CN104193839B - Cationic starch and its preparation method and application - Google Patents
Cationic starch and its preparation method and application Download PDFInfo
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- CN104193839B CN104193839B CN201410453903.5A CN201410453903A CN104193839B CN 104193839 B CN104193839 B CN 104193839B CN 201410453903 A CN201410453903 A CN 201410453903A CN 104193839 B CN104193839 B CN 104193839B
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Abstract
The invention discloses a kind of cationic starch and its preparation method and application, its preparation method includes: starch is mixed with the aqueous solutions of organic solvent that weight/mass percentage composition is 50 90% and is placed in reaction vessel by (1)；(2) add catalyst, stir and be warming up to 50 90 DEG C；(3) add etherifying agent, react 1 5h；(4) add oxidant, react 10 60min；(5) adding the sour pH value to reaction system is 47；(6) vacuum drying, temperature is 50 90 DEG C, and vacuum is 0.07 0.1MPa, obtains described cationic starch.The cationic starch that the preparation method of the present invention prepares, as AKD emulsifying agent, can make AKD emulsion stabilization time at normal temperatures more than 3 months.
Description
Technical field
The present invention relates to macromolecular compound technical field, particularly relate to a kind of cationic starch and preparation thereof
Methods and applications.
Background technology
Native starch be a kind of inexpensive, be easy to get, reproducible industrial chemicals, but owing to its cold water is insoluble,
Stick with paste the shortcomings such as liquid poor heat stability, the most aging, film property is poor, limit its application industrially.And lead to
Ative starch is modified by the modes such as suitable physics, chemistry, enzyme of crossing, and just can significantly improve its performance, system
Become the various starch derivatives products of industrial needs.In starch derivatives, cationic starch is to weigh very much
The class modified starch wanted, has practical value widely.
Alkyl ketene dimer (AKD) is a kind of excellent sizing agent, water insoluble, and paper making pulp body
System is aqueous dispersion, and AKD cannot directly apply to plasm-glue-blending, it is therefore desirable to carry out AKD accordingly
Process.Being typically AKD is carried out emulsifying, cationic starch is then excellent emulsifying agent.Cationic starch
As the emulsifying agent of AKD emulsion, its mechanism is: containing cation gene in cationic starch, cation base
Group can be wrapped in the surface of AKD, forms electric double layer, keeps emulsion intercalation method.
At present, when the cationic starch of large-scale production is applied to AKD, the AKD stability of emulsion obtained
, easily there are the phenomenons such as creaming of emulsion, surface skining in difference.The storage life of AKD emulsion is limited, it is necessary in short-term
Interior use is complete, all causes the biggest pressure to AKD manufacturer and use producer.Different cationic starches should
For AKD emulsion, stability of emulsion has the biggest difference.The reason causing these differences has a lot: one,
The reason of degree ofacationic substitution.Degree ofacationic substitution is high, and positive charge density is the highest, starch and AKD particle
Bond strength is the strongest, and AKD emulsion is the most stable.Its two, the reason of CHARGE DISTRIBUTION uniformity.Cationic starch
The positively charged distribution of institute is the most uniform, when being applied to AKD emulsion, can reach preferably emulsion stabilizing effect.
Prior art causes the reason that the AKD emulsion-stabilizing time is short, is first that current AKD emulsion makes
The degree ofacationic substitution of cationic starch relatively low, generally 0.03-0.05.Low degree ofacationic substitution makes
Obtaining starch low with the bond strength of AKD particle, the electric charge of the electric double layer of formation is low, and electrostatic repulsion is low, holds very much
Easily cause other wild effects such as layering.Next to that, starch is uneven with the reaction of etherifying agent, obtains
Cationic starch positive charge skewness, causes AKD emulsion cannot stablize for a long time.
Summary of the invention
Based on this, it is an object of the invention to provide a kind of preparation method preparing cationic starch, using should
The cationic starch that method prepares is applied to AKD, can make AKD emulsion stabilization time at normal temperatures
Reach more than 3 months.
Concrete technical scheme is as follows:
The preparation method of a kind of cationic starch, comprises the steps:
(1) starch is mixed with the aqueous solutions of organic solvent that weight/mass percentage composition is 50-90% be placed on reaction hold
In device, described starch is 1:2-3 with the mass ratio of described aqueous solutions of organic solvent；
(2) adding catalyst, stir and be warming up to 50-90 DEG C, described starch with the mass ratio of catalyst is
1:0.05-0.25；
(3) adding etherifying agent, react 1-5h, described starch is 1:0.2-1 with the mass ratio of etherifying agent；
(4) adding oxidant, react 10-60min, described starch is 1:0.01-0.1 with the mass ratio of oxidant；
(5) adding the sour pH value to reaction system is 4-7；
(6) vacuum drying, temperature is 50-90 DEG C, and vacuum is 0.07-0.1MPa, obtains described cation
Starch.
