CN105418775A - Cross-linked carboxymethyl hydroxypropylated compound modified starch and preparation method thereof - Google Patents
Cross-linked carboxymethyl hydroxypropylated compound modified starch and preparation method thereof Download PDFInfo
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- CN105418775A CN105418775A CN201510955160.6A CN201510955160A CN105418775A CN 105418775 A CN105418775 A CN 105418775A CN 201510955160 A CN201510955160 A CN 201510955160A CN 105418775 A CN105418775 A CN 105418775A
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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
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
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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
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
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Abstract
The invention relates to the technical field of modified starch and in particular discloses cross-linked carboxymethyl hydroxypropylated compound modified starch and a preparation method thereof. The modified starch is prepared by a method comprising the following steps: firstly, adding an expansion inhibitor, an etherification reagent 1 and a pH adjusting agent into water; after uniformly stirring, adding starch and then adding an etherification reagent 2 to react; adding the pH adjusting agent to adjust the pH of a solution to be 11.1 to 11.5, and heating to be 42 DEG C to 45 DEG C; adding a cross-linking agent to react; then adding the expansion inhibitor and continually reacting; then adding an inorganic acid water solution to adjust the pH of the solution to be 6 to 7.5; then carrying out washing and dehydration treatment to obtain the cross-linked carboxymethyl hydroxypropylated compound modified starch, wherein the etherification reagent 1 is sodium chloroacetate and the etherification reagent 2 is propylene epoxide. The modified starch has good film forming property, flowability and binding power, strong dielectric medium resisting and freezing resisting capabilities, and good properties needed by starch based adhesive.
Description
Technical field
The present invention relates to technical field of modified starch, be specifically related to a kind of cross-linked carboxymethyl hydroxypropyl composite modified starch and preparation method thereof.
Background technology
Wallpaper glue is the abbreviation for sticking wallpaper or wall cloth sizing agent, and it not only will ensure adhibit quality and the work-ing life of wallpaper, also requires environmentally friendly simultaneously.But what human consumer used when fitting up at present mostly is formaldehydes sizing agent, urea-formaldehyde resin adhesive and phenolic resin adhesive, these three kinds of sizing agents in use continuously can discharge formaldehyde and time of releasing long, serious harm is to the health of the mankind and ecotope.Therefore, need badly and research and develop a kind of novel rubber powder and substitute above-mentioned three kinds of sizing agents as wallpaper glue, reduce the harm of building decoration articles for use to human health and environment.
Starch is renewable resources, not only there is good cohesiveness, and wide material sources, cheap, safety non-toxic, environmental protection are easily degraded, due to the above-mentioned characteristic of starch, make it become the research emphasis for emerging Environment-friendlywallpaper wallpaper rubber powder in recent years, starch-base adhesive becomes the natural glue of most potentiality to be exploited.But there is the shortcoming of poor fluidity, poor water resistance, package stability difference due to native starch, amylan application is commercially very restricted, therefore need to research and develop a kind of processing method and modification is carried out to native starch, make it be applicable to be prepared into wallpaper sizing agent.The domestic preparation method for wallpaper sizing agent treated starch is be that medium reacts with organic solvent mostly at present, complex process, be made up of multiple reactions steps, upper and lower step reaction condition difference is large, needing again sizes mixing after washing just can carry out the next step, easily cause environmental pollution, poor continuity, suitability for industrialized production is difficult and cost is high.In addition, the domestic research for wallpaper sizing agent treated starch at present mainly carries out crosslinked and carboxymethyl-modification to starch, as Chinese patent CN102229676A discloses the preparation technology of the special rubber powder of a kind of building coating, successively point oxidizing reaction, crosslinking reaction and etherification reaction three step prepare cross-linked carboxymethyl treated starch, this treated starch coldwater-soluble is poor, complex process, cost are high, and the wallpaper that cannot meet current market popularity wets the requirement of glue complete processing.
