CN110318250B - Silk fibril cracking agent and preparation and use methods thereof - Google Patents
Silk fibril cracking agent and preparation and use methods thereof Download PDFInfo
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- CN110318250B CN110318250B CN201910585814.9A CN201910585814A CN110318250B CN 110318250 B CN110318250 B CN 110318250B CN 201910585814 A CN201910585814 A CN 201910585814A CN 110318250 B CN110318250 B CN 110318250B
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- 238000005336 cracking Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 28
- VLEIUWBSEKKKFX-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid Chemical group OCC(N)(CO)CO.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O VLEIUWBSEKKKFX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 22
- 108010022355 Fibroins Proteins 0.000 claims abstract description 20
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 78
- 238000005406 washing Methods 0.000 claims description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 17
- 239000007983 Tris buffer Substances 0.000 claims description 16
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- 238000012805 post-processing Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
- 235000004443 Ricinus communis Nutrition 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229960000846 camphor Drugs 0.000 claims description 3
- 229930008380 camphor Natural products 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 240000000249 Morus alba Species 0.000 claims description 2
- 235000008708 Morus alba Nutrition 0.000 claims description 2
- 240000000528 Ricinus communis Species 0.000 claims description 2
- 241000124033 Salix Species 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 36
- 229910021641 deionized water Inorganic materials 0.000 description 36
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 241000255789 Bombyx mori Species 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 small molecule compound Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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- 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
- D06M2101/10—Animal fibres
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a silk fibril cracking agent and a preparation and use method thereof. The silk fibril cracking agent consists of a No. 1 reagent and a No. 2 reagent, wherein the No. 1 reagent is a soluble calcium salt/alcohol/water ternary mixed solution, and the No. 2 reagent is a Tris-EDTA solution. And (3) soaking the degummed silk fibroin fibers in a No. 1 reagent at 30-60 ℃ for 1-7 days, and then soaking the degummed silk fibroin fibers in a No. 2 reagent for 0.5-4 h to obtain the silk fibroin fibers with obviously weakened interfibrillary force. The silk fibril cracking agent provided by the invention can obviously improve the cracking and separating efficiency of fibrils and reduce the energy consumption and time required by the separation of the silk micro-nano fibrils.
Description
Technical Field
The invention relates to the technical field of micro-nano materials, in particular to a silk fibril cracking agent and a preparation and use method thereof.
Background
The silk fiber is a natural protein fiber material, and the silk fiber has a remarkable fibril-assembled micro-nano hierarchical structure inside. The assembly of silk fibroin macromolecules forms protofibrils with diameters of tens of nanometers, which are further assembled to form fibrillar structures with dimensions of hundreds of nanometers or even micrometers. The connections between the macromolecular chains of silk fibroin, fibrils and fibrils are mainly hydrogen bonds.
The micro-nano fiber material is widely used for functional materials and devices, and if the natural silk fiber can be efficiently decomposed into the fiber with the micro-nano scale, the additional value of silk resources can be greatly improved.
The silk micro-nano fibrils can be obtained in various ways. At present, microfibrils are obtained mainly by means of mechanical action exerted in chemical agents. However, due to the strong intermolecular forces between the fibrils, the separation is difficult, and the pulverization or refining of the fibers is very energy consuming and inefficient.
In the invention, the invention patent with the publication number of CN109652866A proposes that calcium nitrate/alcohol/water solution is used as an auxiliary agent, and micro-nano fibrils of silk are separated by mechanical action in the solvent. Although calcium ions in the calcium nitrate solution can break hydrogen bonds, the calcium ions are recombined with fibroin macromolecules of fibrils to form a firm structure, which is not beneficial to the loosening and cracking of fibril bundles. Meanwhile, the calcium nitrate/alcohol/water solution needs a long time to destroy the hydrogen bond action, and the calcium nitrate/alcohol/water solution is only used as an auxiliary agent of mechanical action and is difficult to achieve the effect of deeply destroying the hydrogen bond. Before the invention, a preparation method of the silk nanofiber is reported in a patent with the publication number of CN104532365B, degummed silk is soaked in a solution composed of inorganic salt, a small molecular compound of weak acid or weak base, deionized water and alcohol, and then the silk nanofiber with the diameter of 50-150 nm is obtained by mechanical shearing of a crusher. However, the metal ions of the small molecule compound can form firm combination with the silk fibroin macromolecules again. Therefore, the interfibrillar action cannot be completely broken by just the soaking treatment with a solution consisting of small-molecule compound/deionized water/alcohol.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims at providing a silk fibril cracking agent and a preparation and use method thereof, wherein the fibril cracking agent can obviously weaken acting force between fibrils and loosen fibril bundles so as to improve the separation efficiency of the fibrils.