Wherein in an embodiment, described starch is selected from tapioca, corn starch, wheaten starch, wax
One or more in matter corn starch and potato starch；Described organic solvent selected from methanol, isopropanol,
One or more in ethanol or acetone.
Wherein in an embodiment, described aqueous solutions of organic solvent be weight/mass percentage composition be the second of 70-85%
Alcohol-water solution.
Wherein in an embodiment, described catalyst is in sodium hydroxide, potassium hydroxide, calcium hydroxide
One or more.
Wherein in an embodiment, in step (3), reaction temperature is 55-65 DEG C, and described etherifying agent selects
From 2-chloroethyl diethylamine, 2,3-epoxypropyltrimethylchloride chloride or 3-chloro-2-hydroxypropyl-trimethyl ammonia chloride
One or more in ammonium.
Wherein in an embodiment, oxidant is hydrogen peroxide or sodium hypochlorite.
Wherein in an embodiment, described acid one in hydrochloric acid, acetic acid, citric acid, the sulphuric acid or
Several.
Wherein in an embodiment, in step (6), temperature is 60-70 DEG C, and vacuum is 0.09-0.1MPa.
It is a further object of the present invention to provide a kind of cationic starch.
The cationic starch that above-mentioned preparation method prepares.
It is a further object of the present invention to provide the application of above-mentioned cationic starch.
The cationic starch that above-mentioned preparation method prepares is as emulsifying agent application in AKD emulsion.
The principle and advantage of the present invention:
In the basic conditions, hydroxyl is converted into the OR-with nucleophilic reactivity to starch molecule, with etherifying agent, parent occurs
Nuclear reaction obtains cationic starch.Reaction system must be containing certain water, and reaction could preferably be carried out.
But the water yield is very few, reaction can be not exclusively；Hypervolia, reaction efficiency can reduce and easily gelatinizing.
The degree ofacationic substitution that the present invention obtains is high, when being applied to AKD emulsion as emulsifying agent, can play more
Emulsion stabilizing effect well.The present invention takes suitable solvent ratios and addition, both can ensure reaction efficiency
Gelatinizing phenomenon can be reduced again.
The cationic starch conventional method obtaining solid is that reaction suspension is centrifuged, and obtains filter cake, filter cake
Enter back into drying machine to be dried.And the dry run of the present invention is directly to carry out vacuum in reaction vessel to do
Dry, both saving equipment cost, the equipment that also reduces takes up an area space.Additionally, directly in reaction vessel
Solvent removed in vacuo, in this process, due to the continuous rising of moisture, can improve cation electrodeposition
The uniformity of lotus density, improves partial structurtes.
When above advantage makes this cationic starch be applied to AKD emulsion, preferably stable emulsifying can be reached
Effect, general centrifugal drying method does not reaches corresponding effect.
The present invention uses new preparation method to prepare cationic starch, controls starch with organic in this preparation method
The ratio of solvent aqueous solution is 1:2-3, and the mass ratio of the addition and starch that simultaneously control etherifying agent is 0.2-1:
1, and coordinate direct vacuum drying method in reaction vessel to be dried, it is possible to prepare cation and take
Dai Du is 0.1-1, and at 25 DEG C, 1% solution viscosity is the cationic starch of 10～100mPa.S, this cation
Water dissolution is got final product under starch room temperature.The preparation method of the present invention prepares cationic starch should as emulsifying agent
For AKD emulsion, can realize a step emulsifying, the AKD emulsion obtained can exceed that stabilization time at normal temperatures
3 months.
Detailed description of the invention
By the following examples the application is further elaborated.
Embodiment 1
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) 100g corn starch is mixed rearmounted with the ethanol water that 300g weight/mass percentage composition is 75%
In reaction vessel, stir 30min；
(2) add 7g sodium hydroxide, stir and be warming up to 55 DEG C；
(3) add 25g2,3-epoxypropyltrimethylchloride chloride etherifying agent, react 5h；
(4) add 3g hydrogen peroxide, react 30min；
(5) addition glacial acetic acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 60 DEG C, and vacuum is 0.09MPa, pulverizes
Described cationic starch is i.e. obtained after sieving.
