CN102690362B - Preparation method for oxidation cross-linked-carboxymethyl composite modified starch, and oxidation cross-linked-carboxymethyl composite modified starch - Google Patents
Preparation method for oxidation cross-linked-carboxymethyl composite modified starch, and oxidation cross-linked-carboxymethyl composite modified starch Download PDFInfo
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 23
- 238000009413 insulation Methods 0.000 claims description 22
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 19
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Abstract
The invention discloses a preparation method for oxidation cross-linked-carboxymethyl composite modified starch and the oxidation cross-linked-carboxymethyl composite modified starch. According to the preparation method, starch raw materials are subjected to oxidation cross-linking to form cross-linked starch, and the cross-linked starch which is used as a reaction raw material is subjected to carboxymethylation in a microwave reaction system and an infrared heat preservation system to form the required oxidation cross-linked-carboxymethyl composite modified starch. The preparation method is simple, low in cost and high in comprehensive cost performance; an organic solvent is not needed to be adopted; and the prepared oxidation cross-linked-carboxymethyl composite modified starch is high in performance, and coating slurry with high concentration of more than 30 percent can be prepared by using the modified starch, is high in flowability and water-retaining property, can meet the coating requirements of high-end products such as carbonless copy paper, coated paper and the like in papermaking industry well, and the oxidation cross-linked-carboxymethyl composite modified starch has good development and application prospect.
Description
Technical field
The present invention relates to pulp technology for making paper, be specifically related to the coating modified starch technology in paper industry, relate in particular to a kind of oxidation cross-linked-preparation method and the oxidation cross-linked-carboxymethyl composite modified starch of carboxymethyl composite modified starch.
Background technology
Starch distributes very wide at occurring in nature, be a kind of nexhaustible renewable natural resource.Along with the development of production and technology, people recognize the seriousness of the problems such as the energy and environment gradually, and therefore the deep level development to renewable resources and application more and more cause people's attention.Starch is as a kind of abundant renewable resources of originating, and its modified product is because having good performance gradually by extensive concern and application.
The weak points such as native starch is insoluble to cold water, and starch pasting is easily aging, and tunicle is poor, lacks emulsifying power, and resistance and resistance to mechanicalness are poor have limited it and have applied widely.People have developed the sex change technology of starch according to the structure of starch and physico-chemical property, use the method for physics, chemistry or enzyme to process ative starch, make it have the character that is applicable to certain special purpose, this process is called the sex change of starch, and its product is called modified starch.By modification, not only can improve the original character of starch and also can give its new specific function characteristic, it is obtained a wide range of applications in many fields such as food, papermaking, plastics, weaving, daily use chemicals, medicine
Papermaking starch can be divided into 4 large classes by its using method: in slurry, add starch, spray starch (interlaminar improvement is main), surface sizing starch and coating starch.
In coating starch, carboxymethyl starch is owing to having good cohesive strength, film-forming properties, rheological and water-retentivity, and with coating in other chemical substance intermiscibility fabulous, so be used in, in the noncarbon recording paper, enamelled paper of paper industry, to do coating prospect better.But because carboxymethyl starch product has strong water-soluble, substitution value 0.1 or can be dissolved in above cold water, obtain the viscous solution of clear, this just makes in production process with an organic solvent (for example: ethanol, methyl alcohol) as reaction medium, but due to inflammable, the dangerous property of organic solvent itself, and cost costliness, thereby cause carboxymethyl starch to produce in enormous quantities to be applied in paper industry just very difficult, be difficult to universal.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide one good without employing organic solvent, simple, the comprehensive cost performance of preparation method, and the painting slurry of gained modified starch preparation has excellent fluidity and water-retentivity, thus can meet well in paper industry that the coating of the high-end product such as noncarbon recording paper, enamelled paper requires oxidation cross-linked-preparation method of carboxymethyl composite modified starch.
