阅读说明：本技术 一种亲/疏水羽毛蛋白生物基共聚物及其制备方法和应用 (Hydrophilic/hydrophobic feather protein bio-based copolymer and preparation method and application thereof ) 是由 李伟 丁小翠 吴有康 余征宇 吴杰 张正桥 徐珍珍 张国禹 于 2019-11-06 设计创作，主要内容包括：本发明公开了一种亲/疏水羽毛蛋白生物基共聚物及其制备方法和应用,以烯丙基磺酸钠作为亲水性接枝单体,以丙烯酸甲酯作为疏水性接枝单体,采用先将亲水性接枝单体或疏水性接枝单体中的一种接枝到羽毛蛋白分子链上,再将另外一种亲水性接支单体或疏水性接枝单体接枝到羽毛蛋白分子链上的两步接枝共聚方法对羽毛蛋白进行接枝共聚改性处理,制备得到的羽毛蛋白生物基浆料具有独立的亲水性接枝支链和疏水性接枝支链,在中性pH环境下和温水中可以完全溶解,具有很好的水溶性,同时对聚乳酸粗纱具有非常好的低温粘附性能,更加适用于聚乳酸经纱的低温上浆。(The invention discloses a hydrophilic/hydrophobic feather protein bio-based copolymer and a preparation method and application thereof, sodium allylsulfonate is used as a hydrophilic grafting monomer, methyl acrylate is used as a hydrophobic grafting monomer, the feather protein is grafted, copolymerized and modified by a two-step grafting copolymerization method of firstly grafting one of the hydrophilic grafting monomer or the hydrophobic grafting monomer to a feather protein molecular chain and then grafting the other hydrophilic grafting monomer or the hydrophobic grafting monomer to the feather protein molecular chain, and the prepared feather protein bio-based slurry has independent hydrophilic grafting branched chain and hydrophobic grafting branched chain, the polylactic acid roving can be completely dissolved in warm water in a neutral pH environment, has good water solubility, has good low-temperature adhesion performance to the polylactic acid roving, and is more suitable for low-temperature sizing of polylactic acid warp yarns.)

1. The hydrophilic/hydrophobic feather protein bio-based copolymer is characterized in that the hydrophilic/hydrophobic feather protein bio-based copolymer slurry is provided with independent hydrophilic polyallyl sodium sulfonate and hydrophobic polymethyl acrylate grafted branched chains, the two grafted branched chains are grafted to sulfydryl of a protein molecular chain, and the molecular structure is as follows:

2. the method for preparing the lipotropic/hydrophobic feather protein bio-based copolymer of claim 1, which comprises the following steps:

(1) extracting feather protein: washing feather, drying, smashing to obtain feather powder, adding the feather powder into an ethanol and hydrochloric acid aqueous solution, heating, stirring, performing suction filtration, washing for a plurality of times, drying, adding a reducing agent aqueous solution into the feather powder, heating, stirring, performing suction filtration, adding an aqueous solution of urea, alkali and a surface active substance, heating, stirring, centrifuging, taking supernate, adding a hydrochloric acid aqueous solution, adjusting the pH value to 2.0-5.0, precipitating feather protein, washing the precipitate for a plurality of times by ethanol, and performing freeze drying to obtain feather protein;

(2) preparation of lipotropic/hydrophobizing feather protein bio-based copolymer: putting the feather protein extracted in the step (1) into a urea solution, stirring under a water bath condition to completely dissolve the protein, introducing nitrogen, adding a reducing agent, stirring, simultaneously dropwise adding an initiator and a hydrophilic grafting monomer or a hydrophobic grafting monomer, reacting for 1-5 hours, introducing nitrogen again, simultaneously dropwise adding an initiator and another hydrophilic grafting monomer or hydrophobic grafting monomer, reacting for 1-5 hours, performing acid precipitation, washing with ethanol, and drying in a freeze dryer to obtain the feather protein grafted bio-based copolymer.

3. The method for preparing the hydrophilic/hydrophobic feather protein bio-based copolymer as claimed in claim 2, wherein the heating and stirring in step (1) is water bath heating, the water bath temperature is 50-100 ℃, the stirring time is 0.5-5h, the ethanol is 4-15 times the volume of the feather meal, and the hydrochloric acid is added in an amount of 15-50% of the weight of the feather meal.

