CN100436708C - Method for modifying gluten protein used as paper strengthening agent - Google Patents
Method for modifying gluten protein used as paper strengthening agent Download PDFInfo
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- CN100436708C CN100436708C CNB2006101237607A CN200610123760A CN100436708C CN 100436708 C CN100436708 C CN 100436708C CN B2006101237607 A CNB2006101237607 A CN B2006101237607A CN 200610123760 A CN200610123760 A CN 200610123760A CN 100436708 C CN100436708 C CN 100436708C
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- gluten protein
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Abstract
The invention discloses a method of modifying gluten to making paper intensifier. The method includes the following steps: (1) hydroxylation: glutening the gluten powder into regulating suspension, regulating the pH of the reaction system to 2-6 with acid liquor, controlling the reaction temperature in 20~100degreeC water bath, dropping formaldehyde which weight is 5 ~ 15% of gluten powder slowly, reaction 1~8 hours then collecting the intermediate product. (2) cationised reaction: dropping epichlorohydrin which consumption is 1~10% of gluten weight into intermediate product slowly in 20~100degreeC water bath, reaction 1~4 hours and getting the lacte gluten liquid change. The invention synthesizes the products with the raw materials of plant protein which is renewable resources and with biocompatibility; it does not bring secondary pollution, provides a new channels for the processing of agricultural producing by-product utilization of high-value, the synthesized paper fiber intensifier makes the dry tensile index in paper increases more then 35% and the rate of wet strength retention is more then 20%.
Description
Technical field
The present invention relates to the paper strengthening agent of paper technology, particularly a kind of preparation method from paddy Ruan albumen composed paper reinforcing agent is specifically related to the method for modifying gluten protein as paper strengthening agent.
Background technology
Gluten protein (gluten) is the accessory substance of cereal starch processing, contains albumin, globulin, gliadin and four kinds of protein of glutenin, a kind of biodegradable, reproducible natural polymer.Less to its development and use both at home and abroad at present, be scarcely out of swaddling-clothes in the research of China's gluten protein, mainly in the field of food utilization, for example add and make strong muscle noodles, face volume etc. in the flour; Do not see the research report and have than the industrial utilization of high added value.Because the viscoplasticity of gluten protein uniqueness, extensibility, film forming, thermocoagulation etc. not only can be used at field of food, also can be the substitute as some expensive material.Along with wheat, corn yield improve day by day, the amount of this accessory substance improves greatly, develops this renewable gluten protein and prepares Biodegradable material or chemicals, and high-valued and environmental protection is extremely important to plant resources.
The single order molecular structure of gluten protein is a polypeptide, and has the glutamy amino acid more than 50%, reunite easily, and water-soluble and dispersed relatively poor, be difficult for directly as the fiber bond, as paper strengthening agent.Do not find any with the report of gluten protein as paper strengthening agent yet.
Summary of the invention
The object of the present invention is to provide a kind of method for modifying gluten protein as paper strengthening agent, according to the contained chemical group of gluten protein, specific aim is transformed, reducing albumen self reunites, increase cationic group, the synthetic chemical assistant that combines with string can strengthen doing by force with wet strong of paper.
The principle of the invention: protein molecular is disperseed, and connect suitable chemical group, be beneficial to bonding between the fiber, make fiber enhancer with biocompatibility.
The object of the invention is achieved through the following technical solutions.
A kind of method for modifying gluten protein as paper strengthening agent comprises the steps and process conditions:
(1) hydroxymethylation: thermostat is being housed, add the gluten protein powder in the there-necked flask of agitator and feeder, be adjusted to the turbid liquid of 1%～10% weight percent concentration, pH is 2～6 with formic acid conditioned reaction system, 20～100 ℃ of following water-baths, slowly dripping consumption is the formaldehyde of gluten protein grain weight amount 5～15%, reacts 1～8 hour, collects intermediate product;
(2) cationization reaction: under 20～100 ℃ of water-baths, slowly dripping consumption in the intermediate product is the epoxychloropropane of paddy Ruan albumen powder weight 1～10%, reacts 1～4 hour, in the course of reaction, the epoxychloropropane of insoluble in water fades away, and milk yellow albumen keeps liquid and becomes more thorough.Reaction finishes back gluten protein liquid and becomes oyster white.
Making paddy modification PrPC can dissolve each other with arbitrary proportion with water; The pH value is 4.5～5.5; Solid content is 3～5%; Room temperature deposit do not become turbid in 6 months, gelatin phenomenon.
