CN101503834B - Collagen - Na-MMT complex fiber, and spinning technological process thereof - Google Patents
Collagen - Na-MMT complex fiber, and spinning technological process thereof Download PDFInfo
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- CN101503834B CN101503834B CN2009100585071A CN200910058507A CN101503834B CN 101503834 B CN101503834 B CN 101503834B CN 2009100585071 A CN2009100585071 A CN 2009100585071A CN 200910058507 A CN200910058507 A CN 200910058507A CN 101503834 B CN101503834 B CN 101503834B
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Abstract
The invention discloses novel collagen composite fiber mainly comprising collagen and a small amount of Na-MMT, and a spinning technical method thereof. The proportion of collagen and Na-MMT in the composite fiber counted in portion by dry weight is 10,000:1-100. The main preparation method of the composite fiber comprises: stirring and mixing 15 to 50 weight percent collagen solution and 0.1 to 2 weight percent Na-MMT solution according to a set proportion under a water bath condition between 50 and 80 DEG C; carrying out hot filtration at a temperature between 50 and 80 DEG C after the solutions are evenly mixed; obtaining spinning solution used to imitate collagen-Na-MMT composite fiber after defoaming; extruding the spinning solution through a spinneret under the action of gas pressure at a temperature between 50 and 80 DEG C; and entering inorganic salt coagulation bath to prepare the collagen-Na-MMT composite fiber through solidification. In addition, the intensity, swelling capacity, water absorption, and the like of textile composite fiber can be improved through post treatments such as acetalation and oiling. The collagen-Na-MMT composite fiber can be used for textile materials and biomedical materials.
Description
Technical field
The present invention relates to collagen composite fibre technology field, specifically, relate to a kind of collagen-sodium-based montmorillonite (Na-MMT) composite fibre and spinning technological process thereof.
Background technology
Every molecule is a line style, and molecular weight can be made fiber by suitable method at the big molecule more than 3000.Collagen is the rich in protein of mammal in-vivo content, because its unique triple helix design feature, and excellent biological compatibility and biodegradable, the application at aspects such as bio-medical material and polymer composites in recent years receives much concern.Wherein, utilizing collagen to prepare fibrous material is a focus of studying both at home and abroad.The preparation method of collagen fabric mainly contains two kinds: a kind of is chemical cross-linking agent modification method, as preparing (CN 1213191C with metal ion, formaldehyde, glutaraldehyde, epoxide etc. as the crosslinking agent modification; CN 1481461A; CN 1100165C); Another kind is and other synthetic material (CN 1206393C) or natural macromolecular material (CN 1584150A) blending modification method.When adopting crosslinking agent modification method that collagen is carried out modification, must consider the toxicity and the unstability of crosslinking agent itself, and problem such as cross-linking reaction is wayward; In addition, adopt glue crosslinking agent modification method that collagen is carried out modification, the research that has thinks that the collagen tissue engineering material by crosslinking agent modifications such as formaldehyde, glutaraldehydes can suppress the cell growth, produces inflammatory reaction, even causes calcification.And in the report that uses macromolecular material and the spinning of collagen blending and modifying, as collagen and polyvinyl alcohol (PVA) (CN1492087A; CN 1696362A) blend prepares composite fibre, be to take as the leading factor in fact with polyvinyl alcohol (itself being exactly the good chemical fibre raw material of spinnability), and collagen only serves as the role of additive therein, does not give full play to the performance of collagen as main fibre like this, and can limit its application.
Summary of the invention
The deficiency that exists at the collagen composite fibre of prior art, purpose of the present invention aims to provide a kind of based on collagen, utilize a spot of sodium-based montmorillonite (Na-MMT) and collagen blending to be spun into, both can be used as textile material, can be used as the new collagen protein composite fiber and the spinning technological process thereof of bio-medical materials such as operation suture thread, hemostatic gauze again, to improve the mechanical performance and the heat endurance of collagen composite fibre, overcome problems such as simple collagen albumen spinnability difference.
