CN105063995A - Method for enhancing stretching mechanical property of natural protein fiber - Google Patents
Method for enhancing stretching mechanical property of natural protein fiber Download PDFInfo
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- CN105063995A CN105063995A CN201510476570.2A CN201510476570A CN105063995A CN 105063995 A CN105063995 A CN 105063995A CN 201510476570 A CN201510476570 A CN 201510476570A CN 105063995 A CN105063995 A CN 105063995A
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- 239000000835 fiber Substances 0.000 title claims abstract description 261
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 161
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002708 enhancing effect Effects 0.000 title abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 107
- 238000004140 cleaning Methods 0.000 claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 210000002268 wool Anatomy 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 150000002605 large molecules Chemical class 0.000 claims description 33
- 229920002521 macromolecule Polymers 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000007654 immersion Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- 241000283973 Oryctolagus cuniculus Species 0.000 claims description 25
- 238000009792 diffusion process Methods 0.000 claims description 20
- -1 phosphate ester salt Chemical class 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 206010042674 Swelling Diseases 0.000 claims description 16
- 210000004209 hair Anatomy 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 16
- 238000009998 heat setting Methods 0.000 claims description 15
- 238000005728 strengthening Methods 0.000 claims description 14
- 230000002522 swelling effect Effects 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009941 weaving Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 5
- 229920001872 Spider silk Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a method for enhancing stretching mechanical property of natural protein fiber, which belongs to the technical field of weaving material. The method is characterized in that the natural protein fiber is obtained through natural protein fiber pretreatment, preparation of a modification solution, embedding of ammonium salt molecules in natural protein fiber, cleaning of ammonium salt molecules-imbedded natural protein fiber, micro drawing and heat fixing. The natural protein fiber breaking tenacity, young modulus and fracture elongation are simultaneously enhanced, the breaking tenacity of the prepared natural protein fiber is increased by 30-80%, fracture elongation is increased by 60-120%, and the young modulus is increased by 30-70%. The preparation method has the simple equipment, no special equipment, low cost, no pollution on ecological environment, high controllability, easy industrial production and large application prospect.
Description
Technical field
The present invention relates to a kind of method strengthening natural protein fiber tensile mechanical properties, belong to textile material technical field.
Background technology
Natural protein fiber mainly comprises silk, spider silk, wool, eider down, the rabbit hair and yak hair etc.Natural protein fiber is widely used in field of textiles with the performance of its excellence.Wherein, spider silk, with properties such as the heat endurance of its excellence, elasticity and tensions, has the title of " biological steel ", has attracted the interest of numerous scientific research personnel, have high researching value and using value.But its have be difficult to raise, yield poorly and collect difficulty etc. problem, cause it cannot apply in textile industry.Therefore, carry out enhancing modification to silk, wool and the rabbit hair etc., the tensile mechanical properties meeting or exceeding spider silk more and more has great importance.
The prior art that natural protein fiber tensile mechanical properties strengthens comprises following three: 1. make to produce between the large molecule of native protein to be cross-linked by the means of physics or chemistry, and then strengthen natural protein fiber; 2. pass through the method for heat treatment or chemical immersion, remove impurity and a small amount of amorphous substance, readjust the degree of orientation and the regularity of natural protein fiber, realize the object strengthening natural protein fiber tensile mechanical properties; 3. in natural protein fiber, introduce inorganic molecule, nano particle or nano whiskers material etc., realize the enhancing of natural protein fiber tensile mechanical properties.