For further realizing purpose of the present invention, the pH of described step is preferably 3.Described step (1) reaction temperature is preferably 70 ℃.Described step (1) formaldehyde consumption is preferably 8% of gluten protein grain weight amount.Described step (1) reaction time is preferably 6 hours.Reaction temperature is preferably 60 ℃ in the described step (2).The reaction time is preferably 2 hours in the described step (2).
The present invention has following advantage and beneficial effect:
(1), biocompatibility: this product is to be that raw material is synthetic from the renewable resource vegetable protein, has biocompatibility; Can not bring secondary pollution.
(2), agricultural and sideline product is high-valued: this Products Development will provide new way for processing of farm products accessory substance higher value application, the composed paper fiber enhancer.
(3), performance parameter is good: dried tensile index has improved more than 35% in the paper, and wet strength retention is more than 20%.
The specific embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
The mensuration of paper making and paper strength character:
Slurry is transferred to 0.5%, press oven dry stock weight 1% and add modified product, behind the 5min that stirs, manufacturing paper with pulp according to the TAPPI standard quantitatively is 60g/m
2Pattern.Behind 105 ℃ of following slaking 30min,, cut into the wide paper slip of 15mm and carry out tensile strength, pop strength test at the equilibrium water conten 24h of thermostatic constant wet chamber.The detection of wet strong retention rate: after under 25 ℃ of room temperatures paper slip being put into deionized water and soak 1h, blot the pattern surface moisture rapidly, carry out the wet tensile (strength) test with filter paper.
Wet strong retention rate=(wet tensile (strength)/dry tensile strength) * 100%
Embodiment 1
(1) thermostat is being housed, is adding the gluten protein powder in the there-necked flask of agitator and feeder, the concentration of regulating turbid liquid is 5%, pH is 3 with formic acid liquid conditioned reaction system, and the control temperature slowly drips formaldehyde 8%/gluten protein powder in 70 ℃ of water-baths, reacted 2 hours, and collected intermediate product.
(2) under 60 ℃ of water-baths, in intermediate product, slowly drip epoxychloropropane 5%, reaction 2h.In the course of reaction, the epoxychloropropane of insoluble in water fades away, and milk yellow albumen keeps liquid and becomes more thorough.Reaction finishes back gluten protein liquid and becomes oyster white.Can dissolve each other with arbitrary proportion with water; PH value: 4.5; Solid content: 5%; Stability: room temperature deposit do not become turbid in 6 months, gelatin phenomenon.
(3) dried tensile index has improved 35% in the paper, and wet strength retention is 22%.
Embodiment 2
(1) thermostat is being housed, is adding the gluten protein powder in the there-necked flask of agitator and feeder, the concentration of regulating turbid liquid is 1%, pH is 2 with formic acid liquid conditioned reaction system, and the control temperature slowly drips formaldehyde 5%/gluten protein powder in 20 ℃ of water-baths, reacted 2 hours, and collected intermediate product.
(2) under 20 ℃ of water-baths, in intermediate product, slowly drip epoxychloropropane 1%, reaction 2h.In the course of reaction, the epoxychloropropane of insoluble in water fades away, and milk yellow albumen keeps liquid and becomes more thorough.Reaction finishes back gluten protein liquid and becomes oyster white.
(3) dried tensile index has improved 30% in the paper, and wet strength retention is 20%.
Embodiment 3
(1) thermostat is being housed, add the gluten protein powder in the there-necked flask of agitator and feeder, the concentration of regulating turbid liquid is 10%, pH is 6 with formic acid liquid conditioned reaction system, the control temperature is in 100 ℃ of water-baths, slowly drip formaldehyde 15%/gluten protein powder, reacted 1 hour, collect intermediate product.
(2) under 100 ℃ of water-baths, in intermediate product, slowly drip epoxychloropropane 10%, reaction 1h.In the course of reaction, the epoxychloropropane of insoluble in water fades away, and milk yellow albumen keeps liquid and becomes more thorough.Reaction finishes back gluten protein liquid and becomes oyster white.
(3) dried tensile index has improved 33% in the paper, and wet strength retention is 20%.
Embodiment 4
(1) thermostat is being housed, is adding the gluten protein powder in the there-necked flask of agitator and feeder, the concentration of regulating turbid liquid is 1%, pH is 2 with formic acid liquid conditioned reaction system, and the control temperature slowly drips formaldehyde 5%/gluten protein powder in 20 ℃ of water-baths, reacted 8 hours, and collected intermediate product.
(2) under 20 ℃ of water-baths, in intermediate product, slowly drip epoxychloropropane 1%, reaction 4h.In the course of reaction, the epoxychloropropane of insoluble in water fades away, and milk yellow albumen keeps liquid and becomes more thorough.Reaction finishes back gluten protein liquid and becomes oyster white.