Summary of the invention
In order to overcome the defect of prior art, the object of this invention is to provide a kind of cross-linked carboxymethyl hydroxypropyl composite modified starch, the film-forming properties that this treated starch has had, mobility, cohesive force, smear, freeze proof strong with potential resistance to electrolyte contamination ability.
Meanwhile, the present invention also aims to the preparation method providing a kind of cross-linked carboxymethyl hydroxypropyl composite modified starch, take water as reaction medium, the composite modified starch that the dual etherificate of single step reaction synthesis carboxy-methyl hydroxy propyl is crosslinked, Simplified flowsheet step.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of cross-linked carboxymethyl hydroxypropyl composite modified starch, prepared by the method comprising following operation steps and obtain:
1) get swelling inhibitor, etherifying reagent 1, pH adjusting agent, be added to the water, add starch after stirring, furnishing starch slurry breast, then add etherifying reagent 2, reaction, obtains reaction soln 1;
2) in reaction soln 1, add pH=11.1 ~ 11.5 that pH adjusting agent regulates reaction soln 1, be then heated to 42 ~ 45 DEG C, add linking agent, reaction, obtains reaction soln 2;
3) in reaction soln 2, add swelling inhibitor, continue reaction, obtain reaction soln 3;
4) in reaction soln 3, add inorganic acid aqueous solution regulate pH=6 ~ 7.5 of reaction soln 3, then carry out washing, processed, obtain described cross-linked carboxymethyl hydroxypropyl composite modified starch;
Described etherifying reagent 1 is sodium chloroacetate; Described etherifying reagent 2 is propylene oxide.Wherein adopt Mono Chloro Acetic Acid to carry out carboxymethyl-modification as etherifying reagent to starch, compare traditional etherifying reagent using Mono Chloro Acetic Acid as carboxymethyl-modification, reduce the side reaction of whole system, improve reaction efficiency.
Described starch is one in common corn starch, tapioca (flour), waxy corn starch, potato starch or arbitrary combination.
Described step 1) in stir time be 40 ~ 50min.
The mass ratio of described water and starch is 110 ~ 120:100.
Described etherifying reagent 1 is 20 ~ 35:100 with the mass ratio of starch.
Described etherifying reagent 2 is 8 ~ 12:100 with the mass ratio of starch.
Step 1) described in pH adjusting agent be sheet alkali; The mass ratio of described alkali and starch is 0.3 ~ 0.5:100.
Step 2) described in pH adjusting agent to be mass concentration be 2.8% ~ 3.0% aqueous sodium hydroxide solution; The mass ratio of described pH adjusting agent and starch is 55 ~ 60:100.
Described swelling inhibitor is sodium-chlor, sodium sulfate or calcium sulfate; Described step 1) in the mass ratio of swelling inhibitor used and starch be 5 ~ 6:100; Described step 3) in the mass ratio of swelling inhibitor used and starch be 3 ~ 5:100.
Described linking agent is epoxy chloropropane; The mass ratio of described linking agent and starch is 0.01 ~ 0.015:100.
Described inorganic acid aqueous solution to be mass concentration be 10% the HCl aqueous solution.
Step 1) described in reaction time be 1 ~ 1.5 hour.
Step 2) described in reaction time be 12 ~ 14 hours.
Step 3) described in continue react time be 7 ~ 9 hours.
Step 4) described in the concrete grammar of washing be: adopt eddy flow washer to wash, remove reaction residue matter and impurity, until specific conductivity < 2500 μ s/cm.
Step 4) described in dehydration concrete grammar be: adopt vacuum drum dewater, obtain solid substance; Also comprise after described dehydration by solid substance after Air Dried System drying, with 100 order boltings, packaging, obtained described cross-linked carboxymethyl hydroxypropyl composite modified starch.
