CN103923273B - The preparation method of modified fish oil albumen slurry and slurry - Google Patents
The preparation method of modified fish oil albumen slurry and slurry Download PDFInfo
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Abstract
The invention belongs to the modified protein Size Technology field that textile warp starching uses, disclose preparation method and the water-soluble good graft modification feather protein slurry under the neutral condition of preparation in this approach of a kind of modified fish oil albumen slurry. First the present invention selects suitable reductive agent that feather protein raw material is carried out pre-treatment, interrupts the disulfide linkage between Gelucystine in feather protein molecule as far as possible. Subsequently, under the initiation of suitable redox system, being grafted on feather protein molecular chain by a certain amount of hydrophilic monomer (such as vinylformic acid, acrylamide), can obtain under neutral condition can the molten grafting feather protein product of water. The obtained slurry of the inventive method (pH6.5-7.0) under neutral or solutions of weak acidity has good water-soluble, it is possible to obviously improves the use properties of slurry and protects the natural fiber yarns such as main starching object wool, silk by the infringement of alkaline agent.
Description
Technical field
The invention belongs to the modified protein Size Technology field that textile warp starching uses, particularly relate to preparation method and the water-soluble good graft modification feather protein slurry under the neutral condition of preparation in this approach of a kind of modified fish oil albumen slurry.
Background technology
Warp sizing is a most important operation in weaving production, and the textile manufacturing enterprise of China is usually referred to as " tiger mouth ", and external weaving academia was also once commented on: " sizing one minute, cloth machine class ". Spinning sizing agent is the essential material in warp sizing production process, and the annual consumption of China, about 300,000 tons, occupies the 2nd in the consumption of textile raw material, is only second to filamentary material. Slurry is normally made up of jointly tackiness agent and auxiliary agent, and tackiness agent is that a class has adhering material, is the material of main part of preparation slurries. Warp thread is after starching, and the main weavability relying on the tackiness agent in slurries to improve warp thread, reduces the end breakage rate of warp thread, it is ensured that carrying out smoothly of weaving process.
Along with the development of textile industry, the man-made fiber such as terylene, polyamide fibre, acrylic fibers are deep among the life of people day by day, but due to the non-renewable of petroleum-based products and close the reasons such as fine fabric wearing comfort is poor, the advantage of natural fiber (such as cotton, hair, silk) displays again, and the demand of natural fabric and consumption also present the trend risen year by year. Making a general survey of the existing sizing agent being applied to natural fiber, starch is one of kind the most important, accounts for about the 70% of spinning sizing agent total amount consumed. Starch is good to the sizing performance of natural fiber especially cellulosic fibre, environmentally friendly, but, worldwide " crisis in food " is increasingly serious, domestic provision price increased substantially in recent years especially, when the river rises the boat goes up for the price of starch, and the demand of " starching is without grain " seems again urgently; Polyvinyl alcohol (PVA) is also one of main slurry for natural fiber, and its consumption is only second to starch size, accounts for the 20% of spinning sizing agent total amount consumed. Due to the biodegradable performance extreme difference of PVA, being unfavorable for environment protection, more American-European countries are just classified as " not clean slurry " as far back as the beginning of this century and are forbidden, and spinning sizing agent circle of China also started to vigorously advocate in recent years and uses no or little PVA; And as the minimum polyacrylic size of consumption in three big slurries, although the elongation at break of its serous coat is higher, but film phonograph strength is very low, it is referred to as " soft and not hard " by professional person. In addition, sticky phenomenon is very serious again in the moisture absorption of polyacrylic size, and these defects make this slurry that other main slurry usually can only be assisted used in combination with small proportion. Due to the problems referred to above that main slurry in current textile sizing industry exists, from renewable agricultural byproducts, extract wide material sources, cheap macromolecular material become the task of top priority as the substitute species of now main slurry, only so, just can comply with environmental protection trend, promote the Sustainable development of textile sizing industry.