The method of above-mentioned enhancing natural protein fiber tensile mechanical properties from molecular separating force aspect, state of aggregation aspect and add reinforcement aspect carry out design and implementation, it is process natural protein fiber modification being become rigid fiber, the increase of natural protein fiber rigidity will cause its flexible decline, and causes feel and comfortableness to decline.Therefore, increase while the method for above-mentioned enhancing natural protein fiber tensile mechanical properties can only realize its fracture strength and Young's modulus effectively, be but difficult to realize the object that natural protein fiber increases at fracture strength, Young's modulus and elongation at break three mechanical index simultaneously.For the defect of existing natural protein fiber tensile mechanical properties Enhancement Method, the method that the proposition of novelty is a kind of strengthens the fracture strength of natural protein fiber, Young's modulus and elongation at break simultaneously seems very meaningful, and the tensile mechanical properties also for strengthening natural protein fiber provides a new way.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of method strengthening natural protein fiber tensile mechanical properties, to achieve these goals, technical solution of the present invention is,
Strengthen a method for natural protein fiber tensile mechanical properties, described method is carried out according to the following steps:
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, absolute ether is adopted by natural protein fiber to carry out siphon circulation cleaning, putting into temperature after cleaning 2-5h is that the 80-90 DEG C of dry 1-2h of drying box is until the ether on natural protein fiber surface is removed, obtain pretreated natural protein fiber, wherein, the siphon circulation wash number of natural protein fiber is 20-50 time;
The preparation of b modified solution
By following mass percent:
Deionized water 15 ~ 97.5%
Ammonium salt 1 ~ 70%
The polar solvent 0.5 ~ 10% of amide bond
Acetone 0.9 ~ 4.5%
Low relative molecular weight anionic surfactant 0.1 ~ 0.5%
The polar solvent of ammonium salt, amide bond, acetone and low relative molecular weight anionic surfactant are put into deionized water and obtains mixed solution, then the temperature of mixed solution be increased to 25 ~ 98 DEG C and obtain modified solution after mechanical agitation 3-5h, wherein, stir speed (S.S.) is 800-3000r/min;
C ammonium salt molecule embeds natural protein fiber
The pretreated natural protein fiber obtained through step a is put into the modified solution prepared through step b, temperature be 80-130 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 1-5h under being the condition of 0.101-0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated natural protein fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed natural protein fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 18-32 DEG C cleans that the natural protein fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, 5-10% is extended in the length drawing-off of the natural protein fiber embedded by ammonium salt molecule after cleaning 1-5min, then the dry 1-2h of air dry oven that temperature is 65-90 DEG C is put into, obtain fracture strength and increase 30-80%, elongation at break increases 60-120%, and Young's modulus increases the natural protein fiber of 30-70%.
Described natural protein fiber is the one in silk fiber or wool fibre or down fiber or rabbit fur fibre or yak hair fiber.
Conductance≤16M Ω the cm of described deionized water.
Described ammonium salt is the one in ammonium nitrate or ammonium chloride or ammonium sulfate or ammonium hydrogen sulfate or ammonium carbonate or carbonic hydroammonium or ammonium phosphate or ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.
The polar solvent of described amide bond is the one in formamide or DMF or DMA.
Described low relative molecular weight anionic surfactant is the one in sulfate salt surfactant or sulfosalt surfactant or phosphate ester salt surfactant, and relative molecular weight is 200-1000.
Owing to have employed above technical scheme, technical characterstic of the present invention is:
(1) method of existing enhancing natural protein fiber tensile mechanical properties can only strengthen fracture strength and the Young's modulus of natural protein fiber, and technical scheme of the present invention strengthens while can realizing natural protein fiber fracture strength, Young's modulus and elongation at break;
(2) natural protein fiber is after preliminary treatment, put into the mixed solution be made up of the polar solvent of deionized water, ammonium salt, amide bond, acetone and low relative molecular weight anionic surfactant, after High Temperature High Pressure immersion and swelling treatment, between the large molecule of ammonium salt molecule embedding natural protein fiber amorphous region and in hole.When the natural protein fiber of ammonium salt molecule embedding is after micro-drawing-off and HEAT SETTING, the ammonium radical ion of ammonium salt molecule defines more stable Hyarogen-bonding with-NH-group in the large molecule of native protein between the large molecule in the amorphous region of natural protein fiber, constitutes micro-cross-linked structure.In addition, ammonium salt molecule more in the hole of the amorphous region of natural protein fiber crystallization can form the Nano microsphere that diameter is 20-180nm together, in ammonium radical ion on Nano microsphere and the large molecule of native protein ,-NH-group also can form hydrogen bond, thus is linked together by Nano microsphere by multiple native protein macromolecular chain.In drawing process, the large molecule of the amorphous region of natural protein fiber is constantly stretched and mutual slippage, also relative slippage is produced between ammonium radical ion with the large molecule of native protein, after hydrogen bond rupture between them, ammonium radical ion can form new hydrogen bond with the-NH-group closed on new position, and the spinning of Nano microsphere in drawing process, add the sliding displacement between the large molecule of native protein.Therefore, in drawing process, after the strong hydrogen bonding power between ammonium radical ion and the large molecule of native protein and mutually gliding fracture formed again and the spinning of ammonium salt Nano microsphere causes the fracture strength of natural protein fiber, Young's modulus and elongation at break to strengthen simultaneously.