Another object of the present invention be to provide above-mentioned preparation method prepare gained oxidation cross-linked-carboxymethyl composite modified starch.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, this preparation method first carries out oxidation cross-linked processing to starch material to obtain after cross-linking starch, again take Monochloro Acetic Acid and cross-linking starch as reaction raw materials, thereby adopt method that microwave heating and infrared insulation combine to its carry out carboxymethylation reaction obtain required oxidation cross-linked-carboxymethyl composite modified starch, specifically comprise the steps:
Step 1 is oxidation cross-linked
Native starch and water are dropped in dissolving vessel, stirring prepares starch slurry, regulate pH value to 10～11.5 of this starch slurry with caustic alkali after, start to heat up, starch slurry temperature is controlled to 35～42 ℃, keep adding clorox and linking agent under whipped state, under whipped state, carry out crosslinking reaction 90～150 minutes, sampling detects when starch slurry quality is 25% than concentration, starch viscosity reaches 3～10mpa.s and finishes crosslinking reaction, in reaction system, slowly add sodium bisulfite, until survey the variable color of chlorine test paper, stop adding sodium bisulfite, with acid neutralization, regulate whole system PH to 6～8 again, and then washing after filtration successively, sedimentation concentrate, air stream drying obtains required cross-linking starch after processing, this cross-linking starch is powder (moisture content≤15%),
In above-mentioned steps 1, native starch refers to any one or two kinds and the two or more mixing in the conventional W-Gum of those skilled in the art, tapioca (flour) or yam starch etc.
In above-mentioned steps 1, the concentration that gained starch slurry is prepared in native starch and water stirring is 20～24.5 degree Beaume (° B é); The inventor finds by research, if the concentration of starch slurry is less than this scope, starch solid content is inadequate, and production efficiency is low, and manufacturing cost is high, if be greater than this scope, be unfavorable for the homogeneity of reaction, therefore the concentration of optimized choice starch slurry is 20～24.5 degree Beaume by experiment; Degree Beaume is a kind of concentration measurement mode that Starch Production producer generally adopts, and uses B to be easy to detect, and facilitates production operation.
In above-mentioned steps 1, regulate pH value to 10～11.5 of starch slurry with caustic alkali, caustic alkali adopt potassium hydroxide or sodium hydroxide all can, preferably sodium hydroxide, specifically adopting mass percent concentration is the PH that 3～5% sodium hydroxide regulates starch slurry; The inventor optimizes rear discovery by experiment, regulates pH value to 10～11.5 of starch slurry with caustic alkali, and this pH value scope is conducive to crosslinking reaction.
In above-mentioned steps 1, starch slurry temperature is controlled to 35～42 ℃, the selection of this temperature is after contriver contrasts by great many of experiments, to optimize screening to obtain, and contriver finds that efficiency is the highest in this temperature range.
In above-mentioned steps 1, keep adding in clorox and linking agent under whipped state, clorox is the effect of playing oxygenant, 4～8% of native starch (over-dry weight) gross weight that the add-on of clorox is step 1; Described linking agent is any one in phosphorus oxychloride or epoxy chloropropane, the add-on of linking agent be described in step 1 native starch (over-dry weight) gross weight 0.08～0.3%.
In above-mentioned steps 1, carry out crosslinking reaction 90～150 minutes under whipped state, sampling detects when starch slurry quality is 25% than concentration, and starch viscosity reaches 3～10mpa.s and finishes crosslinking reaction; Baume concentration is in production process, to facilitate workman to operate, and quality is to be convenient to Pin Kong department to carry out control indexes than concentration, so the starch slurry concentration in production process adopts Baume concentration, sampling adopts quality to compare concentration while detecting.
In above-mentioned steps 1, sodium bisulfite is to add with the form of powder solid, and the effect of sodium bisulfite is the responseless clorox of reduction.
In above-mentioned steps 1, with acid neutralization adjusting whole system PH to 6～8, described acid is sulfuric acid or hydrochloric acid, specifically adopts the sulfuric acid of 5～10 degree Beaume or the hydrochloric acid of 5～10 degree Beaume.The sulfuric acid of described 5～10 degree Beaume is the sulfuric acid that commercially available vitriol oil water is adjusted to 5～10 degree Beaume; The hydrochloric acid of described 5～10 degree Beaume is the hydrochloric acid that commercially available concentrated hydrochloric acid water is adjusted to 5～10 degree Beaume; With acid neutralization adjusting whole system PH to 6～8, the scope of this pH value is that termination crosslinking reaction is necessary, lower than this pH value, can affect starch viscosity.