Collagen provided by the invention-Na-MMT composite fibre, the formation of its component collagen and Na-MMT is counted collagen: Na-MMT=10000: 1～100 by dry weight part; Preferred ingredients constitutes, and counts collagen by dry weight part: Na-MMT=10000: 2～50; Further preferred ingredients constitutes, and counts collagen by dry weight part: Na-MMT=10000: 5～20.
The preparation of above-mentioned collagen-Na-MMT composite fibre, its preparation technology's method mainly may further comprise the steps:
(1) be that collagen solution and the concentration of 15～50 weight % is that 0.1～2 weight %Na-MMT solution is by preset proportion blended under agitation under 50～80 ℃ of water bath condition with concentration, fully mix the back in 50～80 ℃ of heat filterings, obtain being used for the spinning solution of imitated collagen-Na-MMT composite fibre through deaeration;
(2) spinning solution is extruded through spinning head in 50～80 ℃ under the gas pressure effect, enters in the inorganic salts coagulating bath and promptly prepares collagen-Na-MMT composite fibre through solidifying.
In order to improve the intensity of composite fibre, on the basis of technique scheme, also can further take following technical measures:
To be wound into spiral filament forming machine on axle through collagen-Na-MMT composite fibre that the inorganic salts coagulating bath is solidified, and regulate the slewing rate of spiral filament forming machine, the composite fibre of using coagulating bath is stretched to 3～10 times.
Handle 5～30min through the composite fibre that spiral filament forming machine stretches 60～160 ℃ of following HEAT SETTING.
For the composite fibre that is used for textile material, available formaldehyde or glutaraldehyde solution carry out acetalation to composite fibre to be handled, and concrete technological parameter is: aldehyde concentration is 0.5～2 weight %, and the hydroformylation time is 1～30min, hydroformylation pH value is 7～8, and the hydroformylation temperature is 20～40 ℃.
For the composite fibre that is used for textile material, in order to improve the serviceability of composite fibre, can further carry out oiling treatment to composite fibre with the amino-modified silicone oil aqueous solution, concrete technological parameter is: amino-modified silicone oil concentration is 5～20 weight %, time 10～20min oils, 20～30 ℃ of last oil temperatures, the back that oils uses 50～100 ℃ hot blast that composite fibre is carried out drying.
The Na-MMT aqueous solution described in the technique scheme, after can taking Na-MMT is dispersed in water, again in water fully swelling produced and sonicated 20～60min before use in 1～10 day.
The described composite spinning liquid of technique scheme is to be produced through natural deaeration or ultrasonic deaeration under 50～80 ℃ of keeping warm modes by the filtrate behind the heat filtering.
The present invention has also taked some other technical measures.
Collagen is a kind of fibrous big molecule, and stronger interaction force is arranged between Na-MMT and the collagen, and collagen and Na-MMT blend can be improved the mechanical performance of gained composite fibre greatly, also helps improving the spinning property of composite spinning liquid; Composite fibre easily is orientated in follow-up spin-drawing process and HEAT SETTING, easily forms the oriented crystalline structure.Compared with the prior art the present invention has the following advantages:
(1) the invention provides a kind of collagen-Na-MMT composite fibre and spinning technological process thereof, the fibrous material that makes is based on collagen, can give full play to the biology performance advantage of collagen matrix material, and the nanostructured of Na-MMT also can be used for bio-medical material.
(2) the present invention can take different subsequent treatment process according to the final use difference of composite fibre, and the gained composite fibre is applicable to textile industry as textile material, also can be used for bio-medical material.
(3) first nanometer Na-MMT is incorporated in the collagen spinning solution, has improved the intensity of collagen fabric, and improved the spinnability of collagen; The fibrous material possess hydrophilic property of the two compound spinning, histocompatbility, avirulence etc. not only can be used for textile industry as the DRESS FABRIC material, and are applicable to field of biomedical materials.
(4) because collagen is an ampholytes, when the composite fibre that adopts the present invention to prepare was used for rag trade, making had stronger binding ability between composite fibre and dyestuff, and dyeability is good.