(3) obtain fracture strength by the present invention and increase 30-80%, elongation at break increases 60-120%, and Young's modulus increases the natural protein fiber of 30-70%.
The invention provides a kind of method strengthening natural protein fiber tensile mechanical properties, obtain by the method the natural protein fiber that fracture strength, Young's modulus and elongation at break strengthen simultaneously, opening up a new way for strengthening natural protein fiber.This preparation method's process equipment is simple, and cost is lower, pollution-free to ecological environment, and controllability is high, has great application prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is specifically described.
Strengthen a method for natural protein fiber tensile mechanical properties, described method is carried out according to the following steps:
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, by the one in silk fiber or wool fibre or down fiber or rabbit fur fibre or yak hair fiber, absolute ether is adopted to carry out siphon circulation cleaning, putting into temperature after cleaning 2-5h is that the 80-90 DEG C of dry 1-2h of drying box is until the ether on natural protein fiber surface is removed, obtain pretreated natural protein fiber, wherein, the siphon circulation wash number of natural protein fiber is 20-50 time.
The process stored and transport easily causes natural protein fiber surface adhesion oil stain and dust, the infiltration of serious obstruction modified solution on natural protein fiber surface and sprawling, and then affect the absorption of ammonium salt molecule to natural protein fiber surface, be unfavorable for its diffusion to natural protein fiber amorphous region.Therefore, absolute ether is adopted to carry out siphon circulation cleaning to natural protein fiber, to remove the impurity on natural protein fiber surface.
The preparation of b modified solution
By following mass percent:
Deionized water 15 ~ 97.5%
Ammonium salt 1 ~ 70%
The polar solvent 0.5 ~ 10% of amide bond
Acetone 0.9 ~ 4.5%
Low relative molecular weight anionic surfactant 0.1 ~ 0.5%
By the one in ammonium nitrate or ammonium chloride or ammonium sulfate or ammonium hydrogen sulfate or ammonium carbonate or carbonic hydroammonium or ammonium phosphate or ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, formamide or N, dinethylformamide or N, one in N-dimethylacetylamide, acetone and relative molecular weight are that a kind of deionized water putting into conductance≤16M Ω cm in the sulfate salt surfactant of 200-1000 or sulfosalt surfactant or phosphate ester salt surfactant obtains mixed solution, then the temperature of mixed solution be increased to 25 ~ 98 DEG C and obtain modified solution after mechanical agitation 3-5h, wherein, stir speed (S.S.) is 800-3000r/min.
Ammonium salt is the reinforcement that natural protein fiber obtains high fracture strength, high Young's modulus and high elongation at tear.The polar solvent of amide bond and acetone can carry out certain swelling to natural protein fiber, thus increase the distance between the large molecule in natural protein fiber amorphous region, and then are conducive to diffusion and the embedding of ammonium salt molecule.The interpolation of a small amount of low relative molecular weight anionic surfactant, can improve the wettability on natural protein fiber surface further and provide passage, accelerates the absorption on natural protein fiber surface of ammonium salt molecule and diffusion.
C ammonium salt molecule embeds natural protein fiber
The pretreated natural protein fiber obtained through step a is put into the modified solution prepared through step b, temperature be 80-130 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 1-5h under being the condition of 0.101-0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated natural protein fiber amorphous region large molecule between, obtain ammonium salt molecule embed natural protein fiber.