Cross-linked carboxymethyl hydroxypropyl composite modified starch of the present invention, after adopting carboxymethylation etherifying reagent and hydroxypropylation etherifying reagent to carry out dual etherificate, and then carry out cross-linking modified, formed through crosslinked, carboxymethylation, the triple composite modified starch of hydroxypropylation, make up the drawback of single treated starch, and by adding the mode of swelling inhibitor at twice, improve the substitution value of carboxymethyl and hydroxypropyl, make the modified starch film of preparation, mobility and cohesive force improve, potential resistance to electrolyte contamination and frost resistance strengthen, make it the good characteristic possessed needed for starch-base adhesive, can prepare novel, high-quality, environmental protection, the wallpaper sizing agent of safety.In addition, cross-linked carboxymethyl hydroxypropyl composite modified starch of the present invention is when for the preparation of sizing agent, and the amount of coming unglued is 1.3 ~ 1.5 times of common modified starch, is particularly useful for for the preparation of wall paper and thick and heavy wallpaper sizing agent.
The preparation method of cross-linked carboxymethyl hydroxypropyl composite modified starch of the present invention, take water as reaction medium, the composite modified starch that the dual etherificate of one-step synthesis is crosslinked, not only simplify technique, shorten the reaction times, reduce production cost, and make the treated starch steady quality of preparation, be applicable to industrialization continuous seepage.In addition, the handiness of the method industrial production is strong, and enterprise can according to the cost producing wallpaper sizing agent, is that raw material carries out separately composite modified by the one in common corn starch, tapioca (flour), waxy corn starch, yam starch or arbitrary combination.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
The present embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, prepared by following methods and obtain, concrete operation step is as follows:
1) get 5 parts, sodium-chlor, sodium chloroacetate 20 parts, 0.5 part, sheet alkali adds in 120 parts of water, stir 40min, obtain mixture 1; Then get 100 parts of starch to add in mixture 1, mix, obtain starch slurry breast; Add 0.01 part of propylene oxide 8 parts in starch slurry Ruzhong, stirring reaction 1 hour, obtains reaction soln 1; .
2) in reaction soln 1, add the aqueous sodium hydroxide solution 55 parts that mass concentration is 2.8%, regulate the pH=11.1 of reaction soln 1, be then heated to 42 DEG C, add 0.01 part of epoxy chloropropane, react 12 hours, obtain reaction soln 2;
3) in reaction soln 2, add 3 parts, sodium-chlor, continue reaction 9 hours, obtain reaction soln 3;
4) in reaction soln 3, add the pH=7.5 that mass concentration is the HCl aqueous solution adjustment reaction soln 3 of 10%, then eddy flow washer is adopted to wash, remove reaction residue matter and impurity, until specific conductivity < 2500 μ s/cm, vacuum drum is adopted to dewater again, after Air Dried System drying, with 100 order boltings, packaging, obtained described cross-linked carboxymethyl hydroxypropyl composite modified starch.
In this embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, the substitution value of carboxymethyl is 0.14; The substitution value of hydroxypropyl is 0.19.
Embodiment 2
The present embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, prepared by following methods and obtain, concrete operation step is as follows:
1) get 5.5 parts, sodium sulfate, sodium chloroacetate 30 parts, 0.4 part, sheet alkali adds in 115 parts of water, stir 45min, obtain mixture 1; Then get 100 parts of starch to add in mixture 1, mix, obtain starch slurry breast; Add propylene oxide 10 parts in starch slurry Ruzhong, stirring reaction 1.2 hours, obtains reaction soln 1; .
2) in reaction soln 1, add the aqueous sodium hydroxide solution 57 parts that mass concentration is 2.9%, regulate the pH=11.3 of reaction soln 1, be then heated to 43 DEG C, add 0.012 part of epoxy chloropropane, react 13 hours, obtain reaction soln 2;
3) in reaction soln 2, add 3 parts, sodium sulfate, continue reaction 8 hours, obtain reaction soln 3;
4) in reaction soln 3, add the pH=7.0 that mass concentration is the HCl aqueous solution adjustment reaction soln 3 of 10%, then eddy flow washer is adopted to wash, remove reaction residue matter and impurity, until specific conductivity < 2500 μ s/cm, vacuum drum is adopted to dewater again, after Air Dried System drying, with 100 order boltings, packaging, obtained described cross-linked carboxymethyl hydroxypropyl composite modified starch.