Embodiment 2
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) 100g tapioca is mixed rearmounted with the ethanol water that 250g weight/mass percentage composition is 70%
In reaction vessel, stir 30min；
(2) add 8g potassium hydroxide, stir and be warming up to 60 DEG C；
(3) add 25g2,3-epoxypropyltrimethylchloride chloride etherifying agent, react 4h；
(4) add 4g hydrogen peroxide, react 30min；
(5) addition hydrochloric acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 70 DEG C, and vacuum is 0.09MPa, pulverizes
Described cationic starch is i.e. obtained after sieving.
Embodiment 3
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) 100g wheaten starch is mixed rearmounted with the ethanol water that 200g weight/mass percentage composition is 80%
In reaction vessel, stir 30min；
(2) add 10g potassium hydroxide, stir and be warming up to 65 DEG C；
(3) add 30g3-chloro-2-hydroxypropyl-trimethyl ammonium chloride etherifying agent, react 3h；
(4) add 5g hydrogen peroxide, react 30min；
(5) addition citric acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 75 DEG C, and vacuum is 0.085MPa, powder
Broken sieve after i.e. obtain described cationic starch.
Embodiment 4
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) 100g waxy corn starch is mixed with the ethanol water that 250g weight/mass percentage composition is 85%
It is placed in reaction vessel, stirs 30min；
(2) add 5g potassium hydroxide, stir and be warming up to 50 DEG C；
(3) add the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride etherifying agent of 45g, react 7h；
(4) add 5g sodium hypochlorite, react 30min；
(5) addition sulphuric acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 65 DEG C, and vacuum is 0.095MPa, powder
Broken sieve after i.e. obtain described cationic starch.
Embodiment 5
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) after 100g potato starch being mixed with the ethanol water that 300g weight/mass percentage composition is 60%
It is placed in reaction vessel, stirs 30min；
(2) add 5g sodium hydroxide, stir and be warming up to 60 DEG C；
(3) add the 2-chloroethyl diethylamine etherifying agent of 20g, react 4h；
(4) add 7g sodium hypochlorite, react 30min；
(5) addition glacial acetic acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 70 DEG C, and vacuum is 0.09MPa, pulverizes
Described cationic starch is i.e. obtained after sieving.
Comparative example 1
The preparation method of a kind of cationic starch of this comparative example, comprises the steps:
(1) 100g corn starch is mixed rearmounted with the ethanol water that 100g weight/mass percentage composition is 80%
In reaction vessel, stir 30min；
(2) add 10g sodium hydroxide, stir and be warming up to 60 DEG C；
(3) add 15g3-chloro-2-hydroxypropyl-trimethyl ammonium chloride etherifying agent, react 5h；
(4) add 4g sodium hypochlorite, react 30min；
(5) addition glacial acetic acid is 4-7 to the pH value of reaction system；
(6) centrifugal, dry, after pulverizing and sieving, i.e. obtain described cationic starch.
Comparative example 2
The preparation method of a kind of cationic starch of this comparative example, comprises the steps:
(1) 100g tapioca is mixed rearmounted with the ethanol water that 150g weight/mass percentage composition is 70%
In reaction vessel, stir 30min；
(2) add 10g sodium hydroxide, stir and be warming up to 60 DEG C；
(3) add 15g3-chloro-2-hydroxypropyl-trimethyl ammonium chloride etherifying agent, react 5h；
(4) add 4g sodium hypochlorite, react 30min；
(5) addition glacial acetic acid is 4-7 to the pH value of reaction system；
(6) being directly vacuum dried in reaction vessel, temperature is 70 DEG C, and vacuum is 0.09MPa, pulverizes
Described cationic starch is i.e. obtained after sieving.
Comparative example 3
The preparation method of a kind of cationic starch of the present embodiment, comprises the steps:
(1) after 100g potato starch being mixed with the ethanol water that 300g weight/mass percentage composition is 75%
It is placed in reaction vessel, stirs 30min；
(2) add 7g sodium hydroxide, stir and be warming up to 55 DEG C；
(3) add 25g2-chloroethyl diethylamine, react 5h；
(4) add 3g hydrogen peroxide, react 30min；
(5) addition glacial acetic acid is 4-7 to the pH value of reaction system；
(6) centrifugal, dry, pulverize and after sieving, i.e. obtain described cationic starch.
