CN106220746A - A kind of preparation method and applications of solution-type cationic starch - Google Patents
A kind of preparation method and applications of solution-type cationic starch Download PDFInfo
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- CN106220746A CN106220746A CN201610745884.2A CN201610745884A CN106220746A CN 106220746 A CN106220746 A CN 106220746A CN 201610745884 A CN201610745884 A CN 201610745884A CN 106220746 A CN106220746 A CN 106220746A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses the preparation method of a kind of solution-type cationic starch, comprise the following steps: step one, add water and ative starch in four-hole boiling flask, stirring prepares starch emulsion the heating that heats up system；Step 2, after system is warmed up to 35 DEG C, adds oxidant in starch emulsion；Step 3, after system temperature rises to 40 DEG C, adds modifying agent, etherifying agent, NaOH solution, sustained response 4 8h；Step 4, sustained response terminate before 30min, add pH adjusting agent regulation pH value；Step 5, adds antibacterial after system temperature is down to 35 DEG C, is then sieved by product and i.e. obtain solution-type cationic starch.Solution-type cationic starch prepared by the present invention can be dissolved in water in any proportion, and after can guarantee that again starch dissolution, placement a period of time is not precipitated, the appearance requirement of starch solution clarification, and has reinforced effects and the retention effect of good paper.
Description
Technical field
The present invention relates to starch preparing technical field, particularly relate to a kind of solution-type cationic starch preparation method and
Application.
Background technology
Starch is the depot polysaccharide that higher plant is main, is made up of chain starch and two kinds of macromole glucosans of starch.
Ative starch the most just prepares various product as a kind of raw material, and the most this polysaccharide macro-molecular has good
Toughness with become colloidality, be therefore good food quality modifying agent and stabilizer.The application of starch, it is common that heating starch breast
It is allowed to gelatinizing, the gelatinized corn starch obtained by application, for avoiding the trouble of this Heat Gelatinization, carrying out cold water the most always
The research of soluble starch.
At present, the preparation method of cationic starch is all to be carried out without electrical ative starch by the etherifying agent of positively charged
Etherificate makes becoming positively charged property of ative starch, thus changes into cationic starch.The technology of preparing of cationic starch substantially can be divided into
Three classes: wet method prepares cationic starch, half wet-dry change prepares cationic starch and dry process of preparation of cationic starch.Cold water can at present
Molten starch mainly uses dry process, mainly has four kinds of preparation methoies: 1, double flowing nozzle spray drying method；2, high tcmpcrauire-higb pressure
Alcohol method；3, normal pressure polyol process；4, second alcohol-alkali.Double flowing nozzle spray drying method reaction condition requires strict, needs special
Double flowing nozzle, equipment manufacturing cost is high, needs High Temperature High Pressure to add vapours, and power consumption is big.Although high tcmpcrauire-higb pressure alcohol method can keep former substantially
The graininess of starch, but production process needs High Temperature High Pressure, and the method may not apply to high amylopectin starch.Normal pressure polyhydric alcohol
Method needs high temperature in process of production, and now material is difficult to flowing, conducts heat undesirable, the quality of wayward product.Ethanol-
Alkaline process can make starch while keeping particle shape, reaches optimal solvent swelling state, but starch is placed still after being dissolved in cold water
So can precipitate.
Summary of the invention
The present invention solves a kind of solution-type cationic starch preparation method that the problems referred to above of the prior art propose, both
Can be dissolved in water in any proportion, after can guarantee that again starch dissolution, placement a period of time is not precipitated, outside starch solution clarification
See requirement, and there is reinforced effects and the retention effect of good paper.
In order to realize above-mentioned technical purpose, the taked technical measures of the present invention are:
The preparation method of a kind of solution-type cationic starch, includes following steps:
Step one, adds water and ative starch in four-hole boiling flask, is stirred continuously prepared starch emulsion the heating that heats up system；
Step 2, after system is warmed up to 35 DEG C, adds oxidant in starch emulsion, and is stirred continuously and makes starch emulsion become
The starch solution of all-transparent, continues the heating that heats up；
Step 3, after system temperature rises to 40 DEG C, adds modifying agent, etherifying agent, NaOH solution, sustained response 4-8h；
Step 4, the 30min before step 3 sustained response terminates, add pH adjusting agent regulation pH value, and gradually reduce system
Temperature；
Step 5, adds antibacterial after system temperature is down to 35 DEG C, is then sieved by product and i.e. obtain solution-type cationic starch.