In above-mentioned steps 1, then regulate whole system PH to 6～8 with acid neutralization, and then obtain required cross-linking starch after washing after filtration successively, sedimentation concentrate, air stream drying processing; Described filtration washing is to remove impurity by filtration, adopts tap water to wash; These two steps of described sedimentation concentrate and air stream drying are the routine operations that do not belong to the present application point, are the general treatment scheme of Starch Production and conventional post-processing operation.Sedimentation concentrate refers to use settling centrifuge to carry out sedimentation to starch slurry, removes too much moisture content, and air stream drying is to use commercially available pneumatic conveying dryer to carry out drying treatment to starch.
The sex change of step 2 carboxymethyl
The cross-linking starch that step 1 is prepared drops in mixing tank, and slowly add sodium hydrate solid particle, stir and obtain cross-linking starch mixture after 15～30 minutes, the mixed solution of fatty alcohol-polyoxyethylene ether and water is injected in this cross-linking starch mixture with vaporific form, and the cross-linking starch mixture after being alkalized after heated and stirred, with cross blower fan suction the moisture content of the cross-linking starch mixture after this alkalization is dropped to≤15% after, Monochloro Acetic Acid solution is injected on the cross-linking starch mixture after this alkalization with vaporific form, obtain the required reacting material mixture of carboxymethylation reaction, then by this reacting material mixture after crusher carries out break process, be placed in successively microwave reaction system and infrared heat-insulation system carries out carboxymethylation reaction, carboxymethylation reaction product is taken out and is chilled to after 20～32 ℃ of normal temperature by blower fan, regulates behind its PH to 6～8 with hydrochloric acid, obtain required for the present invention oxidation cross-linked-carboxymethyl composite modified starch.
In above-mentioned steps 2, cross-linking starch that step 1 is prepared drops in mixing tank, and slowly add sodium hydrate solid particle, sodium hydrate particle addition be described in step 1 native starch (over-dry weight) gross weight 6～10%.
In above-mentioned steps 2, the mixed solution of fatty alcohol-polyoxyethylene ether and water refers to the liquid being mixed by fatty alcohol-polyoxyethylene ether and water, in this mixed solution, the consumption of fatty alcohol-polyoxyethylene ether be described in step 1 native starch (over-dry weight) gross weight 3～6%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 7～12%.
In above-mentioned steps 2, the mixed solution of fatty alcohol-polyoxyethylene ether and water is injected in this cross-linking starch mixture with vaporific form, and heated and stirred, the condition of described heated and stirred is: whipping temp is 50～70 ℃, churning time is 30～50 minutes; Because contriver finds by research, under this whipping temp and churning time, can make starch alkalization more abundant, thereby be conducive to the effect of follow-up test.
In above-mentioned steps 2, Monochloro Acetic Acid act as etherifying agent, the compound method of described Monochloro Acetic Acid solution is: Monochloro Acetic Acid is dissolved in water, dissolves completely, obtain Monochloro Acetic Acid solution; In this Monochloro Acetic Acid solution: the consumption of Monochloro Acetic Acid be described in step 1 native starch (over-dry weight) gross weight 6～12%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 7～12%.
In above-mentioned steps 2, this reacting material mixture is carried out to break process through crusher, this break process is that contriver determines after experiment is groped, contriver finds, by fragmentation, can make chemical agent more evenly in starch, and while making microwave reaction, do not have macrobead, thereby cause local gelatinization phenomenon; The screen cloth of crusher is 60～80 orders.
In above-mentioned steps 2, reacting material mixture required carboxymethylation reaction is placed in to the concrete operations that microwave reaction system and infrared heat-insulation system carry out carboxymethylation reaction is successively: first reacting material mixture required carboxymethylation reaction is placed in to microwave reaction system, the temperature of microwave reaction remains on 70～90 ℃, the microwave reaction time is 25～40 minutes, especially the control of microwave reaction temperature is the emphasis that the inventor optimizes, because contriver finds by research, higher or lower than 70～90 ℃ of these temperature ranges, all can greatly reduce reaction efficiency, this temperature range is optimal reaction temperature of the present invention, and then be placed in infrared heat-insulation system, the temperature of infrared insulation is controlled at 70～90 ℃, soaking time is 5～15 minutes, employing be Infrared wavelength.