Under High Temperature High Pressure and swelling effect, distance between the large molecule in amorphous region of natural protein fiber increases, in modified solution, the diffusion velocity of ammonium salt molecule is accelerated, kinetic energy increases, and then impel between its large molecule diffusing to natural protein fiber amorphous region better, finally reach the object strengthening natural protein fiber tensile mechanical properties.
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 18-32 DEG C cleans that the natural protein fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, 5-10% is extended in the length drawing-off of the natural protein fiber embedded by ammonium salt molecule after cleaning 1-5min, then the dry 1-2h of air dry oven that temperature is 65-90 DEG C is put into, obtain fracture strength and increase 30-80%, elongation at break increases 60-120%, and Young's modulus increases the natural protein fiber of 30-70%.
After ammonium salt molecule embeds natural protein fiber, putting it into temperature is carry out cleaning 1-5min in the deionized water of 18-32 DEG C, removes the ammonium salt molecule on natural protein fiber surface.Then, 5-10% is extended in the length drawing-off of natural protein fiber, then the air dry oven dry heat sizing 1-2h that temperature is 65-90 DEG C is put into, to remove the internal stress of natural protein fiber, hydrogen bond effect between solid ammonium-salt molecule and the large molecule of native protein, realizes the at utmost enhancing of natural protein fiber tensile mechanical properties.In the process of ammonium salt molecular diffusion to natural protein fiber amorphous region, temperature, modified solution, high pressure and a series of environmental condition such as swelling cause natural protein fiber to produce internal stress, if do not removed, the strongest enhancing effect cannot be given play to by causing ammonium salt.
The enhancing principle of the natural protein fiber that patent system of the present invention is standby is as follows:
First, ammonium salt molecular diffusion to natural protein fiber amorphous region large molecule between, atom N in ammonium radical ion is with larger electronegativity,-NH-group easily and on the large molecule of native protein forms hydrogen bond, thus more stable Hyarogen-bonding is defined between the large molecule in native protein amorphous region, constitute micro-cross-linked structure, cause the fracture strength of natural protein fiber and Young's modulus to increase.In drawing process, the large molecule of amorphous region is constantly stretched and mutual slippage, also relative slippage is produced between ammonium salt molecule with large molecule, after hydrogen bond rupture between them, ammonium radical ion can form new hydrogen bond with the-NH-group closed on new position, thus causes the elongation at break of natural protein fiber also to increase.
Secondly, ammonium salt molecular diffusion is in the hole of natural protein fiber amorphous region, after cleaning, micro-drawing-off and HEAT SETTING, more ammonium salt molecule crystallization can form the Nano microsphere that yardstick is 20-180nm together, in ammonium radical ion on Nano microsphere and the large molecule of native protein ,-NH-group also can form hydrogen bond, thus is linked together by Nano microsphere by multiple native protein macromolecular chain.In drawing process, the rigidity of Nano microsphere can increase fracture strength and the Young's modulus of natural protein fiber, and the spinning of Nano microsphere in drawing process, add the sliding displacement between the large molecule of native protein, thus add the elongation at break of natural protein fiber.
Below in conjunction with specific embodiment, a kind of method strengthening natural protein fiber tensile mechanical properties of the present invention is described in further detail:
Embodiment 1
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by silk fiber absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 1h is 80 DEG C of dry 1h of drying box until the ether on silk fiber surface is removed, and obtains pretreated silk fiber, wherein, the siphon circulation wash number of silk fiber is 20 times.
The preparation of b modified solution
It is that the 15g deionized water of 16M Ω cm obtains mixed solution that the sulfate salt surfactant being 200 by 70g ammonium nitrate, 10g formamide, 4.5g acetone and 0.5g relative molecular weight puts into conductance, then the temperature of mixed solution be increased to 25 DEG C and obtain modified solution after mechanical agitation 3h, wherein, stir speed (S.S.) is 800r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated silk fiber obtained through step a is put into the modified solution prepared through step b, temperature be 80 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 1h under being the condition of 0.101Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated silk fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed silk fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 18 DEG C cleans that the silk fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the silk fiber embedded by ammonium salt molecule after cleaning 1min extends 5%, then the dry 1h of air dry oven that temperature is 65 DEG C is put into, obtain fracture strength and increase by 30%, elongation at break increases by 60%, and Young's modulus increases by the silk fiber of 30%.
