CN1900413A - Acrylic fiber surface graft protein modified fiber and its producing method - Google Patents
Acrylic fiber surface graft protein modified fiber and its producing method Download PDFInfo
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- CN1900413A CN1900413A CN 200510044184 CN200510044184A CN1900413A CN 1900413 A CN1900413 A CN 1900413A CN 200510044184 CN200510044184 CN 200510044184 CN 200510044184 A CN200510044184 A CN 200510044184A CN 1900413 A CN1900413 A CN 1900413A
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Abstract
The present invention relates to a orlon surface grafting protein modified fibre and manufacturing method. It consists of orlon and protein, featuring that: skin core layer structure surface layer being vegetable protein grafting cover layer, core being orlon fiber, protein cover layer occupying 1-20 per cent of fiber total mass, core orlon occupying 80-90 per cent. Said manufacturing method is firstly to make orlon fiber surface hydrolysis into fiber containing carboxylic acid base group, then reaction with thionyl chloride, grafting with protein, to obtain surface covering protein layered fiber. The present invention made modified fibre surface consists of protein molecule having preferable human body affinity, hygroscopicity and antistatic property.
Description
Affiliated technical field
The present invention relates to a kind of on the acrylic fiber surface grafting tectal modified acrylic fibres of phytoprotein and manufacture method.
Background technology
Acrylic fibers are a kind of synthetic fiber, and it has characteristics such as good warmth retention property, dyeability and simulate wool, but acrylic fibers also have a lot of shortcomings, and are poor as hydrophily, easily produce static, human body compatibility difference etc.For improving the performance of acrylic fibers, the researcher has adopted several different methods that acrylic fiber is carried out the plant animal protein modification, as fibroin, milk protein graft polypropylene nitrile again spinning make modified acrylic fibers; Animal/vegetable protein and polyacrylonitrile blended spinning etc.It is exactly to need to build large-scale fibre spinning production line could produce that these methods have a common feature, thereby cost of investment is very big.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can overcome above-mentioned defective, technology is simple, cost of investment is low acrylic fiber surface graft protein modified fiber and manufacture method thereof.Its technology contents is:
A kind of acrylic fiber surface graft protein modified fiber, form by acrylic fibers and protein, it is characterized in that: core-skin layer structure, its superficial layer is a phytoprotein grafting cover layer, core is an acrylic fiber, the protein cover layer accounts for 1%～20% of total fiber mass, and the core acrylic fibers account for 80%～99% of total fiber mass.
Described acrylic fiber surface graft protein modified fiber, phytoprotein are the isolated proteins of separation and Extraction from the dregs of rice of soybean, peanut or cottonseed, and from various proteinaceous fruits the phytoprotein of separation and Extraction.
The manufacture method of described acrylic fiber surface graft protein modified fiber, it is characterized in that: the fiber that at first acrylic fiber is hydrolyzed into the carboxy-containing acid group, then with thionyl chloride reaction, the fiber of surface coverage protein layer is made in grafting in protein aqueous solution again.
The manufacture method of described acrylic fiber surface graft protein modified fiber, in hydrolyzing process, at first acrylic fiber is put into concentration and is 1%～30%, the NaOH alkaline aqueous solution of temperature 50～120 ℃ (preferably 80～100 ℃), hydrolysis 1～30 minute (preferably 5～15 minutes) is cleaned oven dry again and is obtained the hydrolyzed acrylic fiber.
The manufacture method of described acrylic fiber surface graft protein modified fiber, with the thionyl chloride reaction process in, earlier the acrylic fiber and the thionyl chloride solution of drying are cleaned in hydrolysis and together put into closed container, elevated temperature to 80～140 ℃ again, make the thionyl chloride gas reaction 1～60 minute of acrylic fiber and vaporization, the addition of thionyl chloride accounts for 1%～20% of acrylic fiber amount.
The manufacture method of described acrylic fiber surface graft protein modified fiber, with the thionyl chloride reaction process in, be that chlorination industry sulfolane solution is sprayed on the acrylic fiber of putting into closed container, to airtight good container heating, make the thionyl chloride vaporization then; Perhaps thionyl chloride solution is contained in the uncovered small container, again small container is put into the closed container that holds acrylic fiber, to airtight good container heating, make the thionyl chloride vaporization then.