In this embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, the substitution value of carboxymethyl is 0.17; The substitution value of hydroxypropyl is 0.19.
Embodiment 3
The present embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, prepared by following methods and obtain, concrete operation step is as follows:
1) get 6 parts, calcium sulfate, sodium chloroacetate 35 parts, 0.3 part, sheet alkali adds in 110 parts of water, stir 50min, obtain mixture 1; Then get 100 parts of starch to add in mixture 1, mix, obtain starch slurry breast; Add propylene oxide 12 parts in starch slurry Ruzhong, stirring reaction 1.5 hours, obtains reaction soln 1; .
2) in reaction soln 1, add the aqueous sodium hydroxide solution 60 parts that mass concentration is 3.0%, regulate the pH=11.5 of reaction soln 1, be then heated to 45 DEG C, add 0.015 part of epoxy chloropropane, react 14 hours, obtain reaction soln 2;
3) in reaction soln 2, add 3 parts, sodium-chlor, continue reaction 7 hours, obtain reaction soln 3;
4) in reaction soln 3, add the pH=6.0 that mass concentration is the HCl aqueous solution adjustment reaction soln 3 of 10%, then eddy flow washer is adopted to wash, remove reaction residue matter and impurity, until specific conductivity < 2500 μ s/cm, vacuum drum is adopted to dewater again, after Air Dried System drying, with 100 order boltings, packaging, obtained described cross-linked carboxymethyl hydroxypropyl composite modified starch.
In this embodiment cross-linked carboxymethyl hydroxypropyl composite modified starch, the substitution value of carboxymethyl is 0.18; The substitution value of hydroxypropyl is 0.20.
Comparative example
This comparative example treated starch, prepared by following preparation method and obtain, concrete operation step is:
1) get 5 parts, sodium-chlor, sodium chloroacetate 20 parts, 0.5 part, sheet alkali adds in 120 parts of water, stir 40min, obtain mixture 1; Then getting 100 parts of starch adds in mixture 1, and stirring reaction 1 hour, obtains reaction soln 1; .
2) in reaction soln 1, add the aqueous sodium hydroxide solution 55 parts that mass concentration is 2.8%, regulate the pH=11.1 of reaction soln 1, be then heated to 42 DEG C, add epoxy chloropropane, react 12 hours, obtain reaction soln 2;
3) in reaction soln 2, add 3 parts, sodium-chlor, continue reaction 9 hours, obtain reaction soln 3;
4) in reaction soln 3, add the pH=7.5 that mass concentration is the HCl aqueous solution adjustment reaction soln 3 of 10%, then eddy flow washer is adopted to wash, remove reaction residue matter and impurity, until specific conductivity < 2500 μ s/cm, vacuum drum is adopted to dewater again, after Air Dried System drying, with 100 order boltings, packaging, obtained described treated starch.
