CN105386292B - A kind of method of modifying of collagenous fibres - Google Patents
A kind of method of modifying of collagenous fibres Download PDFInfo
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- CN105386292B CN105386292B CN201510936844.1A CN201510936844A CN105386292B CN 105386292 B CN105386292 B CN 105386292B CN 201510936844 A CN201510936844 A CN 201510936844A CN 105386292 B CN105386292 B CN 105386292B
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- collagenous fibres
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- collagenous
- modifying
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- 238000000034 method Methods 0.000 title claims abstract description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 19
- 102000008186 Collagen Human genes 0.000 claims description 4
- 108010035532 Collagen Proteins 0.000 claims description 4
- 229920001436 collagen Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000002657 fibrous material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 238000005213 imbibition Methods 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 101710172711 Structural protein Proteins 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000000498 stratum granulosum Anatomy 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- 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
- D06M2101/14—Collagen fibres
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of method of modifying of collagenous fibres.The present invention is mainly, and weighs 25 weight portion collagenous fibres and is added in the barium chloride solution that 200 weight portions, concentration are 0.5%~2%, and stirring stands 12 hours after 4 hours；Then sodium sulphate or potassium sulfate solution that 100 weight portions, concentration are 3% are slowly added dropwise under conditions of stirring, the rate of addition control of sodium sulphate or potassium sulfate solution is at 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；It is last to be vacuum dried 5~8 hours under the conditions of temperature is for 60~80 DEG C, that is, obtain collagenous fibres/barium sulfate hybrid material.The modified collagenous fibres of the present invention, water absorption rate is substantially reduced, and the performance such as mechanical strength, heat endurance is also increased considerably, while also having the characteristics such as fire-retardant, antibacterial, the application field of collagenous fiber material has been widened significantly.The present invention is simple to operate, and reaction is carried out at normal temperatures and pressures, low for equipment requirements, and cost of material is low, is adapted to large-scale production.
Description
Technical field
The invention belongs to hybrid inorganic-organic materials technical field, and in particular to one kind in-situ preparation on collagenous fibres
Barium sulfate particle is so as to the method being modified to collagenous fibres.
Background technology
Collagenous fibres are the Natural linear macromolecules of nature rich content, are primarily present in skin, bone, the tendon of animal
It is important structural proteins in connective tissue in Deng tissue.The amount of the useless leather of leather industry generation is very big, and wherein collagenous fibres are accounted for
More than 90%.According to the Research statistics in Britain's leather technology research center, only has input quality for the Animal Skin of process hides
27% leather for being eventually converted into use value.And China is process hides big country, acted on by acid plumping and physical mechanical, can be with
A large amount of collagenous fibres are extracted from discarded shavings.It can be seen that, the source of collagenous fiber material is enriched very much.
Collagenous fibres are white chopped fiber shape solid, and more than 90% is collagen in composition, is not dissolved in hydrophilic
It is the characteristics of water, easily swelling rear in appropriate dispersity in water.Because collagenous fibres have water absorption rate high, easy deliquescence, heat steady
The qualitative low shortcoming of low, perishable, mechanical strength, although the material wide material sources, application industrially is subject to larger
Limitation.Therefore, find suitable method collagenous fibres are modified it is significant.
The content of the invention
It is an object of the invention to provide one kind using barium sulfate as modified material, and in proper proportions with it is appropriate
Technology is modified to collagenous fibres, and obtained hybrid material not only keeps collagenous fibres advantage in itself, also imparts collagen
The method of modifying of simple to operate, the easily prepared collagenous fibres of fiber new features.
The method of modifying of collagenous fibres of the invention, including following steps in sequence：
2-5 weight portion collagenous fibres are weighed to be added in the barium chloride solution that 200 weight portions, concentration are 0.5%~2%,
Stirring stands 12 hours after 4 hours；Then be slowly added dropwise under conditions of stirring sodium sulphate that 100 weight portions, concentration are 3% or
The rate of addition of potassium sulfate solution, sodium sulphate or potassium sulfate solution is controlled at 0.5 drop/sec；After completion of dropping, 5 minutes are stood again
Suction filtration, washing；It is last to be vacuum dried 5~8 hours under the conditions of temperature is for 60~80 DEG C, that is, obtain collagenous fibres/barium sulfate miscellaneous
Change material.