The formula of AKD emulsion is as follows:
| Name of material | Addition/g | Name of material | Addition/g |
| Cationic starch | 20-22 | AKD wax powder | 100-110 |
| Sodium lignin sulfonate | 1-2 | Zirconium oxychloride | 1-2 |
| Aluminum sulfate (40% solid content) | 20-40 | Water | 800-1000 |
According to formula, prepare AKD emulsion.
The cationic starch performance that above-described embodiment and comparative example prepare is as follows:
Remarks:
1% solution viscosity is at 25 DEG C, the viscosity of cationic starch 1% aqueous solution；AKD emulsion-stabilizing
Time is airtight placement at 25 DEG C, records from starting placement to the creaming of emulsion time.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (10)
1. the preparation method of a cationic starch, it is characterised in that comprise the steps:
(1) starch is mixed with the aqueous solutions of organic solvent that weight/mass percentage composition is 50-90% be placed on reaction hold
In device, described starch is 1:2-3 with the mass ratio of described aqueous solutions of organic solvent；
(2) adding catalyst, stir and be warming up to 50-90 DEG C, described starch with the mass ratio of catalyst is
1:0.05-0.25；
(3) adding etherifying agent, react 1-5h, described starch is 1:0.2-1 with the mass ratio of etherifying agent；
(4) adding oxidant, react 10-60min, described starch is 1:0.01-0.1 with the mass ratio of oxidant；
(5) adding the sour pH value to reaction system is 4-7；
(6) vacuum drying, temperature is 50-90 DEG C, and vacuum is 0.07-0.1MPa, obtains described cation
Starch.
Preparation method the most according to claim 1, it is characterised in that described starch selected from tapioca,
One or more in corn starch, wheaten starch, waxy corn starch and potato starch；Described organic
One or more in solvent selected from methanol, isopropanol, ethanol or acetone.
Preparation method the most according to claim 2, it is characterised in that described aqueous solutions of organic solvent is
Weight/mass percentage composition is the ethanol water of 70-85%.
Preparation method the most according to claim 1, it is characterised in that described catalyst is selected from hydroxide
One or more in sodium, potassium hydroxide, calcium hydroxide.
Preparation method the most according to claim 1, it is characterised in that in step (3), reaction temperature
Degree for 55-65 DEG C, described etherifying agent selected from 2-chloroethyl diethylamine, 2,3-epoxypropyltrimethylchloride chloride or
One or more in person 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.
Preparation method the most according to claim 1, it is characterised in that described oxidant is hydrogen peroxide
Or sodium hypochlorite.
Preparation method the most according to claim 1, it is characterised in that described acid selected from hydrochloric acid, acetic acid,
One or more in citric acid, sulphuric acid.
8. according to the preparation method described in any one of claim 1-7, it is characterised in that in step (6),
Temperature is 60-70 DEG C, and vacuum is 0.09-0.1MPa.
9. the cationic starch that the preparation method described in any one of claim 1-8 prepares.
10. the cationic starch described in claim 9 is as emulsifying agent application in AKD emulsion.
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| CN104499363B (en) * | 2015-01-09 | 2017-02-01 | 广州天赐高新材料股份有限公司 | AKD emulsion and preparation method thereof |
| CN105131136A (en) * | 2015-10-19 | 2015-12-09 | 高大元 | Preparation method of cationic starch |
| CN106279451A (en) * | 2016-08-09 | 2017-01-04 | 广州天赐高新材料股份有限公司 | Cationic starch with high substitution degree and preparation method thereof |
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| CN109651517B (en) * | 2018-12-29 | 2021-07-27 | 广州天赐高新材料股份有限公司 | Amphoteric starch for AKD emulsification and preparation method and application thereof |
| CN109988246A (en) * | 2019-04-19 | 2019-07-09 | 广州天赐高新材料股份有限公司 | A kind of high degree of substitution cationic starch and preparation method thereof |
| CN111072790A (en) * | 2019-12-27 | 2020-04-28 | 河南新孚望新材料科技有限公司 | Preparation method of modified starch for glass fiber cloth |
| CN111606631A (en) * | 2020-06-20 | 2020-09-01 | 深圳市亿东阳建材有限公司 | Thin-layer plastering mortar and preparation method thereof |
| CN111926614A (en) * | 2020-08-14 | 2020-11-13 | 山东寿光巨能金玉米开发有限公司 | Production method of corn starch AKD sizing agent special for papermaking |
| CN116621998A (en) * | 2023-05-08 | 2023-08-22 | 山东天成化工有限公司 | Preparation method of emulsifier for high-charge-density AKD (alkyl ketene dimer) |
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