The manufacture method of described acrylic fiber surface graft protein modified fiber, in chloride fiber and protein grafting operation, at first protein is made into concentration and is 0.1%～10% (preferably 1%～5%), PH is 8～13 alkaline aqueous solution, put into fiber by fiber and 1: 3～1: 10 bath raio of protein aqueous solution then, under 50～100 ℃ condition (preferably 80～90 ℃), react 1～30 minute (preferably 5～15 minutes).
The present invention compared with prior art, utilize the method for protein at the acrylic fiber surface graft modification, realize the protein surface modification effect of acrylic fiber, on the basis that keeps the original performance of acrylic fiber, give fiber again with new function, human body compatibility, hygroscopicity and the antistatic property of fiber are improved, thereby have higher surcharge and take performance.Characteristics such as it is simple and feasible that the present invention has implementation method, do not need to build large production equipment, only needs simple fiber aftertreatment equipment just can realize suitability for industrialized production, thereby also have the production small investment, and technology is simple, and production cost is low.
The specific embodiment
Embodiment 1:
(1) extract isolated protein: get dregs of beans and join in 15 times of water, with concentration be 10%, pH value is 9, temperature is to soak 5h in 30 ℃ the NaOH alkaline aqueous solution, mixing speed is 35 rev/mins in the immersion process, stops to stir after 30 minutes filtering with 60 mesh sieves; Residue adds 10 times of water more afterwards, with concentration be 10%, pH value is 8.5, temperature is to soak 90 minutes in 30 ℃ the NaOH alkaline aqueous solution.Twice filtered fluid merges the back and filters with 100 orders, leaches mixed liquor and adds 10% aqueous hydrochloric acid solution while stirring, transfers PH to 4.4, stops stirring, makes protein in isoelectric point quiescent setting 30 minutes, centrifugation.Isolated protein pH value is 5.5, temperature is 60 ℃ water flushing twice, and it is standby that vacuum drying is pulverized the back.
(2) hydrolyzed acrylic fiber: getting acrylic fiber, to join temperature by 1: 6 bath raio be 100 ℃, and concentration is in the middle of 2% the NaOH aqueous solution, and hydrolysis 20 minutes is taken out and cleaned oven dry and obtain the hydrolyzed acrylic fiber.
(3) the said hydrolyzed acrylic fiber is put into closed container, get thionyl chloride solution by 5% of fiber addition simultaneously and join in the uncovered glassware, together put into closed container.Closed container is warming up to 100 ℃, and reaction 30min opens closed container, takes out the acyl chloride reaction fiber, carries out grafting in the middle of directly joining the protein grafting aqueous solution that configures.
(4) grafting is 1: 5 amount preparation with protein aqueous solution by protein content 1%, fiber and aqueous solution bath raio, transfers pH value to 8, is warming up to 80 ℃, then, add the chloride fiber, stirring reaction 5 minutes, take out and clean oven dry, promptly obtain acrylic fibers graft modification fiber.The protein cover layer that records modified fibre accounts for 4% of total fiber mass, and the core acrylic fibers account for 96% of total fiber mass.
Embodiment 2:
(1) extract isolated protein: get the direct crushing grinding of a certain amount of soybean and become powder, join in the cyclohexane solvent in 1: 1 ratio, 55 ℃ of lixiviates 60 minutes, centrifugation or bundle were done, wet dregs of rice desolventizing in 100 ℃ of vacuum drying ovens.Then, defatted soy flour is added in 10 times of water, stir down with 10% hydrochloric acid the pH value transfer to 4.4,50 ℃ of constant temperature stirring and leaching 60 minutes sugar, ash content is molten goes centrifugation.And then with 10 times, 55 ℃ water separator is pressed last method and handle twice.Above-mentioned separator is added in 15 times of water, with NaOH solution adjust pH to 9.0,35 rev/mins were stirred 60 minutes, after stopping to stir 30 minutes, filter in 10 times of water of residue adding afterwards, with 60 orders with NaOH adjust pH to 8.5, under the similarity condition, lixiviate 90 minutes, twice filtrate merges back 100 orders and filters.Filter in the mixed liquor at twice and slowly to add 10% hydrochloric acid adjust pH to 4.4, protein is at isoelectric precipitation, and point electricity such as (note should stop to stir) solution arrival, static 20 to 30 minutes, so that precipitation is complete.Protein after the centrifugal dehydration is 50～60 ℃ of water flushings twice with pH value 5.5, temperature, and vacuum drying is standby.
