and the surface degradable polymer in the invention are greatly different, the polymers are directly bonded in a melting way, the interface bonding effect is poor, and the toughness of the fibers formed by compounding the polymers is poor.
Preferably, the core non-degradable polymer comprises one or more of PP, PE, PET, PA.
Preferably, the skin degradable polymer comprises one or more of PBS, PBAT, PHA, PHB, PES, PHA, PBT, PLA, PPC, PHV, PHBV, PCL, PBSA, PVA.
Preferably, the core layer non-degradable polymer has a melting point higher than the melting point of the skin layer degradable polymer.
Preferably, the interpenetrating network polymer layer is formed by polymerization reaction of a first crosslinking system, a second crosslinking system, a chain extender and a crosslinking agent under the condition of an initiator and a catalyst.
Preferably, the semi-degradable fiber filaments have a titer in the range of 3D-12D.
Preferably, the semi-degradable fiber filaments may be long fibers or short fibers.
The second aspect of the invention provides a process for preparing a semi-degradable fiber, comprising the steps of:
(1) Preparation of core non-degradable polymers
Selecting a core layer non-degradable polymer according to the requirement, reacting in a melting box, removing slag, neutralizing acid and alkali, crystallizing and drying at 100 ℃ for 12 hours, and extruding into a core layer channel containing a spray cavity after drying by melting and extruding, wherein the core layer non-degradable polymer is sprayed out of the spray cavity to form a core layer single fiber;
(2) Preparation of surface degradable Polymer
Selecting a surface layer degradable polymer according to the requirement, and vacuum drying in a melting box, wherein melt is sprayed out through a spray cavity to form surface layer single fibers;
(3) Immersing the core layer single fiber into a mixture of a first crosslinking system, a second crosslinking system, a chain extender and a crosslinking agent to form a network matrix, immersing the surface layer single fiber into a mixture of an initiator and a catalyst to form a network excitation body, mixing and compounding the network matrix and the network excitation body at a spinneret plate to form fiber filaments, cooling the fiber filaments, drawing the fiber filaments by a drawing machine, and adding the fiber filaments by an elasticizer to obtain the semi-degradable fiber.
Preferably, the core layer non-degradable polymer accounts for 50-70% of the total weight of the semi-degradable fiber, the surface layer degradable polymer accounts for 25-40% of the total weight of the semi-degradable fiber, and the interpenetrating network polymer layer accounts for 5-10% of the total weight of the semi-degradable fiber.
Preferably, the interpenetrating network polymer layer comprises, by weight, 80-120 parts of a first crosslinking system, 80-120 parts of a second crosslinking system, 10-15 parts of a chain extender, 15-20 parts of a crosslinking agent, 2-5 parts of an initiator and 1-5 parts of a catalyst.
Preferably, the first crosslinking system is sodium alginate; the second crosslinking system is carboxymethyl chitosan; the chain extender is one or more of styrene, methacrylic acid, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; the cross-linking agent is one or two of glutaraldehyde and N, N-methylene bisacrylamide; the initiator is one or more of benzoyl peroxide, tert-butyl peroxybenzoate and methyl ethyl ketone peroxide; the catalyst is one of an organotin catalyst and an organic amine catalyst.
Preferably, the organotin catalyst is one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, dibutyltin dilaurate or dibutyltin diacetate.
Preferably, the organic amine catalyst is one of triethylamine, p-dimethylaminopyridine, N-dimethylethanolamine, N-dimethylformamide and triethylenediamine.
Wherein sodium alginate is a linear polysaccharide extracted from natural seaweed, and is composed of two components of beta-D-mannuronic acid and alpha-L-guluronic acid, and alginate prepared from sodium alginate has excellent hygroscopicity, biocompatibility and degradability. Carboxymethyl chitosan is a novel chitosan derivative and has good water solubility, biocompatibility and degradability. The interpenetrating network structure can be formed by segment interweaving, functional group electrostatic adsorption and partial chemical reaction between the sodium alginate and the carboxymethyl chitosan, but the crosslinking degree of the interpenetrating network structure is low, so that the cohesiveness between the core layer non-degradable polymer and the surface layer degradable polymer is not high enough. But both belong to degradable substances, which can reduce environmental pollution.