In order to optimize technique scheme further, the technical measures that the present invention is taked also include:
Further, anti-extender described in step one is sodium sulfate or sodium chloride；Described ative starch is selected from corn starch, Maninot esculenta crantz.
One or more in starch, potato starch and pea starch.
Further, oxidant described in step 2 is selected from hydrogen peroxide, sodium hypochlorite, amylase, epoxychloropropane and sulfur
One or more in acid copper.
Further, modifying agent described in step 3 is selected from dodecyl dimethyl benzyl ammonium chloride, aluminum chloride, sulphuric acid
One or more in aluminum, polyacrylamide, polymine, polymer alumina, sodium sulfite and sodium chloride；Described etherifying agent
For 3-chloro-2-hydrocarbon hydroxypropyltrimonium chloride or 2,3-epoxypropyltrimethylchloride chloride.
Further, in step 4 pH adjusting agent regulation pH value to 5-8, described pH adjusting agent selected from citric acid, hydrochloric acid or
Acetic acid.
Further, the antibacterial described in step 5 is BIT.
Further, sieve described in step 5 as crossing 325 mesh mesh screens.
Further, described oxidant accounts for the mass percent of ative starch is 2-20%；Modifying agent accounts for the quality hundred of ative starch
Proportion by subtraction is 0.05-2.0%；It is 5-60% that etherifying agent accounts for the mass percent of ative starch；NaOH solution accounts for ative starch mass percent
For 25-50%；PH adjusting agent is 0.3-0.7:1 with the mol ratio of NaOH；It is 0.01-that antibacterial accounts for the mass percent of ative starch
0.05%；The mass ratio of ative starch and water is 0.10-0.40:1.
On the other hand, the present invention also provides for solution-type cationic starch and this solution-type prepared according to above-mentioned preparation method
Cationic starch is in copy paper chemicals and the application of household chemicals preparing technical field.
The present invention uses technique scheme, compared with prior art, has the following technical effect that the preparation side of the present invention
Method is simple, and the solution-type cationic starch of preparation can solution water in any proportion；The preparation method of the present invention is at normal temperatures and pressures
Just can prepare solution-type cationic starch, it is not necessary to producing under the harsh conditions such as High Temperature High Pressure, operational approach is simple；This
The solution-type cationic starch of bright preparation is placed a period of time after cold water and is remained able to solve homogeneously in water, not stratified, no
Precipitation, good stability；Solution-type cationic starch prepared by the present invention stores with less than 0 DEG C in high/low temperature baking oven still will not
Lamination occurs.
Detailed description of the invention
The invention provides the preparation method of a kind of solution-type cationic starch, its concrete steps include:
(1) in four-hole boiling flask, add a certain amount of deionized water, start stirring, heat up.
(2) when temperature reaches setting value, addition oxidant, after forming starch emulsion completely, is continuously heating to reaction temperature
Degree.
(3), during reaction temperature to be achieved, add modifying agent, etherifying agent, NaOH solution, control etherifying agent and alkali liquor simultaneously
Joining day and the interval time of two kinds of raw materials, reaction continues 4-8h；
(4) before reaction terminates during 30min, adding pH value regulator, regulation pH value is 5-8；
(5) being cooled to room temperature after adding antibacterial after temperature is down to 35 DEG C and stop stirring, cross 325 mesh filter screens, discharging barrelling is i.e.
Obtain solution-type cationic starch.
Below by specific embodiment, the present invention is carried out detailed and concrete introduction, so that being better understood from the present invention,
But following embodiment is not limiting as the scope of the invention.