(2) hydrolyzed acrylic fiber: getting acrylic fiber, to join temperature by 1: 8 bath raio be 90 ℃, and concentration is hydrolysis 15 minutes in the middle of 8% the NaOH aqueous solution, takes out to clean oven dry and obtain the hydrolyzed acrylic fiber.
(3) the said hydrolyzed acrylic fiber is put into closed container, get thionyl chloride solution by 10% of fiber addition simultaneously and join in the uncovered glassware, together put into closed container.Airtight good container is warming up to 105 ℃, reaction 20min.Open closed container, take out the acyl chloride reaction fiber, carry out grafting in the middle of directly joining the protein grafting aqueous solution that configures.
(4) grafting is 1: 6 amount preparation with protein aqueous solution by protein content 2%, fiber and aqueous solution bath raio, transfers pH value to 9, is warming up to 85 ℃, then, adds the chloride fiber, stirring reaction 10 minutes.Take out and clean oven dry, promptly obtain acrylic fibers graft modification fiber.The protein cover layer that records modified fibre accounts for 7.8% of total fiber mass, and the core acrylic fibers account for 92.2% of total fiber mass.
Embodiment 3:
(1) extract isolated protein: get peanut dregs and join in 15 times of water, with concentration be 10%, pH value is 9, temperature is to soak 3h in 50 ℃ the NaOH alkaline aqueous solution, 30 rev/mins of mixing speeds stop to stir after 30 minutes and filter with 80 mesh sieves; Residue adds 10 times of water more afterwards, transfers pH value to 9.0, similarity condition lixiviate 90 minutes.Twice filtered fluid merges the back and filters with 140 orders.Leach mixed liquor and add 10% aqueous hydrochloric acid solution while stirring, transfer PH to 4.5, stop to stir, make protein in isoelectric point quiescent setting 30 minutes, centrifugation.Isolated protein pH value is 5.5, temperature is 50 ℃ of water flushings twice, and it is standby that vacuum drying is pulverized the back.
(2) hydrolyzed acrylic fiber: getting acrylic fiber, to join temperature by 1: 10 bath raio be that 85 ℃, concentration are hydrolysis 10 minutes in the middle of 10% the NaOH aqueous solution, takes out and clean oven dry.
(3) the said hydrolyzed acrylic fiber is put into closed container, get thionyl chloride solution by 15% of fiber addition simultaneously and join in the uncovered glassware, together put into closed container.Airtight good container is warming up to 110 ℃, reaction 10min.Open closed container, take out the acyl chloride reaction fiber, carry out grafting in the middle of directly joining the protein grafting aqueous solution that configures.
(4) grafting is 1: 8 amount preparation with protein aqueous solution by protein content 2.5%, fiber and aqueous solution bath raio, transfers pH value to 8.0, is warming up to 90 ℃, then, adds the chloride fiber, stirring reaction 15 minutes.Take out and clean oven dry, promptly obtain acrylic fibers graft modification fiber.The protein cover layer that records modified fibre accounts for 12.4% of total fiber mass, and the core acrylic fibers account for 87.6% of total fiber mass.
Embodiment 4:
(1) extract isolated protein: get cotton cake dregs and join in 15 times of water, with concentration be 10%, pH value is 9, temperature is to soak 5h in 45 ℃ the NaOH alkaline aqueous solution, 35 rev/mins of mixing speeds stop to stir after 30 minutes and filter with 80 mesh sieves; Residue adds 10 times of water more afterwards, transfers pH value to 9.0, similarity condition lixiviate 90 minutes.Twice filtered fluid merges the back and filters with 100 orders.Leach mixed liquor and add 10% aqueous hydrochloric acid solution while stirring, transfer pH value to 4.4, stop to stir, make protein in isoelectric point quiescent setting 30 minutes, centrifugation.Isolated protein is 60 ℃ of water flushings twice with pH value 5.5, temperature, and it is standby that vacuum drying is pulverized the back.
(2) hydrolyzed acrylic fiber: getting acrylic fiber, to join temperature by 1: 12 bath raio be 80 ℃, and concentration is hydrolysis 5 minutes in the middle of 15% the NaOH aqueous solution, takes out and cleans oven dry.
(3) the said hydrolyzed acrylic fiber is put into closed container, get the thionyl chloride spray solution to fiber by 20% of fiber addition simultaneously.Airtight good container is warming up to 115 ℃, reaction 5min.Open closed container, take out the acyl chloride reaction fiber, carry out grafting in the middle of directly joining the protein grafting aqueous solution that configures.