Embodiment 2
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by wool fibre absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 2h is 85 DEG C of dry 2h of drying box until the ether of wool surface is removed, and obtains pretreated wool fibre, wherein, the siphon circulation wash number of wool fibre is 30 times.
The preparation of b modified solution
By 60g ammonium chloride, 8gN, dinethylformamide, 1.5g acetone and 0.5g relative molecular weight be 400 sulfosalt surfactant to put into conductance be that the 30g deionized water of 14M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 50 DEG C and obtain modified solution after mechanical agitation 4h, wherein, stir speed (S.S.) is 1100r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated wool fibre obtained through step a is put into the modified solution prepared through step b, temperature be 90 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 2h under being the condition of 0.151Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated wool fibre the large molecule in amorphous region between, obtain ammonium salt molecule embed wool fibre;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
Temperature put into by the wool fibre that the ammonium salt molecule prepared by step c embeds is that the deionized water of 22 DEG C cleans, the length drawing-off of the wool fibre embedded by ammonium salt molecule after cleaning 2min extends 6%, then the dry 2h of air dry oven that temperature is 70 DEG C is put into, obtain fracture strength and increase by 40%, elongation at break increases by 70%, and Young's modulus increases by the wool fibre of 40%.
Embodiment 3
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by wool fibre absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 4h is 90 DEG C of dry 1h of drying box until the ether of wool surface is removed, and obtains pretreated wool fibre, wherein, the siphon circulation wash number of wool fibre is 40 times.
The preparation of b modified solution
By 28g ammonium sulfate, 8gN, N-dimethylacetylamide, 3.7g acetone and 0.3g relative molecular weight be 600 phosphate ester salt surfactant to put into conductance be that the 60g deionized water of 14M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 75 DEG C and obtain modified solution after mechanical agitation 5h, wherein, stir speed (S.S.) is 1400r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated wool fibre obtained through step a is put into the modified solution prepared through step b, temperature be 100 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 3h under being the condition of 0.201Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated wool fibre the large molecule in amorphous region between, obtain ammonium salt molecule embed wool fibre;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
Temperature put into by the wool fibre that the ammonium salt molecule prepared by step c embeds is that the deionized water of 24 DEG C cleans, the length drawing-off of the wool fibre embedded by ammonium salt molecule after cleaning 3min extends 7%, then the dry 1h of air dry oven that temperature is 75 DEG C is put into, obtain fracture strength and increase by 60%, elongation at break increases by 90%, and Young's modulus increases by the wool fibre of 50%.
Embodiment 4
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by down fiber absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 5h is 80 DEG C of dry 2h of drying box until the ether on down fiber surface is removed, and obtains pretreated down fiber, wherein, the siphon circulation wash number of down fiber is 50 times.
The preparation of b modified solution
It is that the 90g deionized water of 13M Ω cm obtains mixed solution that the sulfate salt surfactant being 800 by 5g ammonium hydrogen sulfate, 2g formamide, 2.8g acetone and 0.2g relative molecular weight puts into conductance, then the temperature of mixed solution be increased to 98 DEG C and obtain modified solution after mechanical agitation 3h, wherein, stir speed (S.S.) is 1700r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated down fiber obtained through step a is put into the modified solution prepared through step b, temperature be 110 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 4h under being the condition of 0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated down fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed down fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 26 DEG C cleans that the down fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the down fiber embedded by ammonium salt molecule after cleaning 4min extends 8%, then the dry 2h of air dry oven that temperature is 80 DEG C is put into, obtain fracture strength and increase by 50%, elongation at break increases by 100%, and Young's modulus increases by the down fiber of 60%.
Embodiment 5
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by rabbit fur fibre absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 2h is 85 DEG C of dry 1h of drying box until the ether on rabbit fur fibre surface is removed, and obtains pretreated rabbit fur fibre, wherein, the siphon circulation wash number of rabbit fur fibre is 20 times.
