CN101519455B - Method for preparing composite modified starch - Google Patents
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- CN101519455B CN101519455B CN2009100381106A CN200910038110A CN101519455B CN 101519455 B CN101519455 B CN 101519455B CN 2009100381106 A CN2009100381106 A CN 2009100381106A CN 200910038110 A CN200910038110 A CN 200910038110A CN 101519455 B CN101519455 B CN 101519455B
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 229920000881 Modified starch Polymers 0.000 title claims abstract description 19
- 239000004368 Modified starch Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 18
- 229920002472 Starch Polymers 0.000 claims abstract description 49
- 235000019698 starch Nutrition 0.000 claims abstract description 49
- 239000008107 starch Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 12
- 239000011265 semifinished product Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000003518 caustics Substances 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005886 esterification reaction Methods 0.000 claims description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- -1 compound phosphoric acid salts Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 150000003014 phosphoric acid esters Chemical group 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000013016 damping Methods 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 abstract description 11
- 229920000742 Cotton Polymers 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000009990 desizing Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 238000009955 starching Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004925 denaturation Methods 0.000 description 3
- 230000036425 denaturation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for preparing composite modified starch. The method comprises the following steps: 1) slurrying a raw material, namely a natural starch, and adjusting pH value of the natural starch by caustic alkali; 2) adding an oxidizing agent into the starch slurry to carry out oxidation modification treatment; 3) filtering, washing and drying the starch slurry into a powdered semi-finished product for standby; 4) spraying a catalyst and composite phosphate into the semi-finished product to carry out dry modification treatment; and 5) cooling the semi-finished product to a temperature of between 25 and 35 DEG C, adjusting the pH value of the semi-finished product to 6-8 to carry out secondary drying, and crushing the product to obtain a finished product. The product obtained by the method greatly improves dispersibility of the starch slurry, can be easily stewed with stable slurry, cannot be frozen, can completely replace the chemical synthetic slurry to size pure coarse cotton and medium yarns, and can replace the synthetic slurry in large scale to size high grade cotton yarns and union yarns, thereby greatly reducing yarn sizing cost, facilitating desizing, and contributing to environment-friendly waste water treatment.
Description
Technical field
The present invention relates to a kind of method for preparing composite modified starch, especially be applicable to the preparation technology who produces the modified starch in the sizing fabric.
Background technology
At present, the modified starch that is applied in the textile sizing industry is one of three major types spinning sizing agent, and other two classes slurries are polyvinyl alcohol and polyacrylic.Modified starch uses as the main body slurry in cotton yarn and union yarn starching process.
In the prior art, one or both denaturation methods among pre-gelatinization, carboxymethyl etherification, the crosslinked etherificate three are adopted in the sex change of starch mostly.Wherein: pre-gelatinized starch, can in cold water, swelling dissolve, rehydration is good, but its cold bonding degree is lower, easily retrogradation.Carboxymethyl starch dissolves in cold water at substitution value more than 0.1, the solution clear, and viscosity is also high, and bonding force is big, and solvability is good; But its viscosity anti-shearing force is poor, has influenced its use range greatly, and is very responsive to salt, adds small amount of hydrochloric acid in solution, sodium hydroxide solution will make viscosity drop much lower; The cross-linking starch anti-shearing force is strong, and can change the viscose glue of starch paste, has higher freeze-stable and freeze-thaw stability, but its cold water solubility is poor.So far do not retrieve the modified starch and the method thereof that above-mentioned three kinds of methods are merged, make starch generation complex reaction and generate as yet.
Domestic existing spinning sizing agent mainly is that single sex change is main with modified starch, mix in conjunction with polyvinyl alcohol (PVA), oleic series chemical sizwe again and use, although polyvinyl alcohol, oleic series slurry have good sizing performance, especially to the starch finishing effect ideal of synthon and union yarn thereof, but cost an arm and a leg, and destarch difficulty.
Application number: 200710029521.X, the Chinese disclosure of the Invention of publication number: CN101104642A a kind of preparation method of composite modified starch, be earlier yam starch to be carried out oxidation with hydrogen peroxide, oxidizing reaction is carried out under the katalysis of copper sulfate; And then carry out crosslinking reaction with linking agent epoxy chloropropane or Phosphorus Oxychloride, crosslinking reaction is carried out under the caustic alkali katalysis, and linking agent adds in the starch suspension with inert solvent dissolving back, respond and all carry out in the suspension in water, but this method reaction efficiency is low relatively, and is poor to high grade cotton yarn, union yarn starching cohesive force, the destarch difficulty, this invention is to adopt the wet method modified starch, and wastewater discharge is bigger, and environment is polluted.