In order to further increase the cohesiveness between the core layer nondegradable polymer and the surface layer degradable polymer, a chain extender, a cross-linking agent, an initiator and a catalyst are also added, wherein the surface of the core layer single fiber is adhered with the chain extender and the cross-linking agent, the chain extender and the cross-linking agent are easily adhered to the core layer single fiber on the basis that the sodium alginate and the carboxymethyl chitosan form a part of interpenetrating network structure, the surface layer single fiber is adhered with the initiator and the catalyst, and when the core layer single fiber adhered with the chain extender and the cross-linking agent and the surface layer single fiber adhered with the initiator and the catalyst are compounded, the chain extender and the cross-linking agent rapidly perform further polymerization reaction under the action of the initiator and the catalyst to form a complete interpenetrating network structure with higher density, so that the compatibility and the cohesiveness between the core layer single fiber and the surface layer single fiber are improved, and the toughness of the semi-degradable fiber is improved.
The chain extender is a molecular chain extender containing polar groups, and the purpose of increasing the polarity of the polymer can be achieved by introducing the chain extender with the polar groups in the polymerization process of the chain extender, the cross-linking agent, the catalyst and the initiator, so that the compatibility between the polymer blends is improved, and the cohesiveness between the core layer single fiber and the surface layer single fiber is further increased.
The third aspect of the invention provides application of semi-degradable fibers in preparation of absorbent cotton, oil storage cotton, filter cotton, fiber nibs, absorbent sticks and filter sticks.
It should be noted that the practical application of the present invention is not limited to the above applications, and the semi-degradable fiber prepared by the present invention can be used in daily use, electronic and medical fields.
Therefore, the preparation process of the semi-degradable fiber adopting the structure has the following beneficial effects:
(1) The non-degradable polymer of the core layer and the degradable polymer of the surface layer are bonded through the interpenetrating network polymer layer, so that the compatibility between the non-degradable polymer of the core layer and the degradable polymer of the surface layer is improved, and the toughness of the semi-degradable fiber is improved.
(2) The interpenetrating network polymer is formed by two steps, wherein the first step is to form a preliminary interpenetrating network polymer between sodium alginate and carboxymethyl chitosan, the second step is to further crosslink and polymerize a chain extender and a crosslinking agent under the action of a catalyst and an initiator to form a complete interpenetrating network polymer, and the formed interpenetrating network polymer has higher polymerization degree and can bond a core layer single fiber and a surface layer single fiber.
(3) Sodium alginate and carboxymethyl chitosan are degradable materials, and meet the requirement of environmental protection.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment provides a detailed implementation manner and a specific operation procedure on the premise of the present technical solution, but the present invention is not limited to the present embodiment.
Example 1
The prepared semi-degradable fiber comprises a core layer non-degradable polymer and a surface layer degradable polymer coated on the surface layer of the core layer non-degradable polymer, wherein an interpenetrating network polymer layer for increasing the compatibility of the core layer non-degradable polymer and the surface layer degradable polymer is arranged between the core layer non-degradable polymer and the surface layer degradable polymer. Wherein the non-degradable polymer of the core layer is PA, and the degradable polymer of the surface layer is PLA. The melting point of PA is 230 degrees celsius and the melting point of PLA is 175 degrees celsius.
A process for preparing a semi-degradable fiber comprising the steps of:
(1) Preparation of core non-degradable polymers
Selecting a core layer non-degradable polymer according to the requirement, reacting in a melting box, removing slag, neutralizing acid and alkali, crystallizing and drying at 100 ℃ for 12 hours, and extruding into a core layer channel containing a spray cavity after drying by melting and extruding, wherein the core layer non-degradable polymer is sprayed out of the spray cavity to form a core layer single fiber; wherein the core non-degradable polymer comprises 60% of the total weight of the semi-degradable fiber;
(2) Preparation of surface degradable Polymer
Selecting a surface layer degradable polymer according to the requirement, and vacuum drying in a melting box, wherein melt is sprayed out through a spray cavity to form surface layer single fibers; wherein the surface layer degradable polymer accounts for 35% of the total weight of the semi-degradable fiber;
(3) Immersing the core layer single fiber into a mixture of a first crosslinking system, a second crosslinking system, a chain extender and a crosslinking agent to form a network matrix, immersing the surface layer single fiber into a mixture of an initiator and a catalyst to form a network excitation body, mixing and compounding the network matrix and the network excitation body at a spinneret plate to form fiber filaments, cooling the fiber filaments, drawing the fiber filaments by a drawing machine, and adding the fiber filaments by an elasticizer to obtain semi-degradable fibers;
wherein the interpenetrating network polymer layer accounts for 5 percent of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer comprises 80 parts of a first crosslinking system, 120 parts of a second crosslinking system, 10 parts of a chain extender, 15 parts of a crosslinking agent, 3 parts of an initiator and 2 parts of a catalyst according to parts by weight; the first crosslinking system is sodium alginate; the second crosslinking system is carboxymethyl chitosan; the chain extender is methacrylic acid; the cross-linking agent is glutaraldehyde; the initiator is benzoyl peroxide; the catalyst is dibutyl tin dilaurate.