(4) grafting is 1: 10 amount preparation with protein aqueous solution by protein content 3%, fiber and aqueous solution bath raio, transfers pH value to 9.0, is warming up to 95 ℃, then, adds the chloride fiber, stirring reaction 20 minutes.Take out and clean oven dry, promptly obtain acrylic fibers graft modification fiber.The protein cover layer that records modified fibre accounts for 17.6% of total fiber mass, and the core acrylic fibers account for 82.4% of total fiber mass.
Claims (8)
1, a kind of acrylic fiber surface graft protein modified fiber, form by acrylic fibers and protein, it is characterized in that: core-skin layer structure, its superficial layer is a phytoprotein grafting cover layer, core is an acrylic fiber, the protein cover layer accounts for 1%～20% of total fiber mass, and the core acrylic fibers account for 80%～99% of total fiber mass.
2, acrylic fiber surface graft protein modified fiber according to claim 1, it is characterized in that: phytoprotein is the isolated protein of separation and Extraction from the dregs of rice of soybean, peanut or cottonseed, and from various proteinaceous fruits the phytoprotein of separation and Extraction.
3, a kind of manufacture method of acrylic fiber surface graft protein modified fiber as claimed in claim 1, it is characterized in that: the fiber that at first acrylic fiber is hydrolyzed into the carboxy-containing acid group, then with thionyl chloride reaction, the fiber of surface coverage protein layer is made in grafting in protein aqueous solution again.
4, the manufacture method of acrylic fiber surface graft protein modified fiber according to claim 3, it is characterized in that: in the hydrolyzing process, at first acrylic fiber is put into concentration and is 1%～30%, the NaOH alkaline aqueous solution of 50～120 ℃ of temperature, hydrolysis 1～30 minute is cleaned oven dry again and is obtained the hydrolyzed acrylic fiber.
5, the manufacture method of acrylic fiber surface graft protein modified fiber according to claim 3, it is characterized in that: with the thionyl chloride reaction process in, earlier the acrylic fiber and the thionyl chloride solution of drying are cleaned in hydrolysis and together put into closed container, elevated temperature to 80～140 ℃ again, make the thionyl chloride gas reaction 1～60 minute of acrylic fiber and vaporization, the addition of thionyl chloride accounts for 1%～20% of acrylic fiber amount.
6, the manufacture method of acrylic fiber surface graft protein modified fiber according to claim 5 is characterized in that: the thionyl chloride spray solution is being put on the acrylic fiber of closed container, to airtight good container heating, made the thionyl chloride vaporization then.
7, the manufacture method of acrylic fiber surface graft protein modified fiber according to claim 5, it is characterized in that: thionyl chloride solution is contained in the uncovered small container, again small container is put into the closed container that holds acrylic fiber, to airtight good container heating, make the thionyl chloride vaporization then.
8, the manufacture method of acrylic fiber surface graft protein modified fiber according to claim 3, it is characterized in that: in chloride fiber and protein grafting operation, at first protein is made into concentration and is 0.1%～10%, PH is 8～13 alkaline aqueous solution, put into fiber by fiber and 1: 3～1: 10 bath raio of protein aqueous solution then, under 50～100 ℃ condition, reacted 1～30 minute.