The preparation of b modified solution
By 1g ammonium carbonate, 0.5gN, dinethylformamide, 0.9g acetone and 0.1g relative molecular weight be 1000 sulfosalt surfactant to put into conductance be that the 97.5g deionized water of 12M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 25 DEG C and obtain modified solution after mechanical agitation 4h, wherein, stir speed (S.S.) is 2000r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated rabbit fur fibre obtained through step a is put into the modified solution prepared through step b, temperature be 120 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 5h under being the condition of 0.101Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated rabbit fur fibre the large molecule in amorphous region between, obtain ammonium salt molecule embed rabbit fur fibre;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 28 DEG C cleans that the rabbit fur fibre that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the rabbit fur fibre embedded by ammonium salt molecule after cleaning 5min extends 9%, then the dry 1h of air dry oven that temperature is 85 DEG C is put into, obtain fracture strength and increase by 60%, elongation at break increases by 100%, and Young's modulus increases by the rabbit fur fibre of 70%.
Embodiment 6
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, absolute ether is adopted to carry out siphon circulation cleaning yak hair fiber, putting into temperature after cleaning 3h is that 90 DEG C of dry 2h of drying box are until the ether of yak hair fiber surface is removed, obtain pretreated yak hair fiber, wherein, the siphon circulation wash number of yak hair fiber is 30 times.
The preparation of b modified solution
By 70g carbonic hydroammonium, 10gN, N-dimethylacetylamide, 4.5g acetone and 0.5g relative molecular weight be 200 phosphate ester salt surfactant to put into conductance be that the 15g deionized water of 11M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 50 DEG C and obtain modified solution after mechanical agitation 5h, wherein, stir speed (S.S.) is 2300r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated yak hair fiber obtained through step a is put into the modified solution prepared through step b, temperature be 130 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 1h under being the condition of 0.151Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated yak hair fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed yak hair fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
Temperature put into by the yak hair fiber that the ammonium salt molecule prepared by step c embeds is that the deionized water of 30 DEG C cleans, the length drawing-off of the yak hair fiber embedded by ammonium salt molecule after cleaning 1min extends 10%, then the dry 2h of air dry oven that temperature is 90 DEG C is put into, obtain fracture strength and increase by 80%, elongation at break increases by 120%, and Young's modulus increases by the yak hair fiber of 70%.
Embodiment 7
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by silk fiber absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 4h is 80 DEG C of dry 1h of drying box until the ether on silk fiber surface is removed, and obtains pretreated silk fiber, wherein, the siphon circulation wash number of silk fiber is 40 times.
The preparation of b modified solution
Conductance put into by the phosphate ester salt surfactant being 400 by 40g ammonium phosphate, 7g formamide, 2.2g acetone and 0.8g relative molecular weight is that the 50g deionized water of 9M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 75 DEG C and obtain modified solution after mechanical agitation 3h, wherein, stir speed (S.S.) is 2600r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated silk fiber obtained through step a is put into the modified solution prepared through step b, temperature be 80 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 2h under being the condition of 0.201Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated silk fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed silk fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 32 DEG C cleans that the silk fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the silk fiber embedded by ammonium salt molecule after cleaning 2min extends 7%, then the dry 1h of air dry oven that temperature is 70 DEG C is put into, obtain fracture strength and increase by 50%, elongation at break increases by 90%, and Young's modulus increases by the silk fiber of 50%.
Embodiment 8
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by wool fibre absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 5h is 85 DEG C of dry 2h of drying box until the ether of wool surface is removed, and obtains pretreated wool fibre, wherein, the siphon circulation wash number of wool fibre is 50 times.