(5) collagen of this technology use is similar to the human body skin collagen structure, and is because collagen accounts for most proportions in the spinning solution, so the fiber that uses the present invention to obtain has natural texture, comfortable and easy to wear salubrious when being used for rag trade.
The inventor yet there are no the bibliographical information or the patent disclosure of collagen-Na-MMT composite fibre research to so far, and collagen provided by the invention-Na-MMT composite fibre is a kind of brand-new collagen composite fibre.
The specific embodiment
Provide four embodiment of the present invention below, to specify the spinning method for genuine of collagen of the present invention-Na-MMT composite fibre.Be necessary to be pointed out that at this; embodiment only is used for that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; according to the invention described above content improvement and adjustment that the present invention makes non-intrinsically safe are implemented, should still be belonged to protection scope of the present invention.
Among each embodiment, the umber of related component is parts by weight below, and percentage composition is weight content.
Embodiment 1
Take by weighing 40 parts of collagen powder and add in 60 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 40% collagen solution.Take by weighing 0.2 part of Na-MMT simultaneously and add in 99.8 parts the water, the swelling that constantly stirs in water 2 days, obtaining concentration is 0.2 weight %Na-MMT solution.Is 10000: 2 slowly blend and constantly stirring of ratio with the Na-MMT solution of collagen solution and sonicated 20min in collagen and Na-MMT in 60 ℃, after 30 minutes, mixed solution vacuum heat filtering places the interior standing and defoaming 12hrs of 60 ℃ of baking ovens to get composite spinning liquid afterwards.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 60 ℃ of recirculated water preheating spinning heads 10 minutes simultaneously at 60 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter the inorganic salts coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of inorganic salts coagulating bath is 20 ℃, and it consists of: saturated sodium sulphate, NaOH 1 grams per liter.Regulate the slewing rate of cops, fiber be wound on the cops continuously, and make 3 times of tensile fibers, then with fiber in 60 ℃ of HEAT SETTING 30min.Re-use formaldehyde or glutaraldehyde composite fibre is carried out the acetalation processing.Concrete technological parameter is: aldehyde concentration is about 1%, and the hydroformylation time is about 5s; Hydroformylation pH value is 7～8; The hydroformylation temperature is about 40 ℃.With fiber wash, drying, use amino-modified silicone oil to carry out oiling treatment afterwards then, concrete parameter is: amino-modified silicone oil concentration is 15 weight %, the time 15min that oils, 25 ℃ of last oil temperatures.Use 60 ℃ hot blast that composite fibre is carried out drying after oiling.
Prepared collagen-Na-MMT the composite fibre of present embodiment can be used as the DRESS FABRIC material.
Embodiment 2
Take by weighing 30 parts of collagen powder and add in 70 parts of water, it is 30 weight % collagen solutions that 70 ℃ of water-bath heating and continuous stirring obtained concentration in 40 minutes.Take by weighing 0.5 part of Na-MMT simultaneously and add in 99.5 parts the water, the back swelling 3 days in water that constantly stirs, obtaining concentration is 0.5 weight %Na-MMT solution.Is 10000: 5 slowly blend and constantly stirring of ratio with the Na-MMT solution of collagen solution and sonicated 30min in collagen and Na-MMT in 70 ℃, after 1 hour, mixed solution vacuum heat filtering places 60 ℃ of ultrasonic deaeration 2hrs of ultrasonic water bath to get composite spinning liquid afterwards.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 70 ℃ of recirculated water preheating spinning heads after 10 minutes simultaneously at 70 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of inorganic salts coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, NaOH 0.75 grams per liter.Regulate the slewing rate of cops, fiber be wound on the cops continuously, and make 5 times of tensile fibers, then with fiber in 80 ℃ of HEAT SETTING 20min.Re-use formaldehyde or glutaraldehyde composite fibre is carried out the acetalation processing.Concrete technological parameter is: aldehyde concentration is about 0.5%, and the hydroformylation time is about 2min; Hydroformylation pH value is 7～8; The hydroformylation temperature is about 30 ℃.With fiber wash, drying, use amino-modified silicone oil to carry out oiling treatment afterwards then, concrete parameter is: amino-modified silicone oil concentration is 20 weight %, the time 10min that oils, 20 ℃ of last oil temperatures.Use 80 ℃ hot blast that composite fibre is carried out drying after oiling.