Warp sizing operation completes in water system, and this precondition being used as spinning sizing agent with regard to making a kind of macromolecular material possesses water-soluble or water dispersible. Feather is birds and the derivative of bird epidermic cell keratinization, accounts for the 10% of its body weight, and wherein the massfraction of protein (mainly Keratin sulfate) is more than 80%. According to guestimate, the feather by product that the annual processing of poultry industry of China and eider down production produce is more than 1,000,000 tons. Regrettable, this abundant renewable protein resource is usually ignored by people and is used as refuse treatment. In recent years, someone attempts feather protein is used for spinning sizing agent, but due to natural feather albumen, solvability is very poor in neutral conditions, only reliable add a large amount of alkaline agents and feather protein could be dissolved, and this kind of dissolving is that the molecular chain of feather protein interrupts acquisition, it it is substantially the proteolysis relying on alkaline agent and obtaining. During feather protein slurries are deployed into, strong basicity to yarn starching, first can the molecular weight of much slower feather protein, the force of cohesion of damage feather protein, brings disadvantageous effect to the mechanical mechanics property of its sizing performance especially sizing; Secondly, the natural fiber yarn (such as wool, silk) that some can be feared alkali by alkaline slurry brings major injury. A kind of feather protein just can be made in neutral conditions to be dissolved in the method for water therefore, it is necessary to develop, thus make it more to be suitable for being used as spinning sizing agent. There are some researches prove, the existence of disulfide linkage can bring disadvantageous effect to the water-soluble of feather protein and graft polymerization reaction. Some reductive agent (such as sodium bisulfite, sodium sulphite, mercaptoethanol) can effectively interrupt disulfide linkage.
Summary of the invention
The present invention is directed to problems of the prior art, it provides water-soluble good graft modification feather protein slurry under the neutral condition of the preparation method of a kind of modified fish oil albumen slurry and in this approach preparation.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
First the present invention selects suitable reductive agent that feather protein raw material is carried out pre-treatment, interrupts the disulfide linkage between Gelucystine in feather protein molecule as far as possible. Subsequently, under the initiation of suitable redox system, being grafted on feather protein molecular chain by a certain amount of hydrophilic monomer (such as vinylformic acid, acrylamide), can obtain under neutral condition can the molten grafting feather protein product of water. Because containing containing a large amount of carboxyls, amino and sulfydryl on the molecule of a large amount of hydroxyls, hair fibre on the molecule of cotton fibre, according to similar dissolve mutually theory, cotton, hair, silk fiber are all had good adhesivity by this grafting feather protein. In addition, feather protein intermolecular energy is by the disulfide bond crosslinking between hydrogen bond, salt type bond and Gelucystine, and this makes graft modification feather protein possess certain film forming ability. Therefore, the water-soluble branch modified fish oil albumen obtained by hydrophilic vinylic monomer being grafted on the feather protein molecular chain of reductive agent process, it is possible to become the bio-based macromolecular material to natural fiber sizing performance excellence.
Concrete grammar step is as follows:
Pre-treatment: use water as reaction medium, natural feather protein powder is made into the suspension that mass percent is 8%-10%, stir, heat up, after reaching 70 DEG C, in 10-15min, drip reductive agent, stir reduction 4h at keeping 70 DEG C, filter, fully after washing and drying obtained reductive agent process after feather albumen powder;
Preparation graft modification feather protein slurry: add water and above-mentioned feather albumen powder after reductive agent processes is made into the suspension that mass percent is 10%-15%; adopt organic acid that the pH value of suspension is adjusted to 3.0-4.0; drip under the protection of nitrogen and add vinyl monomer and initiator carries out graft polymerization reaction; stirring reaction 1-4 hour at 50-80 DEG C, filters, washs and obtained grafting feather protein slurry after drying.
As preferably, in described pre-treatment step, reductive agent adopts NaHSO3The aqueous solution, wherein NaHSO3Consumption be the 20%-30% of feather albumen powder quality.
As preferably, in described pre-treatment step, in suspension, the mass percent of feather protein is 5%-8%.
As preferably, described initiator adopts K2S2O8And NaHSO3, wherein, described K2S2O8With NaHSO3Mol ratio be 1:1.25-1:1.5. Graft copolymerization is undertaken by free radical triggering mechanism, and the chemical initiator used comprises heat decomposition type and oxidation-reduction type, when with K2S2O8And NaHSO3During for initiator, K2S2O8Consumption be the 10%-15% of feather protein quality, K2S2O8With NaHSO3Mol ratio be 1:1.25-1:1.5.
As preferably, in described preparation graft modification feather protein slurry stage, K2S2O8Consumption be the 10%-15% of feather albumen powder quality.
As preferably, in described preparation graft modification feather protein slurry stage, the mass percent of vinyl monomer and feather albumen powder is 20%-50%.