Summary of the invention
In order to overcome existing sizing modified starch to high grade cotton yarn, union yarn starching cohesive force is poor, the destarch difficulty, this invention is to adopt the wet method modified starch, wastewater discharge is bigger, to deficiencies such as environment pollute, the invention provides and a kind ofly can produce method for preparing composite modified starch, the product that adopts this method to produce has greatly improved the dispersiveness of starch slurry, boiling is easy and slurries stable, can not congeal, and is thick to cotton textiles, the medium yarn starching is the instead of chemical synthetic slurry fully, to high grade cotton yarn, but union yarn starching also vast scale substitutes synthetic slurry, thereby significantly reduce sizing costs, destarch simultaneously is easy, helps environment-protection wastewater and handles.
The technical solution adopted for the present invention to solve the technical problems is: this method for preparing composite modified starch, and its processing step is as follows:
1) with in the starch material input spray medicinal cupping, mix with 30～60 ℃ warm water, concentration is transferred to 17～24 ° of B é, and transfer pH value to 8～11 with caustic alkali;
2) add oxygenant starch slurry is carried out the oxidative deformation processing: add oxygenant 0.5～4% in the starch per ton, then the starch slurry temperature is controlled at 25～45 ℃, keep stirring, reaction 40～120min, after the detection starch viscosity reaches 5～40mpa.s, with the responseless clorox of bisulfite sodium reduction, being neutralized to pH value with 5～15 ° of B é acid is 7～9, wherein oxygenant is one or more in hydrogen peroxide, potassium permanganate, the hypochlorite, preferred clorox, acid are sulfuric acid, hydrochloric acid, EDTA, suitable mineral acid or the organic acid of acetic acid;
3) filter, wash, be dried to the powder semi-finished product for standby;
4) sprinkling catalyzer and composite phosphate carry out dry modification treatment in work in-process: at first spray catalyzer and compound phosphoric acid salts solution in work in-process, and after stirring, mixture is dried to 7～15% moisture content, then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 100～140 ℃, time is 40～120min, make the phosphoric acid ester substitution value reach 0.005～0.05, wherein catalyzer is carboxylamine or urea, its consumption is 2～6% by weight percentage, and composite phosphate is NaH
2PO
4, Na
2HPO
4, POCl
3, its ratio is NaH
2PO
4: Na
2HPO
4: POCl
3=(8～5): (1～4): (0.5～1.5), compound phosphoric acid concentration of salt solution are 3～12%.
5) cool to 25～35 ℃, adjust pH value to 6～8 then, carry out redrying again, it is 7～15% by weight percentage that the starch behind the complex denaturation is dried to water content, last damping, is crushed to finished product.
After the product of gained of the present invention utilizes oxygenant oxidation degraded viscosity earlier, at high temperature starch is carried out the reaction of degeneration of esterification dry method with composite phosphate again, introduce carbamate and starch-phosphate simultaneously, greatly improved the dispersiveness of starch slurry, boiling is easy and slurries stable, can not congeal,, medium yarn starching thick to cotton textiles be the instead of chemical synthetic slurry fully, but high grade cotton yarn, union yarn starching also vast scale are substituted synthetic slurry, thereby significantly reduce sizing costs, destarch simultaneously is easy, helps environment-protection wastewater and handles; Simultaneously preferred urea is made catalyzer, when the sex change of dry method phosphoric acid ester, improve reaction efficiency, chemical modification at high temperature also can take place in urea self and starch simultaneously, form starch carbamate, so both improved reaction of degeneration efficient, simultaneously introduce various chemical ester group again, thereby promoted the chemical property that this product is used for spinning sizing agent.