The preparation of b modified solution
By 20g ammonium hydrogen phosphate, 3gN, dinethylformamide, 1.5g acetone and 0.5g relative molecular weight be 400 sulfosalt surfactant to put into conductance be that the 75g deionized water of 7M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 90 DEG C and obtain modified solution after mechanical agitation 4h, wherein, stir speed (S.S.) is 3000r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated wool fibre obtained through step a is put into the modified solution prepared through step b, temperature be 90 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 3h under being the condition of 0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated wool fibre the large molecule in amorphous region between, obtain ammonium salt molecule embed wool fibre;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
Temperature put into by the wool fibre that the ammonium salt molecule prepared by step c embeds is that the deionized water of 18 DEG C cleans, the length drawing-off of the wool fibre embedded by ammonium salt molecule after cleaning 3min extends 8%, then the dry 2h of air dry oven that temperature is 80 DEG C is put into, obtain fracture strength and increase by 40%, elongation at break increases by 110%, and Young's modulus increases by the wool fibre of 70%.
Embodiment 9
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, absolute ether is adopted by down fiber to carry out siphon circulation cleaning, putting into temperature after cleaning 2h is that 90 DEG C of dry 1.5h of drying box are until the ether on down fiber surface is removed, obtain pretreated down fiber, wherein, the siphon circulation wash number of down fiber is 40 times.
The preparation of b modified solution
By 70g ammonium dihydrogen phosphate (ADP), 10gN, N-dimethylacetylamide, 4.5g acetone and 0.5g relative molecular weight be 800 phosphate ester salt surfactant to put into conductance be that the 15g deionized water of 5M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 25 DEG C and obtain modified solution after mechanical agitation 5h, wherein, stir speed (S.S.) is 800r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated down fiber obtained through step a is put into the modified solution prepared through step b, temperature be 100 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 4h under being the condition of 0.151Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated down fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed down fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 22 DEG C cleans that the down fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the down fiber embedded by ammonium salt molecule after cleaning 4min extends 9%, then the dry 2h of air dry oven that temperature is 75 DEG C is put into, obtain fracture strength and increase by 60%, elongation at break increases by 90%, and Young's modulus increases by the down fiber of 50%.
Embodiment 10
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, adopted by rabbit fur fibre absolute ether to carry out siphon circulation cleaning, putting into temperature after cleaning 5h is 90 DEG C of dry 2h of drying box until the ether on rabbit fur fibre surface is removed, and obtains pretreated rabbit fur fibre, wherein, the siphon circulation wash number of rabbit fur fibre is 50 times.
The preparation of b modified solution
By 1g diammonium hydrogen phosphate, 0.5gN, N-dimethylacetylamide, 0.9g acetone and 0.1g relative molecular weight be 1000 sulfate salt surfactant to put into conductance be that the 97.5g deionized water of 16M Ω cm obtains mixed solution, then the temperature of mixed solution be increased to 98 DEG C and obtain modified solution after mechanical agitation 5h, wherein, stir speed (S.S.) is 3000r/min.
C ammonium salt molecule embeds natural protein fiber
The pretreated rabbit fur fibre obtained through step a is put into the modified solution prepared through step b, temperature be 130 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 5h under being the condition of 0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated rabbit fur fibre the large molecule in amorphous region between, obtain ammonium salt molecule embed rabbit fur fibre;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 32 DEG C cleans that the rabbit fur fibre that the ammonium salt molecule prepared by step c embeds puts into temperature, the length drawing-off of the rabbit fur fibre embedded by ammonium salt molecule after cleaning 5min extends 10%, then the dry 2h of air dry oven that temperature is 90 DEG C is put into, obtain fracture strength and increase by 80%, elongation at break increases by 120%, and Young's modulus increases by the rabbit fur fibre of 70%.