Specifically, the collagenous fibres are that the collagenous fibres for obtaining are extracted from tanning waste.Its wide material sources, system
It is standby simple, it is cheap.
Specifically, the barium chloride, sodium sulphate and potassium sulfate are industry product of the purity of in the market purchase more than 99%
Product, and the aqueous solution prepared by concentration requirement, water used is deionized water.
The present invention is modified to collagenous fibres using the method for in-situ preparation inorganic particle precipitation, modified collagenous fibres with
Compare before modified, water absorption rate is substantially reduced, the performance such as mechanical strength, heat endurance is also increased considerably, at the same also have it is fire-retardant,
The characteristics such as antibacterial, have widened the application field of collagenous fiber material significantly.The present invention is in collagenous fibres in-situ preparation barium sulfate
The method of grain is simple to operate, and reaction is carried out at normal temperatures and pressures, low for equipment requirements, and cost of material is low, is adapted to extensive raw
Produce.Modified collagenous fiber material can be applied to filler, weaving, process hides, papermaking, the field, application prospect ten such as separation material
Divide wide.
It is of the invention compared with existing collagenous fibres method of modifying, have the following advantages：
(1) excellent performance：In-situ preparation barium sulfate particle is firmly combined with collagenous fibres, even particle size, is distributed with
The spies such as sequence, modified collagenous fibres have that water absorption rate is low, are difficult deliquescence, good, the fire-retardant, antibacterial of high mechanical strength, heat endurance
Point, application value is higher.
(2) method of modifying is controllable：Present invention modified collagen fiber by the way of in-situ preparation barium sulfate particle.Experiment hair
Existing, distribution and granular size of the barium sulfate particle on collagenous fibres change with the change of barium chloride solution concentration.Low dense
Under degree, the barium sulfate particle generated on collagenous fibres is larger, disperses sparse on collagenous fibres；As barium chloride concentration increases,
Barium sulfate particle reduces, and more crypto set is distributed on collagenous fibres.Therefore can effectively be controlled by changing the concentration of barium chloride solution
The thickness of the size, distribution and stratum granulosum of the generated barium sulfate particle of system, so as to realize to modified collagenous fibres performance
Regulation.
(3) technological operation is simple：The operating procedure mentioned in the inventive method not only contributes to the original position of barium sulfate particle
Generate, and operating condition is easily controlled, and is prepared into power higher.Whole preparation process without specific condition, to equipment requirement
It is not harsh, it is adapted to large-scale production.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, wherein, the raw material is industry
Change product.
Embodiment 1：
Collagenous fibres 0.2g, 20ml barium chloride solution (concentration is 0.5%) are added in the reaction vessel of agitator,
Stirring stands 12 hours after 4 hours；Then 10ml metabisulfite solutions (concentration is 3%), sulphur are slowly added dropwise under conditions of stirring
The rate of addition of acid sodium solution is about 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；Last is 80 in temperature
It is vacuum dried 8 hours under the conditions of DEG C, that is, obtains collagenous fibres/barium sulfate hybrid material.
The material is observed under ESEM, it is possible to find barium sulfate crystalline particle is attached to collagenous fibres surface, and size is
2-4 μm, the particle of shape such as spindle-type.Collagenous fiber material water absorption rate before modified is 442%, and modified water absorption rate is
179%, water imbibition is substantially reduced.
Embodiment 2：
Collagenous fibres 0.3g, 20ml barium chloride solution (concentration is 1%) are added in the reaction vessel of agitator, are stirred
12 hours are stood after mixing 4 hours；Then 10ml metabisulfite solutions (concentration is 3%), sulfuric acid are slowly added dropwise under conditions of stirring
The rate of addition of sodium solution is about 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；Last is 80 DEG C in temperature
Under the conditions of be vacuum dried 8 hours, that is, obtain collagenous fibres/barium sulfate hybrid material.
The material is observed under ESEM, it is possible to find barium sulfate crystalline particle is attached to collagenous fibres surface, and particle is big
Small is 1-3 μm, the particle of shape such as spindle-type.Collagenous fiber material water absorption rate before modified is 442%, modified water suction
Rate is 147%, and water imbibition is substantially reduced.