4. The method for preparing the hydrophilic/hydrophobic feather protein bio-based copolymer of claim 2, wherein the reducing agent in step (2) is sodium bisulfite, the surface active substance is sodium dodecyl sulfate, and the amounts of urea, alkali and surface active substance added are 0.5-3 times, 5-20% and 15-50% of the weight of feather meal respectively.

5. The method for preparing the hydrophilic/hydrophobic feather protein bio-based copolymer of claim 2, wherein the hydrophilic grafting monomer in step (2) is sodium allylsulfonate, the hydrophobic grafting monomer is methyl acrylate, the initiator is ammonium persulfate, the reducing agent is sodium bisulfite, and the concentration of the urea solution is 8 mol/L.

6. The method for preparing the hydrophilic/hydrophobic feather protein bio-based copolymer as claimed in claim 2, wherein the total amount of sodium allylsulfonate and methyl acrylate used in step (2) is 40% of the feather protein, wherein the mass percent of sodium allylsulfonate to feather protein is 28.6-37.5%, and the mass percent of methyl acrylate to feather protein is 2.5-11.4%.

7. The method for preparing the lipotropic/hydrophobic feather protein bio-based copolymer of claim 5, wherein the molar ratio of the sodium allylsulfonate to the methyl acrylate in the step (2) is 90:10 to 60: 40.

8. The preparation method of the hydrophilic/hydrophobic feather protein bio-based copolymer as claimed in claim 5, wherein the amount of ammonium persulfate is 20% of the feather protein mass, wherein the amount of ammonium persulfate during the grafting reaction of the sodium allylsulfonate monomer is 12% -18% of the feather protein mass, and the amount of ammonium persulfate during the grafting reaction of the methyl acrylate is 2% -8% of the feather protein mass.

9. Use of the lipo/hydrophobin bio-based copolymer according to claim 1, characterised in that the lipo/hydrophobin bio-based copolymer is used as a size for sizing textile warp yarns.

10. The use of the lipo/hydrophobin bio-based copolymer according to claim 1, wherein the textile warp yarn is a polylactic acid warp yarn.

Technical Field

The invention belongs to the technical field of protein modification, and particularly relates to a hydrophilic/hydrophobic feather protein bio-based copolymer, and a preparation method and application thereof.

Background

Textile size is an indispensable material in the sizing process of the whole textile industry. In the production process of textile cloth, warp and weft yarns need to be interwoven into the cloth through a weaving process, and warp sizing is a key process in the weaving process. If good sizing cannot be realized, weaving cannot be smoothly carried out, a large amount of warp yarns are lost, production is seriously influenced, and great economic loss is caused.

Currently, the slurries used on the market are mainly starches, polyvinyl alcohol (PVA) and polyacrylic acids. The starch size is used as the main size of warp sizing, the consumption is large and accounts for more than 70% of the total consumption of the size, and the warp sizing agent has the advantages of wide source, low price, good adhesion to hydrophilic natural fibers, easy biodegradation and the like. However, the worldwide 'grain crisis' has become more severe, the domestic grain price has increased greatly in recent years, the price of starch is also high in water-rising ships, and the demand of 'starching without using grain' is urgent. In addition, starch slurry is aged at low temperature, poor in adhesion and brittle and hard in a formed slurry film, so that the use effect of the starch slurry is unsatisfactory, and therefore, in order to improve the use performance of the starch, a great deal of technical research is carried out by scientific research technicians, but the improvement of the use effect is limited, and the starch slurry is only suitable for warp sizing of low count yarns. It cannot be used alone on high count yarns, and is usually used in combination with PVA. However, since PVA has extremely poor biodegradability and is not favorable for environmental protection, it has been classified as "dirty slurry" and prohibited in some countries in the European and American countries. The textile size sector in our country has also started to advocate heavily in recent years the use of no or little PVA. Therefore, the development of environment-friendly high-performance slurry to replace PVA has become a development trend in the future.