In above-mentioned steps 2, contriver finds by research, and microwave is to water medium sensitivity, and the water yield is many or do not use dehumidifier, can cause the easy gelatinization of starch, therefore, above-mentioned microwave reaction system and infrared heat-insulation system all need to open dehumidifier apparatus simultaneously, if do not open dehumidifier apparatus, the steam giving out is too greatly to reacting unfavorable, and easily in reaction channel, form the condensation globule, and splash in starch, affect starch quality.
In above-mentioned steps 2, regulate its PH to 6～8 with hydrochloric acid, described hydrochloric acid is the hydrochloric acid that adopts 5～10 degree Beaume, and the hydrochloric acid of described 5～10 degree Beaume is the hydrochloric acid that commercially available concentrated hydrochloric acid water is adjusted to 5～10 degree Beaume.
In preparation method of the present invention, microwave reaction system must be in conjunction with infrared heat-insulation system together, because contriver finds by research: microwave reaction is mainly by water molecules conduction heat, and after water medium is dispersed into a certain degree, again will be larger on product whiteness impact with microwave, with infrared insulation, be conducive to reaction and continue, also can not affect whiteness.
The present invention also claimed by above-mentioned preparation method, prepared oxidation cross-linked-carboxymethyl composite modified starch; this modified starch is analyzed and can be found by detection; it can prepare the painting slurry of 30% above high density; and slurries can keep good mobility, water-retentivity; meet the coating requirement of the high-end product such as noncarbon recording paper, enamelled paper in paper industry; at present existing procucts are preced with the noncarbon recording paper of imperial paper industry for the enamelled paper of Chang'an, Dongguan Chang Zhong Paper Co., Ltd and Zhanjiang, and paper coating is satisfactory for result.
Compared with prior art, the present invention has following beneficial effect:
1. for the problem of prior art, the present invention, by having adopted microwave heating and the technology that infrared insulation combines after studying, makes oxidative crosslinked starch under half dry powder, to carry out carboxymethyl reaction, significantly reduces production costs, and is easy to universal production; In addition, through the oxidation cross-linked powder of alkalinisation treatment, add after Monochloro Acetic Acid, the concentrated heating of microwave in microwave reactor, can more effectively improve the efficiency of chemical reaction, and this is that common dry heating does not reach;
2. traditional heating method is to rely on thermal source, by approach such as radiation, conduction, convection current, first make the surface heating of object, then through thermal conduction, inner temperature is from outward appearance to inner essence progressively raise, heat transmission speed is very slow like this, reaching the heating of starch entirety needs for a long time, the ununiformity that easily causes starch heating, even can cause starch flavescence, thereby affect the whiteness index of starch simultaneously; And the present invention adopts microwave heating method, make full use of the absorption of water molecules to microwave in starch, starch is carried out to direct, overall, penetrance heating, rate of heating is fast, good uniformity, and reaction efficiency is high, and is convenient to control the quality of starch;
3. preparation method of the present invention is by the optimization to some key operations in process, thereby guaranteed the performance of final composite modified starch, as reacting material mixture required carboxymethylation reaction is first carried out after break process, carry out again microwave heating and infrared insulation, break process herein can effectively prevent starch conglomeration, avoid the local gelatinization of starch, also make starch epigranular, thereby improve reaction efficiency;
Preparation method of the present invention simple, with low cost, without adopting organic solvent, comprehensive cost performance good, prepare gained oxidation cross-linked-carboxymethyl composite modified starch excellent property, there is excellent fluidity and water-retentivity with the painting slurry of this modified starch preparation, can meet well the high-end product such as noncarbon recording paper, enamelled paper coating requirement in paper industry, there is good development and application prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention is done further and described, but specific embodiment does not do any restriction to the present invention.