Embodiment one
Four-hole boiling flask is added ative starch and a certain amount of water is positioned over thermostat water bath warming middle-JIAO and opens stirring 200r/min, and will
Water-bath is warmed up to 35 DEG C, adds oxidant.Add when temperature reaches reaction temperature 40 DEG C add after temperature stabilization modifying agent,
Etherifying agent and NaOH solution, response time 4h.Question response terminates front 30min and adds PH regulator, treats that temperature is down to 35 DEG C of additions
Antibacterial.In the present embodiment, the concrete numerical value of each component is as follows:
Corn starch: 100g
Deionized water: 667g
3-chloro-2-hydrocarbon hydroxypropyltrimonium chloride: 60g
Dodecyl dimethyl benzyl ammonium chloride: 2g
Aluminum chloride: 3g
NaOH solution: 50g
Secondary record acid sodium: 2g
Hydrogen peroxide: 3g
Copper sulfate: 0.3g
Citric acid: 25g
BIT: 1g
Embodiment two
Four-hole boiling flask is added ative starch and a certain amount of water is positioned over thermostat water bath warming middle-JIAO and opens stirring 650r/min, and will
Water-bath is warmed up to 35 DEG C, adds oxidant.Add when temperature reaches reaction temperature 75 DEG C add after temperature stabilization modifying agent,
Etherifying agent and NaOH solution, response time 8h.Question response terminates front 30min and adds PH regulator, treats that temperature is down to 35 DEG C of additions
Antibacterial.In the present embodiment, the concrete numerical value of each component is as follows:
Tapioca: 100g
Deionized water: 250g
2,3-epoxypropyltrimethylchloride chloride: 5g
Potassium permanganate: 5g
Sodium chloride: 7g
Secondary record acid sodium: 8g
NaOH solution: 25g
Acetic acid: 14.2g
BIT: 3g
Embodiment three
Four-hole boiling flask is added ative starch and a certain amount of water is positioned over thermostat water bath warming middle-JIAO and opens stirring 450r/min, and will
Water-bath is warmed up to 35 DEG C, adds oxidant.Add when temperature reaches reaction temperature 50 DEG C add after temperature stabilization modifying agent,
Etherifying agent and NaOH solution, question response terminates front 30min and adds PH regulator, treats that temperature is down to 35 DEG C and is added antibacterial.This reality
Execute the concrete numerical value of each component in example as follows:
Potato starch: 100g
Deionized water: 250g
2,3-epoxypropyltrimethylchloride chloride: 30g
Hydrogen peroxide: 5g
Secondary record acid sodium: 8g
Sodium sulfite: 2g
Aluminum sulfate: 5g
Polyacrylamide: 4g
NaOH solution: 28.7g
Acetic acid: 10.5g
BIT: 2g
Embodiment four
Four-hole boiling flask is added ative starch and a certain amount of water is positioned over thermostat water bath warming middle-JIAO and opens stirring 550r/min, and will
Water-bath is warmed up to 35 DEG C, adds oxidant.Add when temperature reaches reaction temperature 65 DEG C add after temperature stabilization modifying agent,
Etherifying agent and NaOH solution, question response terminates front 30min and adds PH regulator, treats that temperature is down to 35 DEG C and is added antibacterial.This reality
Execute the concrete numerical value of each component in example as follows:
Potato starch: 100g
Deionized water: 250g
2,3-epoxypropyltrimethylchloride chloride: 22.2g
Hydrogen peroxide: 6g
Secondary record acid sodium: 4g
Potassium permanganate: 5g
Aluminum chloride: 8g
Polyacrylamide: 2g
NaOH solution: 26.7g
Hydrochloric acid: 14.5g
BIT: 1.5g
By the solution-type cationic starch prepared by the present invention and 2 control samples (commercially available cold water solubles particular cationic starch)
Dissolubility contrast, data are as shown in table 1.Experimental technique: solution-type cationic starch of the present invention give money as a gift after etc. weight with
Comparative sample is directly added in the water of 25 DEG C, observes whether solution-type cationic starch of the present invention is completely dissolved in comparative sample
Water.
Table 1 dissolubility contrast and experiment
The moisture such as the solution-type cationic starch prepared by the present invention and comparative sample are carried out are strengthened application test, application test
Effect is as follows.
Application effect shows, solution-type cationic starch tensile strength, fracture length and the tearability etc. prepared by the present invention
Each index is superior to comparative sample.
From above example and contrast experiment, the preparation method of the present invention is simple, and the solution-type cation of preparation is formed sediment
Powder can solution water in any proportion；The preparation method of the present invention the most just can prepare solution-type cationic starch,
Need not produce under the harsh conditions such as High Temperature High Pressure, operational approach is simple；Solution-type cationic starch prepared by the present invention in
After cold water, placement a period of time remains able to solve homogeneously in water, not stratified, does not precipitates, tensile strength, fracture length and tear
The excellent performances such as degree, good stability；Solution-type cationic starch prepared by the present invention stores with less than 0 DEG C in high/low temperature baking oven
Still lamination is not had.
Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention does not limit
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute the most all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Amendment, all should contain within the scope of the invention.