Prepared collagen-Na-MMT the composite fibre of present embodiment can be used as the DRESS FABRIC material.
Embodiment 3
Take by weighing 15 parts of collagen powder and add in 85 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 15% collagen solution.Take by weighing 1 part of Na-MMT simultaneously and add in 99 parts the water, the back swelling 5 days in water that constantly stirs, obtaining concentration is 1 weight %Na-MMT solution.Is 10000: 10 slowly blend and constantly stirring of ratio with the Na-MMT solution of collagen solution and sonicated 40min in collagen and Na-MMT in 60 ℃, after 30 minutes, mixed solution vacuum heat filtering places the interior standing and defoaming 12hrs of 60 ℃ of baking ovens to get composite spinning liquid afterwards.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 60 ℃ of recirculated water preheating spinning heads after 10 minutes simultaneously at 60 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, NaOH 0.75 grams per liter.Regulate the slewing rate of cops, fiber be wound on the cops continuously, and make 8 times of tensile fibers, then with fiber in 100 ℃ of HEAT SETTING 15min.
Prepared collagen-Na-MMT the composite fibre of present embodiment can be used as biomedical material.
Embodiment 4
Take by weighing 30 parts of collagen powder and add in 70 parts of water, 70 ℃ of water-bath heating and continuous the stirring got collagen solution in 40 minutes.Take by weighing 1.5 parts of Na-MMT simultaneously and add in 98.5 parts the water, the back swelling 8 days in water that constantly stirs, obtaining concentration is 1.5 weight %Na-MMT solution.Is 10000: 20 slowly blend and constantly stirring of ratio with the Na-MMT solution of collagen solution and sonicated 50min in collagen and Na-MMT in 70 ℃, after 1 hour, mixed solution vacuum heat filtering places 60 ℃ of ultrasonic deaeration 2hrs of ultrasonic water bath afterwards.
70 ℃ of recirculated water preheating spinning heads added composite spinning liquid in the storage liquid filling that has insulation jacket to after 10 minutes, kept recirculated water at 70 ℃.Slowly pressurize with nitrogen, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, NaOH 0.5 grams per liter.Regulate the slewing rate of cops, fiber be wound on the cops continuously, and make 10 times of tensile fibers, then with fiber in 120 ℃ of HEAT SETTING 10min.
Prepared collagen-Na-MMT the composite fibre of present embodiment can be used as biomedical material.
Claims (10)
1. collagen-sodium-based montmorillonite composite fibre is characterized in that the component collagen in the composite fibre and the formation of sodium-based montmorillonite, counts collagen by dry weight part: sodium-based montmorillonite=10000: 1～100.
2. the described collagen of claim 1-sodium-based montmorillonite composite fibre is characterized in that the component collagen in the composite fibre and the formation of sodium-based montmorillonite, counts collagen by dry weight part: sodium-based montmorillonite=10000: 2～50.
3. the described collagen of claim 2-sodium-based montmorillonite composite fibre is characterized in that the component collagen in the composite fibre and the formation of sodium-based montmorillonite, counts collagen by dry weight part: sodium-based montmorillonite=10000: 5～20.
4. process that spins claim 1 or 2 or 3 described collagen-sodium-based montmorillonite composite fibres is characterized in that may further comprise the steps:
(1) be that collagen solution and the concentration of 15～50 weight % is that 0.1～2 weight % sodium-based montmorillonite solution is by preset proportion blended under agitation under 50～80 ℃ of water bath condition with concentration, fully mix the back in 50～80 ℃ of heat filterings, obtain being used to spin the spinning solution of collagen-sodium-based montmorillonite composite fibre through deaeration;
(2) spinning solution is extruded through spinning head in 50～80 ℃ under the gas pressure effect, enters in the inorganic salts coagulating bath and promptly prepares collagen-sodium-based montmorillonite composite fibre through solidifying.