Test example
1) mensuration of transparency
Sample 1.00g is accurately taken respectively with electronic balance, add the starch milk that 99mL distilled water is mixed with 1% (m/m) respectively, get 50mL starch milk solution to heat 20min while stirring in boiling water bath and make the abundant gelatinization of starch, keep the constancy of volume of starch milk, then in cooling bath, be cooled to 25 DEG C.Do blank with distilled water, arranging its transmittance is 100%, and with the transmittance of 1cm cuvette at 620nm place working sample, each sample determination gets its mean value three times, and result is as shown in table 1 below:
Table 1
| Sample | Transmittance |
| Comparative example | 23.50 |
| Embodiment 1 | 60.25 |
2) mensuration of freeze-thaw stability
Sample 3.00g is accurately taken in 150mL beaker with electronic balance, add 97mL distilled water and be configured to the starch milk that massfraction is 3%, in boiling water bath, heat 20min while stirring make the abundant gelatinization of sample, after being cooled to room temperature, starch paste is poured into respectively in two centrifuge tubes, covering tightly lid is positioned in the deep freezer of-18 ~-20 DEG C, freezing time is one week, then at room temperature thaw 6h naturally, put into whizzer, slowly accelerate to the centrifugal 20min of 3000r/min, discard supernatant liquid and (if anhydrous precipitation, repeatedly put refrigerator freezing into, until there is elutriation to go out), take throw out quality, be calculated as follows syneresis rate: syneresis rate=(sticking with paste weight-throw out weight)/stick with paste heavy × 100%, result is as shown in table 2 below:
Table 2
3) potential resistance to electrolyte contamination ability
Accurately take sample 18.0g in 400mL beaker with electronic balance, add 9g sodium-chlor, add 273g distilled water, in boiling water bath, heat 20min while stirring make the abundant gelatinization of sample, naturally cool to room temperature.Utilize U.S. Brookfield rotational viscosimeter, select suitable rotor, measure the apparent viscosity of sticking with paste liquid, result is as shown in table 3 below:
Table 3
| Sample | Apparent viscosity/mPaS |
| Comparative example | 21300 |
| Embodiment 1 | 52000 |
4) wet according to current industrial production wallpaper sizing agent the formula of glue, and the treated starch adopting embodiment 1 and comparative example to prepare respectively for being mixed with wallpaper sizing agent, and measures the performance of sizing agent, and result is as shown in table 4 below:
Table 4
Claims (10)
1. a cross-linked carboxymethyl hydroxypropyl composite modified starch, is characterized in that, is prepared and obtain by the method comprising following operation steps:
1) get swelling inhibitor, etherifying reagent 1, pH adjusting agent, be added to the water, add starch after stirring, furnishing starch slurry breast, then add etherifying reagent 2, reaction, obtains reaction soln 1;
2) in reaction soln 1, add pH=11.1 ~ 11.5 that pH adjusting agent regulates reaction soln 1, be then heated to 42 ~ 45 DEG C, add linking agent, reaction, obtains reaction soln 2;
3) in reaction soln 2, add swelling inhibitor, continue reaction, obtain reaction soln 3;
4) in reaction soln 3, add inorganic acid aqueous solution regulate pH=6 ~ 7.5 of reaction soln 3, then carry out washing, processed, obtain described cross-linked carboxymethyl hydroxypropyl composite modified starch;
Described etherifying reagent 1 is sodium chloroacetate; Described etherifying reagent 2 is propylene oxide.
2. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, it is characterized in that, the mass ratio of described water and starch is 110 ~ 120:100.
3. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, is characterized in that, described etherifying reagent 1 is 20 ~ 35:100 with the mass ratio of starch; Described etherifying reagent 2 is 8 ~ 12:100 with the mass ratio of starch.
4. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, is characterized in that, step 1) described in pH adjusting agent be sheet alkali; The mass ratio of described alkali and starch is 0.3 ~ 0.5:100.
5. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, it is characterized in that, described swelling inhibitor is sodium-chlor, sodium sulfate or calcium sulfate; Described step 1) in the mass ratio of swelling inhibitor used and starch be 5 ~ 6:100; Described step 3) in the mass ratio of swelling inhibitor used and starch be 3 ~ 5:100.
6. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, it is characterized in that, described linking agent is epoxy chloropropane; The mass ratio of described linking agent and starch is 0.01 ~ 0.015:100.
7. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, is characterized in that, step 1) described in time of reaction be 1 ~ 1.5 hour.
8. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, is characterized in that, step 2) described in time of reaction be 12 ~ 14 hours.
9. cross-linked carboxymethyl hydroxypropyl composite modified starch as claimed in claim 1, is characterized in that, step 3) described in time of continuing to react be 7 ~ 9 hours.
