CN100587159C - Method for synthesizing cation plant fibre strengthening agent by modified glutelin protein - Google Patents
Method for synthesizing cation plant fibre strengthening agent by modified glutelin protein Download PDFInfo
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- CN100587159C CN100587159C CN200710032547A CN200710032547A CN100587159C CN 100587159 C CN100587159 C CN 100587159C CN 200710032547 A CN200710032547 A CN 200710032547A CN 200710032547 A CN200710032547 A CN 200710032547A CN 100587159 C CN100587159 C CN 100587159C
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- protein
- strengthening agent
- glutelin
- plant fibre
- fibre strengthening
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Abstract
The invention discloses a method to synthesize the cation vegetable fiber intensifier with the modified glutelin. The invention comprises the following steps: the grafting reaction of the glutelin andthe substituted diamino compound (with the weight ratio of 1:0.7 to 1:2) is conducted under the catalyzing of the transglutaminase, and then an epoxy compound and the grafted glutelin react with theweight ratio of 0.3:1 to 1:1 to generate the modified glutelin containing the annular quaternary ammonium group.
Description
Technical field
The present invention relates to field of papermaking, particularly a kind of method of modifying glutelin protein synthesis kation plant fibre strengthening agent.
Background technology
Gluten protein is a kind of plant protein, is the residue behind the cereal producing starchs such as wheat, corn.Gluten protein can be used as the intensity enhancing auxiliary agent of paper technology, on its protein molecule chain many active groups are arranged, as amino, hydroxyl, carboxyl etc., has special reactivity, can produce chemical bond with the hydroxyl on the cellulosic molecule in the paper, adhesion between the paper fiber is increased, improve the physical strength of paper.But because gluten protein contains more hydrophobic amino acid and uncharged amino acid, the hydrophobic effect zone is bigger in the molecule, and solubility is lower, often can not satisfy the needs of paper, and its application has a lot of limitation.Therefore, often gluten protein is carried out modification,, widen its Application Areas to improve its function.Method of modifying commonly used at present has method for hydrolysis, acidylate or quaternized method.The method for hydrolysis modification can only improve the solubility of gluten protein, to improving the bad in conjunction with effect of string, because hydrolysis has reduced the molecular weight of protein, can not be used for fortifying fibre intensity simultaneously; Acylation modification can not improve the solubility of albumen, can not be used as fiber enhancer after the modification.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of environmental friendliness, cost are low, the method for the simple modifying glutelin protein synthesis kation plant fibre strengthening agent of technology.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method of modifying glutelin protein synthesis kation plant fibre strengthening agent, comprise the steps: that mass ratio at first is that 1: 0.7～1.5 gluten protein connects the skill reaction with replacing diamino compounds under the catalysis of glutamine transaminase, then mass ratio be 0.3: 1～1: 1 epoxide with connect skill after the gluten protein reaction generate the modifying glutelin albumen that contains the ring-type quaternary ammonium group.
Described gluten protein is a kind of corn protein, and the popular name gluten specifically can be wheat gluten protein matter or corn gluten protein matter.
The chemical structural formula of described replacement diamino compounds is H
2N (CH
2)
nNH (CH
2)
mCH
3, n=2～6 wherein, m=0～1.
The consumption of described glutamine transaminase is 3～6% of a gluten protein quality.
The described reaction temperature that connects the skill reaction is 30～50 ℃, and pH value is 7～9, and the reaction time is 1～4 hour.
Described epoxide is an epoxychloropropane.
Described epoxide with connect that the reaction time of gluten protein is 1～6 hour after the skill, temperature is 30～70 ℃.
During forming according to the amino acid of gluten protein, the present invention contains the glutamine more than 35%, utilize glutamine transaminage catalysis to make grafting on the protein molecular chain contain the side chain of active group, carry out the cationization reaction then, promptly generate the modifying glutelin albumen of ring-type quaternary ammonium group with reactivity with the epoxide reaction, this modified protein has with string reaction and with the performance of covalent bonds, can be used as the paper wet strength agent.
The present invention compared with prior art has following advantage and effect: utilize biology enzyme to carry out grafting on the protein molecule chain, improve the amount of fat amido, help reaction and form the ring-type quaternary ammonium salt, thereby make the albumen and the fiber-reactive of modification, can strengthen the wet strong of paper, and the reaction condition gentleness, the transformation efficiency height.
The specific embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL0.2%KCl and pH=8, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.6 gram glutamine transaminase then, 50 ℃ of reactions 1 hour, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.Product is stable, places and does not have precipitation in 30 days.