As preferably, described natural feather protein raw materials is selected from the Keratin sulfate extracted from poultry feather waste.
As preferably, described feather albumen powder is in pre-treatment and graft polymerization reaction process, and remains graininess in finished product. The preparation method of water-soluble good modified fish oil albumen involved in the present invention, after the percentage of grafting of feather protein-acrylic acid graft copolymer reaches 16%, grafting feather protein slurry pH=6.5-7.0 under neutrality or solutions of weak acidity can be made all to be dissolvable in water water.
Present invention also offers a kind of modified fish oil albumen slurry utilizing aforesaid method obtained.
The present invention, owing to have employed above technical scheme, has significant technique effect:
The present invention finds after a certain amount of hydrophilic vinylic monomer of grafting on reductive agent pretreated feather protein molecular chain, can improve the water-soluble of modified fish oil albumen slurry under neutral condition significantly.
Graft modification feather protein slurry prepared by the inventive method; compared with conventional feather protein slurry; outstanding feature is that (pH6.5-7.0) has good water-soluble under neutral or solutions of weak acidity, it is possible to obviously improves the use properties of slurry and protects the natural fiber yarns such as main starching object wool, silk by the infringement of alkaline agent. Therefore present invention efficiently solves the intrinsic problem that early stage, feather protein slurry existed, i.e. water-soluble poor problem under neutral condition.
Water-soluble good grafting feather protein slurry prepared by the present invention, is applicable to textile warp starching field. Feather protein is in reductive agent pre-treatment and graft polymerization reaction process, and remains graininess in finished product, easy to use.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
Embodiment 1
The natural feather albumen that dry weight is 100g is scattered in 1150g distilled water, it is mixed with the feather protein suspension that mass concentration is 8%, then moving into is equipped with in the three-necked flask of 2000mL of mechanical stirring, thermometer and dropping funnel, stir, heat up, after suspension reaches 70 DEG C, in 15min, drip reductive agent NaHSO3The aqueous solution, wherein NaHSO3Consumption be the 25% of feather protein quality, in whole suspension, the mass percent of feather protein is 6%, stirs reduction 4h, filters, with distilled water wash 2-3 time at keeping 70 DEG C, the feather protein after the obtained reductive agent process of recycling cooling driers drying;
Take the feather protein 50g obtained by above-mentioned reaction to add in 200g distilled water, it is made into the feather protein suspension that mass concentration is 20%, regulate reaction medium pH value as 3��4 taking acetum, move in the four neck flasks of 500ml. Flask is put into water bath with thermostatic control, loads onto agitator, thermometer, dropping funnel and nitrogen tube, lead to into nitrogen and stir, to get rid of in four mouthfuls of flasks the oxygen existed. By K2S2O8And NaHSO3It is made into the solution that massfraction is 9%��15%, K2S2O8Consumption be the 15%, K of feather protein quality2S2O8With NaHSO3Mol ratio be 1:1.5. Drip with three dropping funnels after suspension temperature reaches 60 DEG C of insulation 30min simultaneously and add Acrylic Acid Monomer (monomer mass in 2#-5# experiment is respectively the 20%, 30%, 40% and 50% of feather protein dry weight), K2S2O8The aqueous solution and NaHSO3The aqueous solution, the speed added is dripped in control, makes it to complete in 15min��20min, and whole polyreaction stirs 3.5h under the protection of nitrogen, adds the Resorcinol solution termination reaction of 10mL2%, filters, washs and the obtained product of drying. Water-soluble when pH=6.5 of the feather protein recorded by appearance method and spectrophotometry-acrylic acid graft copolymer slurry sees attached list 1.
The water soluble characteristic of table 1 feather protein-acrylic acid graft copolymer slurry
Remarks: in table 1, the mass percent of feather protein in dispersion/solution is 1%.
The adhesion property of cotton fibre is seen attached list 2 by feather protein-acrylic acid graft copolymer slurry respectively.
Table 2 feather protein-acrylic acid graft copolymer slurry is to the adhesion property of cotton fibre
Remarks: in table 2, the linear density of textile rove is 479tex.
Embodiment 2
Adopting the Methods and steps of embodiment 1, only change grafted monomer kind, change monomer into acrylamide, water-soluble when pH=6.5 of the feather protein recorded by appearance method and spectrophotometry-acrylamide grafted copolymer slurry sees attached list 3.