embodiment 1 is oxidation cross-linked-carboxymethyl composite modified starch
The present embodiment oxidation cross-linked-carboxymethyl composite modified starch, its preparation method comprises the steps:
Step 1 is oxidation cross-linked to drop into W-Gum and water in dissolving vessel, stirring prepares the starch slurry that concentration is 20 degree Beaume, regulate pH value to 10～11.5 of this starch slurry with the sodium hydroxide that mass percent concentration is 4% after, start to heat up, starch slurry temperature is controlled to 35～42 ℃, keep adding clorox and phosphorus oxychloride under whipped state, under whipped state, carry out crosslinking reaction 90～150 minutes, sampling detects when starch slurry quality is 25% than concentration, starch viscosity reaches 3～10mpa.s and finishes crosslinking reaction, in reaction system, slowly add sodium bisulfite, until survey the variable color of chlorine test paper, stop adding sodium bisulfite, again with in the hydrochloric acid of 5 degree Beaume and adjusting whole system PH to 6～8, and then successively after filtration, after washing and drying treatment, obtain required cross-linking starch (moisture content≤15%),
In above-mentioned steps 1,8% of native starch (over-dry weight) gross weight that the add-on of clorox is step 1; The add-on of phosphorus oxychloride be described in step 1 native starch (over-dry weight) gross weight 0.08%.
The sex change of step 2 carboxymethyl
The cross-linking starch that step 1 is prepared drops in mixing tank, and slowly add sodium hydrate solid particle (sodium hydrate particle addition be native starch described in step 1 over-dry weight gross weight 6%), stir and obtain cross-linking starch mixture after 15～30 minutes, the mixed solution of fatty alcohol-polyoxyethylene ether and water is injected in this cross-linking starch mixture with vaporific form, and heated and stirred (whipping temp is 50～70 ℃, churning time is 30～50 minutes) after cross-linking starch mixture after being alkalized, with cross blower fan suction the moisture content of the cross-linking starch mixture after this alkalization is dropped to≤15% after, Monochloro Acetic Acid solution is injected on the cross-linking starch mixture after this alkalization with vaporific form, obtain the required reacting material mixture of carboxymethylation reaction, then this reacting material mixture is carried out after break process through crusher (screen cloth of crusher is 60～80 orders), be placed in successively microwave reaction system and infrared heat-insulation system carries out carboxymethylation reaction, carboxymethylation reaction product is taken out and is chilled to after 20～32 ℃ of normal temperature by blower fan, regulates behind its PH to 6～8 with the hydrochloric acid of 5 degree Beaume, obtain the present embodiment oxidation cross-linked-carboxymethyl composite modified starch.
In above-mentioned steps 2, in the mixed solution of fatty alcohol-polyoxyethylene ether and water, the consumption of fatty alcohol-polyoxyethylene ether be described in step 1 native starch (over-dry weight) gross weight 6%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 7%.
In above-mentioned steps 2, in Monochloro Acetic Acid solution: the consumption of Monochloro Acetic Acid be described in step 1 native starch (over-dry weight) gross weight 6%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 12%.
In above-mentioned steps 2, the temperature of microwave reaction remains on 70～90 ℃, and the microwave reaction time is 25～40 minutes, and then be placed in infrared heat-insulation system, the temperature of infrared insulation is controlled at 70～90 ℃, and soaking time is 5～15 minutes, employing be Infrared wavelength; Microwave reaction system and infrared heat-insulation system are all opened dehumidifier apparatus simultaneously.
The present embodiment is prepared oxidation cross-linked-carboxymethyl composite modified starch after conventional crusher, powder shifter are processed, weigh, be packaged to be finished product.
The present embodiment oxidation cross-linked-carboxymethyl composite modified starch carries out performance test, found that:
The present embodiment product is oxidation cross-linked-and the degree of substitution by carboxymethyl of carboxymethyl composite modified starch is 0.15～0.28, and product is soluble in hot water, and viscosity stability is higher, good water-retaining property, starch paste liquid normal temperature is placed 24 hours, and surface is skinning not.