10. a preparation method for cross-linked carboxymethyl hydroxypropyl composite modified starch, is characterized in that, comprises following operation steps:
1) get swelling inhibitor, etherifying reagent 1, pH adjusting agent, be added to the water, add starch after stirring, furnishing starch slurry breast, then add etherifying reagent 2, reaction, obtains reaction soln 1;
2) in reaction soln 1, add pH=11.1 ~ 11.5 that pH adjusting agent regulates reaction soln 1, be then heated to 42 ~ 45 DEG C, add linking agent, reaction, obtains reaction soln 2;
3) in reaction soln 2, add swelling inhibitor, continue reaction, obtain reaction soln 3;
4) in reaction soln 3, add inorganic acid aqueous solution regulate pH=6 ~ 7.5 of reaction soln 3, then carry out washing, processed, obtain described cross-linked carboxymethyl hydroxypropyl composite modified starch;
Described etherifying reagent 1 is sodium chloroacetate; Described etherifying reagent 2 is propylene oxide.
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Cited By (7)
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| CN106675443A (en) * | 2016-11-29 | 2017-05-17 | 安徽索亚装饰材料有限公司 | Starch adhesive applied to household decoration wallpaper |
| CN107502227A (en) * | 2017-08-30 | 2017-12-22 | 广州市高士实业有限公司 | A kind of non-ionic starch based adhesive and preparation method thereof |
| CN107602713A (en) * | 2017-09-25 | 2018-01-19 | 山东神州翔宇科技集团有限公司 | A kind of one-step method carries out the preparation method of cross-linked hydroxypropyl base composite modified starch |
| CN109503726A (en) * | 2018-07-02 | 2019-03-22 | 山东神州翔宇科技集团有限公司 | A kind of one-step method carries out the preparation method of cross-linked hydroxypropyl base composite modified starch |
| CN113150176A (en) * | 2021-04-27 | 2021-07-23 | 山东光大赛路新材料科技有限公司 | Preparation method of multi-group cross-linked modified hydroxypropyl starch ether |
| CN113980617A (en) * | 2021-12-02 | 2022-01-28 | 承德亮美环保科技有限公司 | Preparation process of rare salt mud environment-friendly wall material |
| CN114848888A (en) * | 2022-05-12 | 2022-08-05 | 上海威高医疗技术发展有限公司 | Absorbable starch hemostatic material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675443A (en) * | 2016-11-29 | 2017-05-17 | 安徽索亚装饰材料有限公司 | Starch adhesive applied to household decoration wallpaper |
| CN107502227A (en) * | 2017-08-30 | 2017-12-22 | 广州市高士实业有限公司 | A kind of non-ionic starch based adhesive and preparation method thereof |
| CN107602713A (en) * | 2017-09-25 | 2018-01-19 | 山东神州翔宇科技集团有限公司 | A kind of one-step method carries out the preparation method of cross-linked hydroxypropyl base composite modified starch |
| CN109503726A (en) * | 2018-07-02 | 2019-03-22 | 山东神州翔宇科技集团有限公司 | A kind of one-step method carries out the preparation method of cross-linked hydroxypropyl base composite modified starch |
| CN113150176A (en) * | 2021-04-27 | 2021-07-23 | 山东光大赛路新材料科技有限公司 | Preparation method of multi-group cross-linked modified hydroxypropyl starch ether |
| CN113150176B (en) * | 2021-04-27 | 2022-11-22 | 山东光大赛路新材料科技有限公司 | Preparation method of multi-group cross-linked modified hydroxypropyl starch ether |
| CN113980617A (en) * | 2021-12-02 | 2022-01-28 | 承德亮美环保科技有限公司 | Preparation process of rare salt mud environment-friendly wall material |
| CN114848888A (en) * | 2022-05-12 | 2022-08-05 | 上海威高医疗技术发展有限公司 | Absorbable starch hemostatic material and preparation method thereof |
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| CN105418775B (en) | 2017-12-22 |
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Denomination of invention: A cross linked carboxymethyl hydroxypropylated composite modified starch and its preparation method Effective date of registration: 20210122 Granted publication date: 20171222 Pledgee: Bank of China Limited by Share Ltd. Luohe branch Pledgor: HENAN HENGRUI STARCH TECHNOLOGY Co.,Ltd. Registration number: Y2021980000615 |
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