In order to achieve the above purpose of the invention, the invention adopts the following technical scheme:
the first aspect of the invention is a silk fibril cracking agent, which consists of a No. 1 reagent and a No. 2 reagent, wherein the No. 1 reagent is a soluble calcium salt/alcohol/water ternary mixed solution, and the No. 2 reagent is a Tris-EDTA solution.
Preferably, the concentration of the soluble calcium salt in the soluble calcium salt/alcohol/water ternary mixed solution is 1-7 mol/L; the Tris-EDTA solution comprises 1-50 mM Tris and 1-10 mM EDTA.
Preferably, the soluble calcium salt is one or both of calcium nitrate and calcium chloride.
Preferably, the alcohol is one or more of methanol, ethanol, propanol and butanol.
Preferably, the volume ratio of water to alcohol in the ternary mixed solution is 1: 1-5.
The second aspect of the invention is a preparation and use method of a silk fibril cracking agent, comprising the following steps:
s1 preparation solution: preparing a No. 1 reagent soluble calcium salt/alcohol/water ternary mixed solution and a No. 2 reagent Tris-EDTA solution with preset concentrations;
s2 cracking treatment: adding degummed silk fibroin fibers into a soluble calcium salt/alcohol/water ternary mixed solution for carrying out first-step cracking treatment; then, washing the silk fibroin fibers subjected to the cracking treatment in the first step, and then placing the silk fibroin fibers in a Tris-EDTA solution for carrying out cracking treatment in the second step;
and S3 post-processing: and (3) washing and drying the fibers treated by the cracking agent to obtain the silk fibroin fibers with obviously weakened interfibrillary force, and performing fibril separation.
Preferably, the first cracking treatment in step S2 is soaking treatment at 30-60 ℃ for 1-7 days.
Preferably, the second cracking treatment in step S2 is soaking in a Tris-EDTA solution for 0.5-4 hours.
Preferably, the silk includes, but is not limited to, one or more of mulberry silk, tussah silk, camphor silk, castor-oil plant silk or willow silk.
The invention breaks the acting force between the silk fibrils by adopting a two-step processing method of a No. 1 reagent soluble calcium/alcohol/deionized water ternary mixed solution and a No. 2 reagent Tris-EDTA solution. The silk fibers are expanded under the action of ethanol and water in the No. 1 reagent, and calcium ions enter the fibers to break the hydrogen bond between fibroin macromolecules. After calcium ions enter the silk fibers, the calcium ions can be combined with fibroin macromolecules to form firm combination again, and the loosening of fibrils is not facilitated. To completely destroy the force between the fibrils, EDTA and calcium ions form a complex, which is extracted from the fibrils by the treatment with the reagent No. 2 Tris-EDTA solution, thereby further destroying the force between the fibrils. Sufficient time is provided to weaken the forces between the fibrils to achieve the effect of deeply breaking the forces between the fibrils. The solvent of the invention has mild action, can deeply destroy the acting force between fibrils, but can not obviously destroy the structure of the fibrils.
Advantageous effects
1. The invention provides a silk fibril cracking agent, which consists of a No. 1 reagent and a No. 2 reagent, wherein the No. 1 reagent is soluble calcium salt/alcohol/water, the No. 2 reagent is a Tris-EDTA solution, the cracking agent can break intermolecular forces such as hydrogen bonds and the like between silk fibrils, the action of a solvent is mild, the fibril structure cannot be damaged, the cracking and separating efficiency of the fibrils can be obviously improved, and the energy consumption and the time required by the separation of the silk micro-nano fibrils are reduced.
2. The invention provides a silk fibril cracking agent and a preparation and use method thereof, and particularly adopts a soluble calcium/alcohol/deionized water ternary mixed solution and a Tris-EDTA solution to carry out two-step cracking treatment on silk fibers, so as to provide sufficient time for weakening acting force between fibrils, thereby achieving the effect of deeply destroying hydrogen bonds between fibrils, further remarkably improving the separation efficiency of the fibrils and overcoming the defects of the prior art.
3. The silk fibril cracking agent and the preparation and use methods thereof disclosed by the invention have the advantages of simple operation, short process time consumption and low cost, and have large-scale industrial application value.
Drawings
FIG. 1 is a schematic diagram of the effect of a fibril-cleaving agent of the present invention on silk fibrils.