embodiment 2 is oxidation cross-linked-carboxymethyl composite modified starch
The present embodiment oxidation cross-linked-carboxymethyl composite modified starch, its preparation method comprises the steps:
Step 1 is oxidation cross-linked
Yam starch and water are dropped in dissolving vessel, stirring prepares the starch slurry that concentration is 24 degree Beaume, regulate pH value to 10～11.5 of this starch slurry with the sodium hydroxide that mass percent concentration is 5% after, start to heat up, starch slurry temperature is controlled to 35～42 ℃, keep adding clorox and epoxy chloropropane under whipped state, under whipped state, carry out crosslinking reaction 90～150 minutes, sampling detects when starch slurry quality is 25% than concentration, starch viscosity reaches 3～10mpa.s and finishes crosslinking reaction, in reaction system, slowly add sodium bisulfite, until survey the variable color of chlorine test paper, stop adding sodium bisulfite, again with in the hydrochloric acid of 8 degree Beaume and adjusting whole system PH to 6～8, and then successively after filtration, after washing and drying treatment, obtain required cross-linking starch (moisture content≤15%),
In above-mentioned steps 1,4% of native starch (over-dry weight) gross weight that the add-on of clorox is step 1; The add-on of epoxy chloropropane be described in step 1 native starch (over-dry weight) gross weight 0.3%.
The sex change of step 2 carboxymethyl
The cross-linking starch that step 1 is prepared drops in mixing tank, and slowly add sodium hydrate solid particle (sodium hydrate particle addition be native starch described in step 1 over-dry weight gross weight 9%), stir and obtain cross-linking starch mixture after 15～30 minutes, the mixed solution of fatty alcohol-polyoxyethylene ether and water is injected in this cross-linking starch mixture with vaporific form, and heated and stirred (whipping temp is 50～70 ℃, churning time is 30～50 minutes) after cross-linking starch mixture after being alkalized, with cross blower fan suction the moisture content of the cross-linking starch mixture after this alkalization is dropped to≤15% after, Monochloro Acetic Acid solution is injected on the cross-linking starch mixture after this alkalization with vaporific form, obtain the required reacting material mixture of carboxymethylation reaction, then this reacting material mixture is carried out after break process through crusher (screen cloth of crusher is 60～80 orders), be placed in successively microwave reaction system and infrared heat-insulation system carries out carboxymethylation reaction, carboxymethylation reaction product is taken out and is chilled to after 20～32 ℃ of normal temperature by blower fan, regulates behind its PH to 6～8 with the hydrochloric acid of 8 degree Beaume, obtain the present embodiment oxidation cross-linked-carboxymethyl composite modified starch.
In above-mentioned steps 2, in the mixed solution of fatty alcohol-polyoxyethylene ether and water, the consumption of fatty alcohol-polyoxyethylene ether be described in step 1 native starch (over-dry weight) gross weight 3%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 11%.
In above-mentioned steps 2, in Monochloro Acetic Acid solution: the consumption of Monochloro Acetic Acid be described in step 1 native starch (over-dry weight) gross weight 11%, the consumption of water be described in step 1 native starch (over-dry weight) gross weight 7%.
In above-mentioned steps 2, the temperature of microwave reaction remains on 70～90 ℃, and the microwave reaction time is 25～40 minutes, and then be placed in infrared heat-insulation system, the temperature of infrared insulation is controlled at 70～90 ℃, and soaking time is 5～15 minutes, employing be Infrared wavelength; Microwave reaction system and infrared heat-insulation system are all opened dehumidifier apparatus simultaneously.
The present embodiment is prepared oxidation cross-linked-carboxymethyl composite modified starch after conventional crusher, powder shifter are processed, weigh, be packaged to be finished product.
The present embodiment oxidation cross-linked-carboxymethyl composite modified starch carries out performance test, found that:
The present embodiment product is oxidation cross-linked-and its degree of substitution by carboxymethyl of carboxymethyl composite modified starch is 0.15～0.28, and product is soluble in hot water, and viscosity stability is higher, good water-retaining property, starch paste liquid normal temperature is placed 24 hours, and surface is skinning not.