The water soluble characteristic of table 3 feather protein-acrylamide grafted copolymer slurry
Remarks: in table 3, the mass percent of feather protein in dispersion/solution is 1%.
The adhesion property of cotton fibre is seen attached list 4 by feather protein-acrylamide grafted copolymer slurry respectively.
Table 4 feather protein-acrylamide grafted copolymer slurry is to the adhesion property of cotton fibre
Remarks: in table 4, the linear density of textile rove is 479tex.
In a word, the foregoing is only the better embodiment of the present invention, all impartial changes done according to the present patent application patent scope, with modifying, all should belong to the covering scope of patent of the present invention.
Claims (9)
1. the preparation method of modified fish oil albumen slurry, it is characterised in that, comprise the following steps:
Pre-treatment: use water as reaction medium, natural feather protein powder is made into the suspension that mass percent is 8%-10%, stir, heat up, after reaching 70 DEG C, in 10-15min, drip reductive agent, stir reduction 4h at keeping 70 DEG C, filter, fully after washing and drying obtained reductive agent process after feather albumen powder;
Preparation graft modification feather protein slurry: add water and above-mentioned feather albumen powder after reductive agent processes is made into the suspension that mass percent is 10%-15%; adopt organic acid that the pH value of suspension is adjusted to 3.0-4.0; drip under the protection of nitrogen and add hydrophilic vinylic monomer and initiator carries out graft polymerization reaction; stirring reaction 1-4 hour at 50-80 DEG C, filters, washs and obtained grafting feather protein slurry after drying.
2. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: in described pre-treatment step, reductive agent adopts NaHSO3The aqueous solution, wherein NaHSO3Consumption be the 20%-30% of feather albumen powder quality.
3. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: in described pre-treatment step, in suspension, the mass percent of feather protein is 5%-8%.
4. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: described initiator adopts K2S2O8And NaHSO3, wherein, described K2S2O8With NaHSO3Mol ratio be 1:1.25-1:1.5.
5. the preparation method of modified fish oil albumen slurry according to claim 4, it is characterised in that: in described preparation graft modification feather protein slurry stage, K2S2O8Consumption be the 10%-15% of feather albumen powder quality.
6. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: in described preparation graft modification feather protein slurry stage, the mass percent of hydrophilic vinylic monomer and feather albumen powder is 20%-50%.
7. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: described natural feather protein raw materials is selected from the Keratin sulfate extracted from poultry feather waste.
8. the preparation method of modified fish oil albumen slurry according to claim 1, it is characterised in that: described feather albumen powder is in pre-treatment and graft polymerization reaction process, and remains graininess in finished product.
9. the modified fish oil albumen slurry utilizing claim 1-8 either method obtained.
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| CN201410109907.1A CN103923273B (en) | 2014-03-24 | 2014-03-24 | The preparation method of modified fish oil albumen slurry and slurry |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106519146B (en) * | 2016-10-31 | 2019-06-07 | 江南大学 | A method of discarded hair composite material is prepared using ionic liquid |
| CN106750043A (en) * | 2017-01-17 | 2017-05-31 | 绍兴文理学院 | A kind of feather protein graft copolymer slurry and preparation method thereof |
| CN106978723B (en) * | 2017-04-28 | 2019-09-03 | 江南大学 | A kind of Cottonseed Meal protein compound size preparation method |
| CN110845675B (en) * | 2019-11-06 | 2020-09-29 | 安徽工程大学 | Feather protein bio-based copolymer with independent hydrophilic and oleophylic graft branched chains, preparation method and application thereof |
| CN116459807B (en) * | 2023-05-26 | 2024-07-09 | 广东省科学院生物与医学工程研究所 | Modified keratin-based formaldehyde adsorbent and preparation method thereof |
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|---|---|---|---|---|
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102796232A (en) * | 2012-09-07 | 2012-11-28 | 山东大学 | Preparation method of feather-protein-base high-water-absorptivity resin |
| CN103087147A (en) * | 2013-01-05 | 2013-05-08 | 成都起点投资有限公司 | Method for preparing silk feather protein powder for preparation of protein filament |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102796232A (en) * | 2012-09-07 | 2012-11-28 | 山东大学 | Preparation method of feather-protein-base high-water-absorptivity resin |
| CN103087147A (en) * | 2013-01-05 | 2013-05-08 | 成都起点投资有限公司 | Method for preparing silk feather protein powder for preparation of protein filament |
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