Example 2
The structure of the semi-degradable fiber prepared was the same as in example 1, except that: wherein the core layer non-degradable polymer is PET, and the surface layer degradable polymer is PES. The melting point of PET is 250 degrees Celsius and the melting point of PES is 200 degrees Celsius.
The semi-degradable fiber was prepared in the same manner as in example 1 except that: wherein the core layer non-degradable polymer accounts for 50% of the total weight of the semi-degradable fiber, and the surface layer degradable polymer accounts for 40% of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer accounts for 10 percent of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer comprises 100 parts by weight of a first crosslinking system, 100 parts by weight of a second crosslinking system, 15 parts by weight of a chain extender, 20 parts by weight of a crosslinking agent, 4 parts by weight of an initiator and 3 parts by weight of a catalyst; the first crosslinking system is sodium alginate; the second crosslinking system is carboxymethyl chitosan; the chain extender is ethyl acrylate; the cross-linking agent is N, N-methylene bisacrylamide; the initiator is tert-butyl peroxybenzoate; the catalyst is p-dimethylaminopyridine.
Example 3
The structure of the semi-degradable fiber prepared was the same as in example 1, except that: wherein the core layer non-degradable polymer is PA and the surface layer degradable polymer is PBAT. The melting point of PA is 220 degrees celsius and the melting point of PBAT is 180 degrees celsius.
The semi-degradable fiber was prepared in the same manner as in example 1 except that: wherein the core layer non-degradable polymer accounts for 70% of the total weight of the semi-degradable fiber, and the surface layer degradable polymer accounts for 25% of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer accounts for 5 percent of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer comprises 90 parts of a first crosslinking system, 110 parts of a second crosslinking system, 15 parts of a chain extender, 18 parts of a crosslinking agent, 3 parts of an initiator and 2 parts of a catalyst according to parts by weight; the first crosslinking system is sodium alginate; the second crosslinking system is carboxymethyl chitosan; the chain extender is 2-methyl methacrylate; the cross-linking agent is glutaraldehyde; the initiator is methyl ethyl ketone peroxide; the catalyst is stannous oxalate.
Example 4
The structure of the prepared semi-degradable fiber is the same as in example 1, except that: wherein the non-degradable polymer of the core layer is PE, and the degradable polymer of the surface layer is PHB. The melting point of PE is 230 ℃ and the melting point of PHB is 180 ℃.
The semi-degradable fiber was prepared in the same manner as in example 1 except that: wherein the core layer non-degradable polymer accounts for 65% of the total weight of the semi-degradable fiber, and the surface layer degradable polymer accounts for 27% of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer accounts for 8 percent of the total weight of the semi-degradable fiber; the interpenetrating network polymer layer comprises 110 parts of a first crosslinking system, 100 parts of a second crosslinking system, 11 parts of a chain extender, 12 parts of a crosslinking agent, 3 parts of an initiator and 3 parts of a catalyst according to parts by weight; the first crosslinking system is sodium alginate; the second crosslinking system is carboxymethyl chitosan; the chain extender is 2-ethyl methacrylate; the cross-linking agent is N, N-methylene bisacrylamide; the initiator is methyl ethyl ketone peroxide; the catalyst is N, N-dimethylethanolamine.
Comparative example 1
Comparative example 1 differs from example 1 in that: sodium alginate was not added.