Claims (8)
1. the preparation method of oxidation cross-linked-carboxymethyl composite modified starch, it is characterized in that this preparation method first carries out oxidation cross-linked processing to starch material to obtain after cross-linking starch, again take Monochloro Acetic Acid and cross-linking starch as reaction raw materials, thereby in microwave reaction system and infrared heat-insulation system, carry out carboxymethylation reaction obtain required oxidation cross-linked-carboxymethyl composite modified starch, the temperature of described microwave reaction system is 70～90 ℃, the microwave reaction time is 25～40 minutes, the temperature of infrared heat-insulation system is 70～90 ℃, and soaking time is 5～15 minutes; This preparation method specifically comprises the steps:
Step 1 is oxidation cross-linked
Native starch and water are dropped in dissolving vessel, stirring prepares the starch slurry that concentration is 20～24.5 degree Beaume, regulate pH value to 10～11.5 of this starch slurry with caustic alkali after, start to heat up, starch slurry temperature is controlled to 35～42 ℃, keep adding clorox and linking agent under whipped state, under whipped state, carry out crosslinking reaction 90～150 minutes, sampling detects when starch slurry quality is 25% than concentration, starch viscosity reaches 3～10mpa.s and finishes crosslinking reaction, in crosslinking reaction system, slowly add sodium bisulfite, until survey the variable color of chlorine test paper, stop adding sodium bisulfite, with acid neutralization, regulate whole system PH to 6～8 again, and then successively after filtration, after washing and drying treatment, obtain required cross-linking starch,
The sex change of step 2 carboxymethyl
The cross-linking starch that step 1 is prepared drops in mixing tank, and slowly add sodium hydrate solid particle, stir and obtain cross-linking starch mixture after 15～30 minutes, the mixed solution of fatty alcohol-polyoxyethylene ether and water is injected in this cross-linking starch mixture with vaporific form, and at 50～70 ℃, stir the cross-linking starch mixture after being alkalized after 30～50 minutes, with cross blower fan suction the moisture content of the cross-linking starch mixture after this alkalization is dropped to≤15% after, Monochloro Acetic Acid solution is injected on the cross-linking starch mixture after this alkalization with vaporific form, obtain the required reacting material mixture of carboxymethylation reaction, then this reacting material mixture is placed in to microwave reaction system successively and infrared heat-insulation system carries out carboxymethylation reaction, carboxymethylation reaction product is taken out and is chilled to after 20～32 ℃ of normal temperature by blower fan, regulates behind its PH to 6～8 with the hydrochloric acid of 5～10 degree Beaume, obtain required for the present invention oxidation cross-linked-carboxymethyl composite modified starch.
According to claim 1 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in described step 1, native starch refers to any one or two or more the mixing in W-Gum, tapioca (flour) or yam starch.
According to claim 1 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in described step 1, caustic alkali is that mass percent concentration is 3～5% sodium hydroxide.
According to claim 1 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in described step 1, the add-on of clorox be described in step 1 native starch over-dry weight gross weight 4～8%; Described linking agent is any one in phosphorus oxychloride or epoxy chloropropane, the add-on of linking agent be described in step 1 native starch over-dry weight gross weight 0.08～0.3%.
According to described in any one in claim 1 to 4 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in described step 2, sodium hydrate particle addition be described in step 1 native starch over-dry weight gross weight 6～10%.
According to claim 5 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in the fatty alcohol-polyoxyethylene ether of described step 2 and the mixed solution of water, the consumption of fatty alcohol-polyoxyethylene ether be described in step 1 native starch over-dry weight gross weight 3～6%, the consumption of water be described in step 1 native starch over-dry weight gross weight 7～12%.
According to claim 5 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that in the Monochloro Acetic Acid solution of described step 2, the consumption of Monochloro Acetic Acid be described in step 1 native starch over-dry weight gross weight 6～12%, the consumption of water be described in step 1 native starch over-dry weight gross weight 7～12%.
According to claim 1 a kind of oxidation cross-linked-preparation method of carboxymethyl composite modified starch, it is characterized in that the required reacting material mixture of described carboxymethylation reaction needs first after the break process of crusher, to be just placed in successively microwave reaction system and infrared heat-insulation system carries out carboxymethylation reaction, the screen cloth of described crusher is 60～80 orders.
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| US6299907B1 (en) * | 1998-06-12 | 2001-10-09 | Kansas State University Research Foundation | Reversibly swellable starch products |
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