Claims (6)
1. strengthen a method for natural protein fiber tensile mechanical properties, it is characterized in that, described method is carried out according to the following steps:
The preliminary treatment of a natural protein fiber
In soxhlet's extractor, absolute ether is adopted by natural protein fiber to carry out siphon circulation cleaning, putting into temperature after cleaning 2-5h is that the 80-90 DEG C of dry 1-2h of drying box is until the ether on natural protein fiber surface is removed, obtain pretreated natural protein fiber, wherein, the siphon circulation wash number of natural protein fiber is 20-50 time;
The preparation of b modified solution
By following mass percent:
Deionized water 15 ~ 97.5%
Ammonium salt 1 ~ 70%
The polar solvent 0.5 ~ 10% of amide bond
Acetone 0.9 ~ 4.5%
Low relative molecular weight anionic surfactant 0.1 ~ 0.5%
The polar solvent of ammonium salt, amide bond, acetone and low relative molecular weight anionic surfactant are put into deionized water and obtains mixed solution, then the temperature of mixed solution be increased to 25 ~ 98 DEG C and obtain modified solution after mechanical agitation 3-5h, wherein, stir speed (S.S.) is 800-3000r/min;
C ammonium salt molecule embeds natural protein fiber
The pretreated natural protein fiber obtained through step a is put into the modified solution prepared through step b, temperature be 80-130 DEG C, air pressure carries out High Temperature High Pressure immersion and swelling treatment 1-5h under being the condition of 0.101-0.270Mpa, under High Temperature High Pressure immersion and swelling effect, ammonium salt molecular diffusion in modified solution to pretreated natural protein fiber the large molecule in amorphous region between, obtain ammonium salt molecule embed natural protein fiber;
The cleaning of the natural protein fiber that d ammonium salt molecule embeds, micro-drawing-off and HEAT SETTING
It is that the deionized water of 18-32 DEG C cleans that the natural protein fiber that the ammonium salt molecule prepared by step c embeds puts into temperature, 5-10% is extended in the length drawing-off of the natural protein fiber embedded by ammonium salt molecule after cleaning 1-5min, then the dry 1-2h of air dry oven that temperature is 65-90 DEG C is put into, obtain fracture strength and increase 30-80%, elongation at break increases 60-120%, and Young's modulus increases the natural protein fiber of 30-70%.
2. a kind of method strengthening natural protein fiber tensile mechanical properties according to claims 1, is characterized in that: described natural protein fiber is the one in silk fiber or wool fibre or down fiber or rabbit fur fibre or yak hair fiber.
3. a kind of method strengthening natural protein fiber tensile mechanical properties according to claims 1, is characterized in that: the conductance≤16M Ω cm of described deionized water.
4. a kind of method strengthening natural protein fiber tensile mechanical properties according to claims 1, is characterized in that: described ammonium salt is the one in ammonium nitrate or ammonium chloride or ammonium sulfate or ammonium hydrogen sulfate or ammonium carbonate or carbonic hydroammonium or ammonium phosphate or ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate.
5. a kind of method strengthening natural protein fiber tensile mechanical properties according to claims 1, is characterized in that: the polar solvent of described amide bond is the one in formamide or DMF or DMA.
6. a kind of method strengthening natural protein fiber tensile mechanical properties according to claims 1, it is characterized in that: described low relative molecular weight anionic surfactant is the one in sulfate salt surfactant or sulfosalt surfactant or phosphate ester salt surfactant, and relative molecular weight is 200-1000.
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| CN106380701A (en) * | 2016-08-28 | 2017-02-08 | 安徽省华晟塑胶股份有限公司 | Automobile handgrip with high mechanical strength |
| CN106380656A (en) * | 2016-08-28 | 2017-02-08 | 安徽省华晟塑胶股份有限公司 | Car roof bracket |
| CN108178589A (en) * | 2017-12-30 | 2018-06-19 | 安徽城洁环境科技有限公司 | A kind of impact resistance water-permeable brick |
| CN108642873A (en) * | 2018-04-26 | 2018-10-12 | 海斯摩尔生物科技有限公司 | A method of crosslinking stretches enhancing chitin fiber in the swollen state |
| CN108660748A (en) * | 2018-04-26 | 2018-10-16 | 海斯摩尔生物科技有限公司 | A kind of method that enhancing chitin fiber is stretched under solvent swelling state |
| CN108893997A (en) * | 2018-06-01 | 2018-11-27 | 苏州先蚕丝绸有限公司 | A kind of preparation method being swollen natural silk fibrous material |
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| CN108893997A (en) * | 2018-06-01 | 2018-11-27 | 苏州先蚕丝绸有限公司 | A kind of preparation method being swollen natural silk fibrous material |
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