Comparative example 2
Comparative example 2 is different from example 1 in that: no carboxymethyl chitosan was added.
Comparative example 3
Comparative example 3 is different from example 1 in that: sodium alginate and carboxymethyl chitosan were not added.
Comparative example 4
Comparative example 4 differs from example 1 in that: no chain extender, crosslinking agent, catalyst and initiator are added.
Comparative example 5
Comparative example 5 is different from example 1 in that: sodium alginate, carboxymethyl chitosan, a chain extender, a cross-linking agent, a catalyst and an initiator are not added, and the core layer single fiber and the surface layer single fiber are directly compounded.
The semi-degradable fibers were subjected to fiber mechanical property testing according to the method specified in GB/T19975-2005 under the following conditions: the nip was 500mm and the speed was 250mm/min. The test results are shown in Table 1.
As can be seen from table 1, when the core single fiber and the surface single fiber are directly compounded in comparative example 5, the toughness of the formed semi-degradable fiber is lower, because the property difference between the core single fiber and the surface single fiber is larger in the stretching process, the compatibility is poorer, and the core single fiber and the surface single fiber are easily separated under the same stretching effect, so that the toughness is reduced. Examples 1-4 an interpenetrating network polymerized layer was formed between the core and skin filaments by polymerization, which increased the cohesiveness and compatibility between the core and skin filaments, and thus increased the toughness of the semi-degraded fibers. The sodium alginate and the carboxymethyl chitosan are not added in the comparative example 1 and the comparative example 2 respectively, the sodium alginate and the carboxymethyl chitosan cannot be utilized to form an initial interpenetrating network structure on the surface of the single fiber of the core layer at the initial stage, the complete interpenetrating network polymer formed by the polymerization reaction of the surface single fiber adhered with the catalyst and the initiator at the later stage is influenced to a certain extent, the cohesiveness of the interpenetrating network polymer is lowered, and the toughness of the semi-degradable fibers prepared in the comparative example 1 and the comparative example 2 is lowered compared with that of the examples. In comparative example 3, sodium alginate and carboxymethyl chitosan are not added, and only the crosslinking agent and the chain extender adhered to the surface of the core layer single fiber and the catalyst and the initiator adhered to the surface of the surface layer single fiber are subjected to polymerization reaction, so that the compactness and cohesiveness of the formed interpenetrating network polymer are obviously reduced, and the toughness of the semi-degradable fiber prepared in comparative example 3 is reduced. In comparative example 4, no chain extender, cross-linking agent, catalyst and initiator are added, the core layer single fiber and the surface layer single fiber form an initial interpenetrating network structure only through acting force and chemical reaction between sodium alginate and carboxymethyl chitosan, and the chemical reaction between sodium alginate and carboxymethyl chitosan is limited, and not all sodium alginate and carboxymethyl chitosan completely polymerize, so that the cross-linking degree and cohesiveness of the interpenetrating network structure formed at the initial stage are smaller.
The semi-degradable fiber has better toughness, and can be applied to the preparation of absorbent cotton, oil storage cotton, filter cotton, fiber pen points, absorbent rods and filter rods according to the requirement by utilizing the toughness of the semi-degradable fiber, and can be widely applied to the daily use, electronic and medical fields.