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Cited By (11)
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| CN101831806A (en) * | 2010-05-05 | 2010-09-15 | 山东理工大学 | Manufacturing method of protein modified fiber in acrylic fiber surface ingrafted bean juice |
| CN103266381A (en) * | 2013-05-31 | 2013-08-28 | 东华大学 | Preparation method for moisture-absorbing and heat-radiating polyacrylonitrile yarn |
| CN103866572A (en) * | 2012-12-14 | 2014-06-18 | 罗莱家纺股份有限公司 | Acrylic fiber rich in amino acids, preparing method thereof, applications thereof and quilt core |
| CN105862165A (en) * | 2016-06-20 | 2016-08-17 | 苗晓光 | Protein-modified acrylic fiber spinning solution with phase-change temperature regulating function and preparation method thereof |
| CN105951421A (en) * | 2016-05-13 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of soy protein modified lotus fiber fabric |
| CN108070262A (en) * | 2017-12-29 | 2018-05-25 | 常州市阿曼特化工有限公司 | A kind of preparation method of tensile type gelatin film |
| CN108442110A (en) * | 2018-04-09 | 2018-08-24 | 武汉纺织大学 | A kind of amino acid covalent coupling modified milk protein fiber material and preparation method thereof |
| CN108978213A (en) * | 2018-06-27 | 2018-12-11 | 苏州市天翱特种织绣有限公司 | A kind of method of modifying of flax fiber |
| CN109735952A (en) * | 2018-12-29 | 2019-05-10 | 合肥必更赢科技有限公司 | A kind of wear-resisting milk protein fiber and its fabric preparation method, application |
| CN110067134A (en) * | 2019-05-23 | 2019-07-30 | 叶盛 | The preparation method of intelligent thermoregulating microcapsules cyst membrane and its application in textile |
| CN114232337A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Double-protein acrylic fiber and preparation method thereof |
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| US5208075A (en) * | 1990-09-15 | 1993-05-04 | Basf Aktiengesellschaft | Sizing agent for staple fiber and filament yarns |
| US5593779A (en) * | 1994-06-15 | 1997-01-14 | Kao Corporation | Fiber for clothing and production method therefor |
| JPH08199481A (en) * | 1995-01-18 | 1996-08-06 | Mitsubishi Rayon Co Ltd | Production of wool-like acrylic fiber fabric having durable pill resistance |
| JP2004360147A (en) * | 2003-06-09 | 2004-12-24 | Takamatsu Oil & Fat Co Ltd | Fiber-treating composition |
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| CN101831806A (en) * | 2010-05-05 | 2010-09-15 | 山东理工大学 | Manufacturing method of protein modified fiber in acrylic fiber surface ingrafted bean juice |
| CN103866572A (en) * | 2012-12-14 | 2014-06-18 | 罗莱家纺股份有限公司 | Acrylic fiber rich in amino acids, preparing method thereof, applications thereof and quilt core |
| CN103266381A (en) * | 2013-05-31 | 2013-08-28 | 东华大学 | Preparation method for moisture-absorbing and heat-radiating polyacrylonitrile yarn |
| CN103266381B (en) * | 2013-05-31 | 2015-06-24 | 东华大学 | Preparation method for moisture-absorbing and heat-radiating polyacrylonitrile yarn |
| CN105951421B (en) * | 2016-05-13 | 2018-10-16 | 王珍丽 | A kind of preparation method of Soybean Protein Modification lotus fabric |
| CN105951421A (en) * | 2016-05-13 | 2016-09-21 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of soy protein modified lotus fiber fabric |
| CN105862165A (en) * | 2016-06-20 | 2016-08-17 | 苗晓光 | Protein-modified acrylic fiber spinning solution with phase-change temperature regulating function and preparation method thereof |
| CN105862165B (en) * | 2016-06-20 | 2017-10-17 | 苗晓光 | A kind of protein modified acrylic fiber spinning solution with phase-changing and temperature-regulating function and preparation method thereof |
| CN108070262A (en) * | 2017-12-29 | 2018-05-25 | 常州市阿曼特化工有限公司 | A kind of preparation method of tensile type gelatin film |
| CN108442110A (en) * | 2018-04-09 | 2018-08-24 | 武汉纺织大学 | A kind of amino acid covalent coupling modified milk protein fiber material and preparation method thereof |
| CN108442110B (en) * | 2018-04-09 | 2019-12-03 | 武汉纺织大学 | A kind of amino acid covalent coupling modified milk protein fiber material and preparation method thereof |
| CN108978213A (en) * | 2018-06-27 | 2018-12-11 | 苏州市天翱特种织绣有限公司 | A kind of method of modifying of flax fiber |
| CN108978213B (en) * | 2018-06-27 | 2020-11-06 | 上海兆妩品牌管理有限公司 | Modification method of flax fibers |
| CN109735952A (en) * | 2018-12-29 | 2019-05-10 | 合肥必更赢科技有限公司 | A kind of wear-resisting milk protein fiber and its fabric preparation method, application |
| CN109735952B (en) * | 2018-12-29 | 2022-04-01 | 湖州草本源新材料有限公司 | Wear-resistant milk protein fiber and fabric preparation method and application thereof |
| CN110067134A (en) * | 2019-05-23 | 2019-07-30 | 叶盛 | The preparation method of intelligent thermoregulating microcapsules cyst membrane and its application in textile |
| CN114232337A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Double-protein acrylic fiber and preparation method thereof |
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