FIG. 2 is an SEM photograph of example 1 degummed silkworm silk after treatment with a fibril-disrupting agent.
Fig. 3 is an SEM picture of the micro-nano fibrils obtained after the tussah silk degummed in example 2 is treated with a fibril cracking agent and then mechanically crushed for 5 min.
Fig. 4 is an SEM picture of degummed silkworm silk fibrils of comparative example 1 after treatment with a calcium nitrate/alcohol/water solution.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 7mol/L, and the ratio of deionized water to alcohol is 1: 5;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 10mM Tris and 2mM EDTA;
s2 cracking treatment: immersing degummed silkworm silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared in S11, soaking for 3 days at 45 ℃, and fully washing with water; soaking the silk fiber treated in the first step in Tris-EDTA solution for 2 h;
and S3 post-processing: and fully washing and drying the fibers obtained in the step S2 to obtain the silk with weakened fibril force.
Example 2
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 5mol/L, and the ratio of deionized water to alcohol is 1: 3;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 50mM Tris and 10mM EDTA;
s2 cracking treatment: immersing degummed tussah silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared by S11, soaking for 5 days at 60 ℃, and fully washing; soaking the silk fiber treated in the first step in Tris-EDTA solution for 0.5 h;
and S3 post-processing: and fully washing and drying the fibers obtained in the step S2 to obtain the silk with weakened fibril force.
Example 3
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 4mol/L, and the ratio of deionized water to alcohol is 1: 1;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 1mM Tris and 1mM EDTA;
s2 cracking treatment: immersing degummed tussah silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared by S11, soaking for 7 days at 30 ℃, and fully washing; soaking the silk fiber treated in the first step in Tris-EDTA solution for 4 h;
and S3 post-processing: and fully washing and drying the poured fibers processed in the step S2 to obtain the silk with weakened fibril force.
Example 4
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 6mol/L, and the ratio of deionized water to alcohol is 1: 4;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 50mM Tris and 10mM EDTA;
s2 cracking treatment: immersing degummed tussah silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared in S11, soaking for 2 days at 50 ℃, and fully washing with water; soaking the silk fiber treated in the first step in Tris-EDTA solution for 1 h;
and S3 post-processing: and fully washing and drying the poured fibers processed in the step S2 to obtain the silk with weakened fibril force.
Example 5
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 1mol/L, and the ratio of deionized water to alcohol is 1: 2;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 25mM Tris and 5mM EDTA;
s2 cracking treatment: soaking degummed castor silk in ternary solution of calcium nitrate, ethanol and deionized water prepared in S11 at 55 deg.C for 2 days, and washing with water; soaking the silk fiber treated in the first step in Tris-EDTA solution for 0.5 h;
and S3 post-processing: and fully washing and drying the fibers obtained by the step S2 to obtain the silk with weakened fibril force.
Example 6
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 3mol/L, and the ratio of deionized water to alcohol is 1: 2.5;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 40mM Tris and 8mM EDTA;
s2 cracking treatment: immersing degummed camphor silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared in S11, soaking for 6 days at 35 ℃, and fully washing with water; soaking the silk fiber treated in the first step in Tris-EDTA solution for 1 h;
and S3 post-processing: and fully washing and drying the fibers obtained by the step S2 to obtain the silk with weakened fibril force.
Example 7
A silk fibril cracking agent and a preparation and use method thereof, wherein the method comprises the following steps:
s1 preparation solution:
s11 ternary mixed solution consisting of calcium nitrate, ethanol and deionized water is prepared. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 6mol/L, and the ratio of deionized water to alcohol is 1: 4;
s12 preparing a solution consisting of Tris and EDTA, wherein the ratio is as follows: 50mM Tris and 10mM EDTA;
s2 cracking treatment: immersing degummed tussah silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared in S11, soaking for 2 days at 50 ℃, and fully washing with water; soaking the silk fiber treated in the first step in Tris-EDTA solution for 1 h;
and S3 post-processing: and fully washing and drying the fibers obtained in the step S3 to obtain the silk with weakened fibril force.
Comparative example 1
S1 preparation solution: preparing a ternary mixed solution consisting of calcium nitrate, ethanol and deionized water. The concentration and ratio of calcium nitrate/ethanol/deionized water were: the concentration of calcium nitrate is 7mol/L, and the ratio of deionized water to alcohol is 1: 5;
s2 cracking treatment: immersing degummed silkworm silk into a ternary solution composed of calcium nitrate, ethanol and deionized water prepared in S1, soaking for 3 days at 45 ℃, and fully washing with water;
and S3 post-processing: and fully washing and drying the fibers obtained in the step S2 to obtain the silk with weakened fibril force.