The feather is from aquatic bird breeding companion, belongs to the natural protein category, and has the advantages of rich source, low raw material price and the like; china is a big country for feather down production, and the yield of feather down raw materials accounts for more than 80% of the world. According to rough statistics, about 100 million tons of down feather wastes are generated in poultry processing industry and down feather manufacturing industry every year in China, the content of protein (mainly keratin) in the wastes is more than 80%, the abundant renewable protein resources are often ignored by people as garbage treatment, and the traditional treatment methods (such as incineration and landfill) are adopted, so that the protein characteristic problem of the waste down feather is difficult to degrade in a short time, the environment is greatly burdened, and the environment pollution problem is generated. Therefore, if feather protein in feather down can be extracted, and a chemical modification technology is utilized, the regulation and control of the performance and the molecular structure of a novel protein material are realized, novel high-performance environment-friendly bio-based protein slurry which can be used as textile slurry is obtained, and the industrialization of the bio-based protein slurry is cultivated. The method is a great measure for changing waste feather down into valuable, not only cultivates a new economic growth point, but also further extends the economy of the feather down. The down economy is a green economy, compared with other industrial economies, the down economy has the characteristics of less energy consumption, less environmental pollution and large value-added potential, and is beneficial to the sustainable development of the economy in China.

At present, the research on applying feather protein bio-based graft copolymer as sizing agent to warp sizing is still in the laboratory exploration stage, and systematic research is lacked. Meanwhile, due to the fact that a proper amount of alkali liquor needs to be added in the dissolving process of feather protein, when the feather protein slurry is used for sizing alkaline yarns (wool yarns, polylactic acid yarns and the like), the technical problem that the cohesive strength of a feather protein serous membrane covered on the surface of warp yarns is greatly reduced due to the hydrolysis of alkali is easily caused, Chinese patent with patent application number 201410109907.1 discloses a modified feather protein slurry, hydrophilic monomer acrylic acid is grafted on the molecular chain of the feather protein subjected to reduction pretreatment, so that the feather protein is endowed with water solubility under a neutral condition, the technical problem caused by dissolving the feather protein by adding alkali is avoided, but because the feather protein is subjected to single hydrophilic grafting modification, it is only suitable for hydrophilic warp yarns, not for hydrophobic warp yarns, and furthermore it is not suitable for some warp yarns that require low temperature sizing (e.g. polylactic acid warp yarns). The polylactic acid warp yarns have poor cohesion, are easy to tangle and bond, and are not high in temperature resistance, so that the polylactic acid warp yarns have to undergo a sizing procedure before weaving, and a low-temperature sizing mode is adopted, so that the development of the feather protein bio-based sizing agent suitable for sizing the polylactic acid warp yarns is of great significance.

Disclosure of Invention

Aiming at the problems, the invention provides an hydrophilic/hydrophobic feather protein bio-based copolymer, a preparation method thereof and application thereof in textile sizing agent.

One of the technical schemes of the invention is as follows: providing an hydrophilic/hydrophobic feather protein bio-based copolymer, wherein the hydrophilic/hydrophobic feather protein bio-based copolymer slurry is provided with independent hydrophilic polyallyl sodium sulfonate and hydrophobic polymethyl acrylate grafted branched chains, the two grafted branched chains are grafted to sulfydryl of a protein molecular chain, and the molecular structure is as follows:

the second technical scheme of the invention is as follows: the preparation method of the lipotropic/hydrophobic feather protein bio-based copolymer comprises the following steps:

(1) extracting feather protein: washing feather, drying, smashing to obtain feather powder, adding the feather powder into an ethanol and hydrochloric acid aqueous solution, heating, stirring, performing suction filtration, washing for a plurality of times, drying, adding a reducing agent aqueous solution into the feather powder, heating, stirring, performing suction filtration, adding an aqueous solution of urea, alkali and a surface active substance, heating, stirring, centrifuging, taking supernate, adding a hydrochloric acid aqueous solution, adjusting the pH value to 2.0-5.0, precipitating feather protein, washing the precipitate for a plurality of times by ethanol, and performing freeze drying to obtain feather protein;

(2) preparation of lipotropic/hydrophobizing feather protein bio-based copolymer: putting the feather protein extracted in the step (1) into a urea solution, stirring under a water bath condition to completely dissolve the protein, introducing nitrogen, adding a reducing agent, stirring, simultaneously dropwise adding an initiator and a hydrophilic grafting monomer or a hydrophobic grafting monomer, reacting for 1-5 hours, introducing nitrogen again, simultaneously dropwise adding an initiator and another hydrophilic grafting monomer or hydrophobic grafting monomer, reacting for 1-5 hours, performing acid precipitation, washing with ethanol, and drying in a freeze dryer to obtain the feather protein grafted bio-based copolymer.