Embodiment 2
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH=8, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=6 m=1), stirs, and adds 0.6 gram glutamine transaminase then, 30 ℃ of reactions 4 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 4 hours 30 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.2.
Embodiment 3
At first, 5 gram gluten proteins are dissolved in the cushioning liquid of 50mL 0.2%KCl and pH 9, add 0.017 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.3 gram glutamine transaminase then, 30 ℃ of reactions 2 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 2 hours 50 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.
Embodiment 4
At first, 5 gram gluten proteins are dissolved in the cushioning liquid of 50mL 0.2%KCl and pH 9, add 0.017 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=4 m=1), stirs, and adds 0.3 gram glutamine transaminase then, 50 ℃ of reactions 2 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.6.
Embodiment 5
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH 7, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.5 gram biology enzyme then, 40 ℃ of reactions 4 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.2.
Embodiment 6
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH 7, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=1), stirs, and adds 0.6 gram glutamine transaminase then, 30C reaction 4 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 3 hours 30 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.
Embodiment 7
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH=8, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.3 gram glutamine transaminase then, 50 ℃ of reactions 3 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1.1) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.Product is stable, places and does not have precipitation in 30 days
Embodiment 8
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH=8, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.4 gram glutamine transaminase then, 50 ℃ of reactions 4 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 0.4) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.Product is stable, places and does not have precipitation in 30 days.
Embodiment 9
At first, 10 gram gluten proteins are dissolved in the cushioning liquid of 100mL 0.2%KCl and pH=8, add 0.024 mole replacement diamino compounds H
2N (CH
2)
nNH (CH
2)
mCH
3(n=2 m=0), stirs, and adds 0.5 gram glutamine transaminase then, 40 ℃ of reactions 2 hours, obtains grafted protein matter.
Then, in grafted protein matter solution, drip epoxychloropropane (mass ratio is 1: 1) again, continue to react 1 hour 60 ℃ of water-baths, obtain modifying glutelin protein synthesis kation plant fibre strengthening agent, the pH value is 7.5.Product is stable, places and does not have precipitation in 30 days.
Claims (4)
1, a kind of method of modifying glutelin protein synthesis kation plant fibre strengthening agent, it is characterized in that comprising the steps: that mass ratio at first is that 1: 0.7～1.5 gluten protein connects the skill reaction with replacing diamino compounds under the catalysis of glutamine transaminage, the chemical structural formula of described replacement diamino compounds is H
2N (CH
2)
nNH (CH
2)
mCH
3, n=2～6 wherein, m=0～1; Mass ratio is that the gluten protein reaction generates the modifying glutelin albumen that contains the ring-type quaternary ammonium group after 0.3: 1～1: 1 epoxide and the grafting then, and described epoxide is an epoxychloropropane.
2, the method for modifying glutelin protein synthesis kation plant fibre strengthening agent according to claim 1 is characterized in that: the consumption of described glutamine transaminage is 3～6% of a gluten protein quality.
3, the method for modifying glutelin protein synthesis kation plant fibre strengthening agent according to claim 1 is characterized in that: the described reaction temperature that connects the skill reaction is 30～50 ℃, and the pH value is 7～9, and the reaction time is 1～4 hour.
4, the method for modifying glutelin protein synthesis kation plant fibre strengthening agent according to claim 1 is characterized in that: described epoxide with connect that the reaction time of gluten protein is 1～6 hour after the skill, temperature is 30～70 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710032547A CN100587159C (en) | 2007-12-14 | 2007-12-14 | Method for synthesizing cation plant fibre strengthening agent by modified glutelin protein |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710032547A CN100587159C (en) | 2007-12-14 | 2007-12-14 | Method for synthesizing cation plant fibre strengthening agent by modified glutelin protein |
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|---|---|
| CN101182688A CN101182688A (en) | 2008-05-21 |
| CN100587159C true CN100587159C (en) | 2010-02-03 |
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| CN108138445B (en) * | 2015-09-03 | 2021-02-09 | 索理思科技公司 | Method for making lignocellulosic paper and paper products |
| CN107894500A (en) * | 2017-10-26 | 2018-04-10 | 华南理工大学 | A kind of method of quantitative measurment plant micro-nano cellulose retention in paper making process |
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Non-Patent Citations (2)
| Title |
|---|
| 谷朊蛋白的改性及应用. 尹覃伟等.高分子通报，第5期. 2007 |
| 谷朊蛋白的改性及应用. 尹覃伟等.高分子通报，第5期. 2007 * |
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| CN101182688A (en) | 2008-05-21 |
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