Embodiment
It is poor to high grade cotton yarn, union yarn starching cohesive force when using with starch that the inventive method efficiently solves existing sizing, the destarch difficulty, and wastewater discharge is bigger, and to insufficient problems such as environment pollute, it is as follows that this invents concrete technology:
1) with in the starch material input spray medicinal cupping, mix with 30～60 ℃ warm water, concentration is transferred to 17～24 ° of B é, and transfer pH value to 8～11 with caustic alkali;
2) add oxygenant starch slurry is carried out the oxidative deformation processing: add oxygenant 0.5～4% in the starch per ton, then the starch slurry temperature is controlled at 25～45 ℃, keep stirring, reaction 40～120min, after the detection starch viscosity reaches 5～40mpa.s, with the responseless clorox of bisulfite sodium reduction, being neutralized to pH value with 5～15 ° of B é acid is 7～9, wherein oxygenant is one or more in hydrogen peroxide, potassium permanganate, the hypochlorite, preferred clorox, acid are sulfuric acid, hydrochloric acid, EDTA, suitable mineral acid or the organic acid of acetic acid;
3) filter, wash, be dried to the powder semi-finished product for standby;
4) sprinkling catalyzer and composite phosphate carry out dry modification treatment in work in-process: at first spray catalyzer and compound phosphoric acid salts solution in work in-process, and after stirring, mixture is dried to 7～15% moisture content, then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 100～140 ℃, time is 40～120min, make the phosphoric acid ester substitution value reach 0.005～0.05, wherein catalyzer is carboxylamine or urea, its consumption is 2～6% by weight percentage, and composite phosphate is NaH
2PO
4, Na
2HPO
4, POCl
3, its ratio is NaH
2PO
4: Na
2HPO
4: POCl
3=(8～5): (1～4): (0.5～1.5), compound phosphoric acid concentration of salt solution are 3～12%.
5) cool to 25～35 ℃, adjust pH value to 6～8 then, carry out redrying again, it is 7～15% by weight percentage that the starch behind the complex denaturation is dried to water content, last damping, is crushed to finished product.
Below it will be appreciated by those skilled in the art that, illustrate with regard to embodiment.
Embodiment 1
With the starch slurry of 30 ℃ an amount of warm water, and its pH value is transferred to 8 with 17 ° of B é of 1 ton of native starch furnishing; Add 0.5% oxygenant clorox by weight percentage again, then the starch slurry temperature is controlled at 25 ℃, keep stirring, reaction 40min, after detecting starch viscosity and reaching 5mpa.s, with the responseless clorox of bisulfite sodium reduction, and to be neutralized to pH value with 5 ° of B é acid be 7; Then filter, wash, be dried to the powder semi-finished product for standby; Spray in work in-process is that 2% catalyzer and concentration are that 3% composition is than being NaH by weight percentage again
2PO
4: Na
2HPO
4: POCl
3=5: 1: 0.5 compound phosphoric acid salts solution, and after stirring, mixture is dried to 7～15% moisture content, and then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 100 ℃, the time is 40min; After the phosphoric acid ester substitution value reaches 0.005, cool to 25 ℃, adjust pH value to 6 then, last damping, be crushed to finished product.
Embodiment 2
With the starch slurry of 45 ℃ an amount of warm water, and its pH value is transferred to 9.5 with 20 ° of B é of 1 ton of native starch furnishing; Add 2% oxygenant clorox by weight percentage again, then the starch slurry temperature is controlled at 30 ℃, keep stirring, reaction 80min, after detecting starch viscosity and reaching 5～40mpa.s, with the responseless clorox of bisulfite sodium reduction, and to be neutralized to pH value with 10 ° of B é acid be 8; Then filter, wash, be dried to the powder semi-finished product for standby; Spray in work in-process is that 4% catalyzer and concentration are that 7% composition is than being NaH by weight percentage again
2PO
4: Na
2HPO
4: POCl
3=6.5: 2.5: 1.0 compound phosphoric acid salts solution, and after stirring, mixture is dried to 7～15% moisture content, and then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 120 ℃, the time is 80min; After the phosphoric acid ester substitution value reaches 0.02, cool to 30 ℃, adjust pH value to 7 then, last damping, be crushed to finished product.
Embodiment 3
With the starch slurry of 60 ℃ an amount of warm water, and its pH value is transferred to 11 with 24 ° of B é of 1 ton of native starch furnishing; Add 4% oxygenant clorox by weight percentage again, then the starch slurry temperature is controlled at 45 ℃, keep stirring, reaction 120min, after detecting starch viscosity and reaching 40mpa.s, with the responseless clorox of bisulfite sodium reduction, and to be neutralized to pH value with 15 ° of B é acid be 9; Then filter, wash, be dried to the powder semi-finished product for standby; Spray in work in-process is that 6% catalyzer and concentration are that 12% composition is than being NaH by weight percentage again
2PO
4: Na
2HPO
4: POCl
3=8: 4: 1.5 compound phosphoric acid salts solution, and after stirring, mixture is dried to 7～15% moisture content, and then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 140 ℃, the time is 120min; After the phosphoric acid ester substitution value reaches 0.05, cool to 35 ℃, adjust pH value to 8 then, last damping, be crushed to finished product.