Therefore, the preparation process of the semi-degradable fiber adopts the structure, and the non-degradable polymer of the core layer and the degradable polymer of the surface layer are bonded through the interpenetrating network polymer layer, so that the compatibility between the non-degradable polymer of the core layer and the degradable polymer of the surface layer is improved, and the toughness of the semi-degradable fiber is improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (9)
1. The semi-degradable fiber is characterized by comprising a core layer non-degradable polymer and a surface layer degradable polymer coated on a surface layer of the core layer non-degradable polymer, wherein an interpenetrating network polymer layer for increasing the compatibility of the core layer non-degradable polymer and the surface layer degradable polymer is arranged between the core layer non-degradable polymer and the surface layer degradable polymer;
the preparation process of the semi-degradable fiber comprises the following steps:
(1) Preparation of core non-degradable polymers
Selecting a core layer non-degradable polymer according to the requirement, reacting in a melting box, removing slag, neutralizing acid and alkali, crystallizing and drying at 100 ℃ for 12 hours, and extruding into a core layer channel containing a spray cavity after drying by melting and extruding, wherein the core layer non-degradable polymer is sprayed out of the spray cavity to form a core layer single fiber;
(2) Preparation of surface degradable Polymer
Selecting a surface layer degradable polymer according to the requirement, and vacuum drying in a melting box, wherein melt is sprayed out through a spray cavity to form surface layer single fibers;
(3) Immersing the core layer single fiber into a mixture of a first crosslinking system, a second crosslinking system, a chain extender and a crosslinking agent to form a network matrix, immersing the surface layer single fiber into a mixture of an initiator and a catalyst to form a network excitation body, mixing and compounding the network matrix and the network excitation body at a spinneret plate to form fiber filaments, cooling the fiber filaments, drawing the fiber filaments by a drawing machine, and adding the fiber filaments by an elasticizer to obtain semi-degradable fibers;
the first crosslinking system is sodium alginate, the second crosslinking system is carboxymethyl chitosan, and the crosslinking agent is one or two of glutaraldehyde and N, N-methylene bisacrylamide.
2. A semi-degradable fiber according to claim 1, characterized in that the core non-degradable polymer comprises one or several of PP, PE, PET, PA.
3. A semi-degradable fiber according to claim 1, characterized in that the surface degradable polymer comprises one or several of PBS, PBAT, PHB, PES, PHA, PBT, PLA, PPC, PHV, PHBV, PCL, PBSA, PVA.
4. A semi-degradable fiber according to claim 1, characterized in that the melting point of the non-degradable polymer of the core layer is higher than the melting point of the degradable polymer of the surface layer.
5. The semi-degradable fiber of claim 1, wherein the interpenetrating network polymer layer is formed by polymerizing a first crosslinking system, a second crosslinking system, a chain extender, and a crosslinking agent in the presence of an initiator and a catalyst.
6. The semi-degradable fiber of claim 1, wherein the core non-degradable polymer comprises 50-70% of the total weight of the semi-degradable fiber, the skin degradable polymer comprises 25-40% of the total weight of the semi-degradable fiber, and the interpenetrating network polymer layer comprises 5-10% of the total weight of the semi-degradable fiber.
7. The semi-degradable fiber of claim 1, wherein the interpenetrating network polymer layer comprises, by weight, 80-120 parts of a first crosslinking system, 80-120 parts of a second crosslinking system, 10-15 parts of a chain extender, 15-20 parts of a crosslinking agent, 2-5 parts of an initiator, and 1-5 parts of a catalyst.
8. The semi-degradable fiber of claim 7, wherein the chain extender is one or more of styrene, methacrylic acid, ethyl acrylate, 2-methyl methacrylate, and 2-ethyl methacrylate; the initiator is one or more of benzoyl peroxide, tert-butyl peroxybenzoate and methyl ethyl ketone peroxide; the catalyst is one of an organotin catalyst and an organic amine catalyst.
9. The use of a semi-degradable fiber according to claims 1-5, characterized in that the semi-degradable fiber is used for the production of absorbent cotton, oil storage cotton, filter cotton, fiber nibs, absorbent sticks, filter sticks.
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| CN111876848A (en) * | 2020-08-04 | 2020-11-03 | 江苏江南高纤股份有限公司 | Biodegradable polyester composite short fiber and preparation method thereof |
| CN112999402A (en) * | 2021-03-01 | 2021-06-22 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Electrostatic spinning gel fiber membrane and preparation method and application thereof |
| CN114395809A (en) * | 2022-01-24 | 2022-04-26 | 广东鑫球新材料科技有限公司 | Partially degradable composite filament and manufacturing method and application thereof |
| CN116236854A (en) * | 2023-05-11 | 2023-06-09 | 广东鑫球新材料科技有限公司 | Filter element with variable degradation material |
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| CN111876848A (en) * | 2020-08-04 | 2020-11-03 | 江苏江南高纤股份有限公司 | Biodegradable polyester composite short fiber and preparation method thereof |
| CN112999402A (en) * | 2021-03-01 | 2021-06-22 | 中国科学院大学温州研究院(温州生物材料与工程研究所) | Electrostatic spinning gel fiber membrane and preparation method and application thereof |
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