Introducing nitrogen to mainly expel air in a reaction system, playing a role in nitrogen protection during a grafting reaction, and because feather protein is insoluble in water, the prepared feather protein needs to be completely dissolved in a urea solution at 50-80 ℃, adding a reducing agent for treatment so as to increase the number of sulfydryl on a molecular chain of the feather protein, then dropwise adding an initiator and a grafting monomer, wherein the initiator and the sulfydryl on the feather protein generated by the treatment of the reducing agent form a redox system, and further grafting a hydrophilic or hydrophobic monomer onto the molecular chain of the feather protein, so that the grafting copolymerization modification treatment of the feather protein is realized, and the feather protein bio-based copolymer with independent hydrophilic and hydrophobic grafting branched chains is prepared.

Further, the heating and stirring in the step (1) is water bath heating, the water bath temperature is 50-100 ℃, the stirring time is 0.5-5h, the volume of ethanol is 4-15 times of the volume of the feather powder, and the adding amount of hydrochloric acid is 15-50% of the weight of the feather powder.

Further, the reducing agent in the step (1) is sodium bisulfite, the surface active substance is sodium dodecyl sulfate, and the adding amounts of the urea, the alkali and the surface active substance are respectively 0.5-3 times, 5-20% and 15-50% of the weight of the feather powder.

Further, the hydrophilic grafting monomer in the step (2) is sodium allylsulfonate, the hydrophobic grafting monomer is methyl acrylate, the initiator is ammonium persulfate, the reducing agent is sodium bisulfite, and the concentration of the urea solution is 8 mol/L.

Further, the total amount of the sodium allylsulfonate and the methyl acrylate in the step (2) is 40% of the feather protein amount, wherein the mass percentage of the sodium allylsulfonate to the feather protein is 28.6% -37.5%, and the mass percentage of the methyl acrylate to the feather protein is 2.5% -11.4%.

Further, the molar ratio of the sodium allylsulfonate to the methyl acrylate in the step (2) is 90:10-60:40 respectively.

Further, the using amount of the initiator is 20% of the feather protein, wherein the using amount of ammonium persulfate in the grafting reaction process of the sodium allylsulfonate monomer is 12% -18% of the feather protein, and the using amount of ammonium persulfate in the grafting reaction process of the methyl acrylate is 2% -8% of the feather protein.

In the third technical scheme of the invention, the hydrophilic/hydrophobic feather protein bio-based copolymer is used as sizing agent in textile warp sizing.

Further, the textile warp yarns are polylactic acid warp yarns.

The invention introduces hydrophilic and hydrophobic grafting branch chains on the feather protein molecular chain simultaneously, improves the bonding effect of the feather protein on polylactic acid warp yarn while improving the water solubility of the protein, and develops the feather protein bio-based slurry with independent hydrophilic and lipophilic grafting branch chains suitable for low-temperature sizing of polylactic acid.

Taking sodium allylsulfonate and methyl acrylate as an example, firstly hydrophilic grafting is carried out, and then hydrophobic grafting is carried out, the two-step grafting reaction equation of the invention is as follows:

the first step is as follows: grafting reaction of feather protein and sodium allylsulfonate:

the second step is that: further grafting reaction with methyl acrylate:

compared with the prior art, the technical scheme of the invention has the following beneficial effects:

1) according to the invention, a hydrophilic or hydrophobic grafting branched chain is firstly connected, and then another hydrophobic or hydrophilic grafting branched chain is connected, so that the same grafting branched chain connected to the feather protein only contains one structural unit (the grafting branched chain only contains a hydrophilic structural unit and the grafting branched chain only contains a hydrophobic structural unit), and the effect of the grafting branched chain is better exerted.

2) The feather protein-polyallyl sodium sulfonate-polymethyl acrylate bio-based sizing agent prepared by the method has independent hydrophilic grafted branched chains and hydrophobic grafted branched chains, can be completely dissolved in water at the temperature of 60 ℃ and the pH value is neutral, has very good water solubility, has very good low-temperature adhesion performance to polylactic acid roving, and is completely suitable for low-temperature sizing of polylactic acid warp yarns.

Drawings

FIG. 1 is a flow chart of the feather protein extraction process of the present invention;

FIG. 2 is an infrared spectrum of the feather protein (a) extracted and the feather protein bio-based slurry (b) prepared in example 1;

FIG. 3 is a scanning electron micrograph of the extracted feather protein;

FIG. 4 is a scanning electron micrograph of the feather protein bio-based slurry prepared.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.