Embodiment 3：
Collagenous fibres 0.4g, 20ml barium chloride solution (concentration is 1.5%) are added in the reaction vessel of agitator,
Stirring stands 12 hours after 4 hours；Then 10ml metabisulfite solutions (concentration is 3%), sulphur are slowly added dropwise under conditions of stirring
The rate of addition of acid sodium solution is about 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；Last is 80 in temperature
It is vacuum dried 8 hours under the conditions of DEG C, that is, obtains collagenous fibres/barium sulfate hybrid material.
The material is observed under ESEM, it is possible to find barium sulfate crystalline particle is intensive to be attached to collagenous fibres surface,
Grain size is 1-2 μm, the particle of shape such as spindle-type.Collagenous fiber material water absorption rate before modified is 442%, modified
Water absorption rate is 142%, and water imbibition is substantially reduced.
Embodiment 4：
Collagenous fibres 0.5g, 20ml barium chloride solution (concentration is 2%) are added in the reaction vessel of agitator, are stirred
12 hours are stood after mixing 4 hours；Then 10ml metabisulfite solutions (concentration is 3%), sulfuric acid are slowly added dropwise under conditions of stirring
The rate of addition of sodium solution is about 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；Last is 80 DEG C in temperature
Under the conditions of be vacuum dried 8 hours, that is, obtain collagenous fibres/barium sulfate hybrid material.
The material is observed under ESEM, it is possible to find barium sulfate crystalline particle is very intensive to be attached to collagenous fibres table
Face, granular size is 0.5-1 μm, the particle of shape such as spindle-type.Collagenous fiber material water absorption rate before modified is 442%,
Modified water absorption rate is 139%, and water imbibition is substantially reduced.
Claims (3)
1. a kind of method of modifying of collagenous fibres, it is characterised in that including following steps in sequence：Weigh 2-5 weight portions collagen fine
Dimension is added in the barium chloride solution that 200 weight portions, concentration are 0.5%~2%, and stirring stands 12 hours after 4 hours；Then exist
Sodium sulphate or potassium sulfate solution that 100 weight portions, concentration are 3% are slowly added dropwise under conditions of stirring, sodium sulphate or potassium sulfate are molten
The rate of addition of liquid is controlled at 0.5 drop/sec；After completion of dropping, 5 minutes suction filtrations again, washing are stood；Last is 60~80 in temperature
It is vacuum dried 5~8 hours under the conditions of DEG C, that is, obtains collagenous fibres/barium sulfate hybrid material.
2. the method for modifying of collagenous fibres according to claim 1, it is characterised in that：The collagenous fibres are from leather-making waste
The collagenous fibres for obtaining are extracted in thing.
3. the method for modifying of collagenous fibres according to claim 1, it is characterised in that：The barium chloride, sodium sulphate and sulfuric acid
Potassium is the industrial products of the purity more than 99% of in the market purchase, and is configured to the aqueous solution by concentration requirement, and water used is to go
Ionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936844.1A CN105386292B (en) | 2015-12-16 | 2015-12-16 | A kind of method of modifying of collagenous fibres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936844.1A CN105386292B (en) | 2015-12-16 | 2015-12-16 | A kind of method of modifying of collagenous fibres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105386292A CN105386292A (en) | 2016-03-09 |
| CN105386292B true CN105386292B (en) | 2017-06-09 |
Family
ID=55419037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510936844.1A Expired - Fee Related CN105386292B (en) | 2015-12-16 | 2015-12-16 | A kind of method of modifying of collagenous fibres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105386292B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002052099A1 (en) * | 2000-12-22 | 2002-07-04 | Kaneka Corporation | Process for producing regenerated collagen fiber and proecss for setting the same |
| CN102863002B (en) * | 2012-09-26 | 2014-01-08 | 中国科学院宁波材料技术与工程研究所 | In-situ controllable synthesis method of nano-barium sulfate powder |
| CN104594026B (en) * | 2015-02-02 | 2017-07-14 | 中国人民解放军总后勤部军需装备研究所 | A kind of fire resistance fibre and preparation method thereof |
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2015
- 2015-12-16 CN CN201510936844.1A patent/CN105386292B/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN105386292A (en) | 2016-03-09 |
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