S4 silk fiber fibril splitting and separating: mechanically crushing the obtained silk by a high-speed mixer for 10min at 40000r/min to obtain micro-nano fibrils.
TABLE 1
The results were analyzed in conjunction with Table 1, FIGS. 1-4.
The silk obtained in example 1 was subjected to mechanical crushing treatment using the same crushing conditions as in comparative example 1. Comparing example 1 and comparative example 1, it can be seen from FIGS. 1 and 4 that surface fibrillation of silk fibers was not evident without treatment with Tris-EDTA solution. The two-step treatment of the silk fibril cracking agent of the invention leads the surface of the silk to have obvious fibrillation and promotes the release of fibrils. As can be seen from Table 1, the yield of fibrils after mechanical action was significantly improved after treatment with the fibril-cleaving agent of the present invention.
Fig. 2 is an SEM picture of degummed silkworm silk treated with the fibril crazing agent of example 1 of the present invention, and it can be seen from the figure that the surface of the silk fiber treated with the fibril crazing agent of the present invention has a significant fibrillation effect, and the loosened fibrils have been exposed on the surface of the fiber in a large amount.
Fig. 3 is an SEM picture of the micro-nano fibrils obtained after the tussah silk degummed in example 2 is treated with a fibril cracking agent and then mechanically crushed for 5 min. As can be seen from the figure, the tussah silk is treated by the fibril cracking agent and then is mechanically crushed for 5min to obtain the micro-nano fiber, and the silk fibril separation efficiency is obviously higher than that in the prior art by 30 min-6 h.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A silk fibril cracking agent is characterized in that: the silk fibril cracking agent consists of a No. 1 reagent and a No. 2 reagent, wherein the No. 1 reagent is a soluble calcium salt/alcohol/water ternary mixed solution, and the No. 2 reagent is a Tris-EDTA solution;
performing two-step cracking treatment on silk fibers by using a No. 1 reagent soluble calcium/alcohol/water ternary mixed solution and a No. 2 reagent Tris-EDTA solution; the specific two-step cracking process comprises the following steps: adding degummed silk fibroin fibers into a soluble calcium salt/alcohol/water ternary mixed solution for carrying out first-step cracking treatment; and then, washing the silk fibroin fibers subjected to the cracking treatment in the first step, and then placing the silk fibroin fibers in a Tris-EDTA solution for carrying out cracking treatment in the second step.
2. The silk fibril dehiscent agent according to claim 1, characterized in that: the volume concentration of the soluble calcium salt in the soluble calcium salt/alcohol/water ternary mixed solution is 1-7 mol/L; the Tris-EDTA solution comprises 1-50 mM Tris and 1-10 mM EDTA.
3. The silk fibril dehiscent agent according to claim 1, characterized in that: the soluble calcium salt is one or two of calcium nitrate and calcium chloride.
4. The silk fibril dehiscent agent according to claim 1, characterized in that: the alcohol is one or more of methanol, ethanol, propanol and butanol.
5. The silk fibril dehiscent agent according to claim 1, characterized in that: the volume ratio of water to alcohol in the ternary mixed solution is 1: 1-5.
6. A silk fibril dehiscent agent according to any one of claims 1 to 5, characterized in that: the silk is one or more of mulberry silk, tussah silk, camphor silk, castor-oil plant silk or willow silk.
7. Use of a silk fibril dehiscent agent according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
s1 preparation solution: preparing a No. 1 reagent soluble calcium salt/alcohol/water ternary mixed solution and a No. 2 reagent Tris-EDTA solution with preset concentrations;
s2 cracking treatment: adding degummed silk fibroin fibers into a soluble calcium salt/alcohol/water ternary mixed solution for carrying out first-step cracking treatment; then, washing the silk fibroin fibers subjected to the cracking treatment in the first step, and then placing the silk fibroin fibers in a Tris-EDTA solution for carrying out cracking treatment in the second step;
and S3 post-processing: and (3) washing and drying the fibers treated by the cracking agent to obtain the silk fibroin fibers with obviously weakened interfibrillary force, and performing fibril separation.
8. The use method of the silk fibril dehiscent agent according to claim 7, characterized in that: the first cracking treatment in step S2 is soaking treatment at 30-60 ℃ for 1-7 days.
9. The use method of the silk fibril dehiscent agent according to claim 7, characterized in that: and the second cracking treatment in the step S2 is soaking treatment in a Tris-EDTA solution for 0.5-4 hours.
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