Claims (3)
1. method for preparing composite modified starch, this method processing step is:
1) the native starch raw material is sized mixing---in starch material input spray medicinal cupping, mix, concentration is transferred to 17～24 ° of B é with 30～60 ℃ warm water, and with caustic alkali adjust pH to 8～11;
2) one or more in adding oxidants hydrogen peroxide, potassium permanganate, the hypochlorite carry out the oxidative deformation processing to starch slurry,
It is to add oxygenant clorox 0.5～4% in the starch per ton that described oxidative deformation is handled, then the starch slurry temperature is controlled at 25～45 ℃, keep stirring, reaction 40～120min, after the detection starch viscosity reaches 5～40mpa.s, with the responseless clorox of bisulfite sodium reduction, and to be neutralized to the pH value with mineral acid or organic acid be 7～9, and described mineral acid or organic acid are one or more in the sulfuric acid, hydrochloric acid, EDTA, acetic acid of 5～15 ° of B é;
3) filter, wash, be dried to the powder semi-finished product for standby;
4) sprinkling catalyzer and composite phosphate carry out dry modification treatment in work in-process---at first in work in-process, spray catalyzer and compound phosphoric acid salts solution, and after stirring, mixture is dried to 7～15% moisture content, then this mixture is dropped in the esterification reaction tank, again temperature of reaction in the esterification reaction tank is transferred to 100～140 ℃, time is 40～120min, makes the phosphoric acid ester substitution value reach 0.005～0.05;
5) cool to 25～35 ℃, adjust pH value to 6～8 then, last damping, be crushed to finished product.
2. method for preparing composite modified starch according to claim 1 is characterized in that: described catalyzer is carboxylamine or urea, and its consumption is 2～6% by weight percentage.
3. method for preparing composite modified starch according to claim 1 is characterized in that: described composite phosphate is NaH
2PO
4, Na
2HPO
4, POCl
3Mixture, its mixture ratio is NaH
2PO
4: Na
2HPO
4: POCl
3=(8～5): (1～4): (0.5～1.5); The compound phosphoric acid concentration of salt solution is 3～12%.
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| CN2009100381106A CN101519455B (en) | 2009-03-21 | 2009-03-21 | Method for preparing composite modified starch |
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|---|---|---|---|
| CN2009100381106A CN101519455B (en) | 2009-03-21 | 2009-03-21 | Method for preparing composite modified starch |
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| CN101519455B true CN101519455B (en) | 2011-06-08 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212143A (en) * | 2011-05-17 | 2011-10-12 | 东华大学 | Pollution-free preparation method for oxidized phosphated double-modified starch |
| CN103820997A (en) * | 2012-11-19 | 2014-05-28 | 苏州黑蚂蚁物资有限公司 | Polybasic composite esterified starch |
| CN103012680B (en) * | 2013-01-07 | 2013-09-04 | 江西宏大化工有限公司 | Preparation method of composite modified starch size |
| CN106749708A (en) * | 2016-12-02 | 2017-05-31 | 中山华方包装有限公司 | Glutinous agent of Phosphation Modified Oxidize Starth Adhesive and preparation method thereof |
| CN106987030A (en) * | 2017-03-30 | 2017-07-28 | 天长市天达纸箱纸品厂 | A kind of preparation method of collagen aluminium ion modified chlorinated starch compound |
| SE541492C2 (en) * | 2017-08-11 | 2019-10-15 | Lyckeby Starch Ab | Method for preparing an inhibited starch |
| CN107869056A (en) * | 2017-11-30 | 2018-04-03 | 天峨县平昌生态农业有限公司 | A kind of preparation method of preparation method for sizing agent cassava modified starch |
| CN109338725B (en) * | 2018-10-10 | 2021-04-30 | 湖北双迅纺织有限公司 | Textile size composition and preparation method thereof |
| CN113773405B (en) * | 2021-11-01 | 2023-03-10 | 保龄宝生物股份有限公司 | Acetylated distarch phosphate modified starch and preparation method and application thereof |
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