(3) dried tensile index has improved 32% in the paper, and wet strength retention is 22%.
Claims (7)
1, a kind of method for modifying gluten protein as paper strengthening agent is characterized in that comprising the steps and process conditions:
(1) hydroxymethylation: thermostat is being housed, add the gluten protein powder in the there-necked flask of agitator and feeder, be adjusted to the turbid liquid of 1%～10% weight percent concentration, pH is 2～6 with formic acid conditioned reaction system, 20～100 ℃ of following water-baths, slowly dripping consumption is the formaldehyde of gluten protein grain weight amount 5～15%, reacts 1～8 hour, collects intermediate product;
(2) cationization reaction: under 20～100 ℃ of water-baths, slowly the dropping consumption is the epoxychloropropane of paddy Ruan albumen powder weight 1～10% in the intermediate product, reacts 1～4 hour, makes oyster white gluten protein liquid.
2, the method for modifying gluten protein as paper strengthening agent according to claim 1, the pH that it is characterized in that described step (1) is 3.
3, the method for modifying gluten protein as paper strengthening agent according to claim 1 is characterized in that described step (1) reaction temperature is 70 ℃.
4, the method for modifying gluten protein as paper strengthening agent according to claim 1 is characterized in that described step (1) formaldehyde consumption is 8% of a gluten protein grain weight amount.
5, the method for modifying gluten protein as paper strengthening agent according to claim 1 is characterized in that described step (1) reaction time is 6 hours.
6, the method for modifying gluten protein as paper strengthening agent according to claim 1 is characterized in that reaction temperature is 60 ℃ of temperature in the described step (2).
7, the method for modifying gluten protein as paper strengthening agent according to claim 1 is characterized in that the reaction time is 2 hours in the described step (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101237607A CN100436708C (en) | 2006-11-27 | 2006-11-27 | Method for modifying gluten protein used as paper strengthening agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101237607A CN100436708C (en) | 2006-11-27 | 2006-11-27 | Method for modifying gluten protein used as paper strengthening agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1963018A CN1963018A (en) | 2007-05-16 |
| CN100436708C true CN100436708C (en) | 2008-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006101237607A Expired - Fee Related CN100436708C (en) | 2006-11-27 | 2006-11-27 | Method for modifying gluten protein used as paper strengthening agent |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810785A (en) * | 1987-07-17 | 1989-03-07 | A. E. Staley Manufacturing Company | Crosslinked corn bran and utilization in papermaking |
| JPH02232A (en) * | 1987-10-16 | 1990-01-05 | Kao Corp | Production of n-substituted amine |
| WO1997001965A1 (en) * | 1995-07-06 | 1997-01-23 | Shoalhaven Starches Pty. Ltd. | Processes for the modification of wheat gluten |
| EP0960922A1 (en) * | 1998-05-26 | 1999-12-01 | Aventis Research & Technologies GmbH & Co KG | Method for preparing a protein coating and articles thereof |
-
2006
- 2006-11-27 CN CNB2006101237607A patent/CN100436708C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810785A (en) * | 1987-07-17 | 1989-03-07 | A. E. Staley Manufacturing Company | Crosslinked corn bran and utilization in papermaking |
| JPH02232A (en) * | 1987-10-16 | 1990-01-05 | Kao Corp | Production of n-substituted amine |
| WO1997001965A1 (en) * | 1995-07-06 | 1997-01-23 | Shoalhaven Starches Pty. Ltd. | Processes for the modification of wheat gluten |
| EP0960922A1 (en) * | 1998-05-26 | 1999-12-01 | Aventis Research & Technologies GmbH & Co KG | Method for preparing a protein coating and articles thereof |
Non-Patent Citations (2)
| Title |
|---|
| 谷朊粉应用概述. 严忠军，卞科，司建中.中国粮油学报，第20卷第5期. 2005 |
| 谷朊粉应用概述. 严忠军，卞科，司建中.中国粮油学报，第20卷第5期. 2005 * |
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| Publication number | Publication date |
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| CN1963018A (en) | 2007-05-16 |
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Assignee: GUANGZHOU PAPER Co., LTD. Assignor: South China University of Technology Contract fulfillment period: 2008.12.7 to 2014.12.6 contract change Contract record no.: 2009440001545 Denomination of invention: Method for modifying gluten protein used as paper strengthening agent Granted publication date: 20081126 License type: Exclusive license Record date: 20091012 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.12.7 TO 2014.12.6; CHANGE OF CONTRACT Name of requester: GUANGZHOU PAPER CO., LTD. Effective date: 20091012 |
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Granted publication date: 20081126 Termination date: 20111127 |