Claims (10)
1. the preparation method of a solution-type cationic starch, it is characterised in that comprise the following steps:
Step one, adds water and ative starch in four-hole boiling flask, is stirred continuously prepared starch emulsion the heating that heats up system；
Step 2, after system is warmed up to 35 DEG C, adds oxidant in starch emulsion, and is stirred continuously and makes starch emulsion become
The starch solution of all-transparent, continues the heating that heats up；
Step 3, after system temperature rises to 40 DEG C, adds modifying agent, etherifying agent, NaOH solution, sustained response 4-8h；
Step 4, the 30min before step 3 sustained response terminates, add pH adjusting agent regulation pH value, and gradually reduce system
Temperature；
Step 5, adds antibacterial after system temperature is down to 35 DEG C, is then sieved by product and i.e. obtain solution-type cationic starch.
Preparation method the most according to claim 1, it is characterised in that anti-extender described in step one is sodium sulfate or chlorine
Change sodium；One or more in corn starch, tapioca, potato starch and pea starch of described ative starch.
Preparation method the most according to claim 1, it is characterised in that oxidant described in step 2 is selected from hydrogen peroxide, secondary
One or more in sodium chlorate, amylase, epoxychloropropane and copper sulfate.
Preparation method the most according to claim 1, it is characterised in that modifying agent described in step 3 is selected from dodecyl two
Methyl-benzyl ammonium chloride, aluminum chloride, aluminum sulfate, polyacrylamide, polymine, polymer alumina, sodium sulfite and chlorination
One or more in sodium；Described etherifying agent is 3-chloro-2-hydrocarbon hydroxypropyltrimonium chloride or 2,3-epoxy chlorine
Change ammonium.
Preparation method the most according to claim 1, it is characterised in that in step 4, pH adjusting agent regulation pH value is to 5-8, institute
State pH adjusting agent selected from citric acid, hydrochloric acid or acetic acid.
Preparation method the most according to claim 1, it is characterised in that the antibacterial described in step 5 is benzisothiazole
Quinoline ketone.
Preparation method the most according to claim 1, it is characterised in that sieve described in step 5 as crossing 325 mesh mesh screens.
Preparation method the most according to claim 1, it is characterised in that described oxidant accounts for the mass percent of ative starch and is
2-20%；It is 0.05-2.0% that modifying agent accounts for the mass percent of ative starch；It is 5-that etherifying agent accounts for the mass percent of ative starch
60%；It is 25-50% that NaOH solution accounts for ative starch mass percent；PH adjusting agent is 0.3-0.7:1 with the mol ratio of NaOH；Kill
It is 0.01-0.05% that microbial inoculum accounts for the mass percent of ative starch；The mass ratio of ative starch and water is 0.10-0.40:1.
9. the solution-type cationic starch prepared according to preparation method described in claim 1-8 any one.
Solution-type cationic starch the most according to claim 9 is led at copy paper chemicals and household chemicals technology of preparing
The application in territory.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109989292A (en) * | 2019-03-01 | 2019-07-09 | 徐扣华 | A kind of preparation method of starch base sticking agent |
| CN110357976A (en) * | 2019-08-01 | 2019-10-22 | 诸城兴贸玉米开发有限公司 | A kind of production technology of novel cation nanometer drying strengthening agent |
| CN112029003A (en) * | 2020-08-24 | 2020-12-04 | 上海东升新材料有限公司 | Solution type corn cationic starch and preparation method thereof |
| CN113622222A (en) * | 2021-07-28 | 2021-11-09 | 上海昶法新材料有限公司 | ASA sizing agent, preparation method thereof, mixed pulp and paper |
| CN113880967A (en) * | 2021-11-01 | 2022-01-04 | 上海昶法新材料有限公司 | Cationic hemicellulose solution and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109989292A (en) * | 2019-03-01 | 2019-07-09 | 徐扣华 | A kind of preparation method of starch base sticking agent |
| CN110357976A (en) * | 2019-08-01 | 2019-10-22 | 诸城兴贸玉米开发有限公司 | A kind of production technology of novel cation nanometer drying strengthening agent |
| CN112029003A (en) * | 2020-08-24 | 2020-12-04 | 上海东升新材料有限公司 | Solution type corn cationic starch and preparation method thereof |
| CN113622222A (en) * | 2021-07-28 | 2021-11-09 | 上海昶法新材料有限公司 | ASA sizing agent, preparation method thereof, mixed pulp and paper |
| CN113880967A (en) * | 2021-11-01 | 2022-01-04 | 上海昶法新材料有限公司 | Cationic hemicellulose solution and preparation method thereof |
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