5. the spinning technological process of collagen according to claim 4-sodium-based montmorillonite composite fibre, it is characterized in that and to be wound into spiral filament forming machine on axle through collagen-sodium-based montmorillonite sodium-based montmorillonite T composite fibre that the inorganic salts coagulating bath is solidified, regulate the slewing rate of spiral filament forming machine, the composite fibre of using coagulating bath is stretched to 3～10 times.
6. the spinning technological process of collagen according to claim 5-sodium-based montmorillonite composite fibre, the composite fibre that it is characterized in that stretching through spiral filament forming machine is at 60～160 ℃ of following HEAT SETTING processing 5～30min.
7. according to the spinning technological process of claim 4 or 5 or 6 described collagen-sodium-based montmorillonite composite fibres, it is characterized in that with formaldehyde or glutaraldehyde solution composite fibre being carried out acetalation handles, concrete technological parameter is: aldehyde concentration is 0.5～2 weight %, the hydroformylation time is 1～30min, hydroformylation pH value is 7～8, and the hydroformylation temperature is 20～40 ℃.
8. the spinning technological process of collagen according to claim 7-sodium-based montmorillonite composite fibre, it is characterized in that composite fibre being carried out oiling treatment with the amino-modified silicone oil aqueous solution, concrete technological parameter is: amino-modified silicone oil concentration is 5～20 weight %, time 10～20min oils, 20～30 ℃ of last oil temperatures, the back that oils uses 50～100 ℃ hot blast that composite fibre is carried out drying.
9. the spinning technological process of collagen according to claim 8-sodium-based montmorillonite composite fibre, after it is characterized in that the described sodium-based montmorillonite aqueous solution is taked sodium-based montmorillonite is dispersed in water, again in water fully swelling produced and sonicated 20～60min before use in 1～10 day.
10. the spinning technological process of collagen according to claim 8-sodium-based montmorillonite composite fibre is characterized in that through the filtrate behind the heat filtering nature deaeration or ultrasonic deaeration under 50～80 ℃ of keeping warm modes.
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| CN102268092A (en) * | 2011-05-23 | 2011-12-07 | 天津大学 | Bovine serum albumin-montmorillonite nano composite material and preparation method thereof |
| CN103013138B (en) * | 2012-12-11 | 2014-10-15 | 四川大学 | Gelatin-based nano-composite material and preparation method thereof |
| CN110886025B (en) * | 2019-12-17 | 2022-07-05 | 上海里奥纤维企业发展有限公司 | Solvent method high wet modulus protein fiber and preparation method thereof |
| CN114182363B (en) * | 2020-10-12 | 2022-10-14 | 青岛尼希米生物科技有限公司 | Cellulose fiber capable of adsorbing and quickly deeply dyeing and preparation method and application thereof |
| CN113813369B (en) * | 2021-11-09 | 2023-09-22 | 浙江省农业科学院 | EGF/MMT complex for preventing/treating intestinal injury of piglets |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318657A (en) * | 2000-04-04 | 2001-10-24 | 石美秀 | Manufacture of fibre containing functional mineral powder and fibre prepared by the same |
| CN1576303A (en) * | 2003-07-28 | 2005-02-09 | 财团法人工业技术研究院 | High polymer / clay nano composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318657A (en) * | 2000-04-04 | 2001-10-24 | 石美秀 | Manufacture of fibre containing functional mineral powder and fibre prepared by the same |
| US6669882B2 (en) * | 2000-04-04 | 2003-12-30 | Mi Soo Seok | Process of making fiber having functional mineral powder |
| CN1576303A (en) * | 2003-07-28 | 2005-02-09 | 财团法人工业技术研究院 | High polymer / clay nano composite material |
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