CN102617797B - Preparation method of nano grafting starch - Google Patents
Preparation method of nano grafting starch Download PDFInfo
- Publication number
- CN102617797B CN102617797B CN 201210103807 CN201210103807A CN102617797B CN 102617797 B CN102617797 B CN 102617797B CN 201210103807 CN201210103807 CN 201210103807 CN 201210103807 A CN201210103807 A CN 201210103807A CN 102617797 B CN102617797 B CN 102617797B
- Authority
- CN
- China
- Prior art keywords
- reaction
- nanometer
- hour
- preparation
- weight part
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Graft Or Block Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
The invention discloses a preparation method of nano grafting starch. Tapioca and sour are subjected to acid splitting nanocrystallization reaction in microwave environment, and then subjected to grafting reaction. 5 to 10 weight portions of industrial phosphoric acid with the mass concentration of 85 percent is sprayed into 100 weight portions of tapioca, then radiation for 0.5 to 1 hour is performed in microwave environment of 2450 plus or minus 50 MHz, and acid splitting nanocrystallization reaction is carried out; then the mixture enters in a reaction kettle, vacuum-pumping is performed, 1 to 3 weight portions of initiating agent ammonium persulfate is sprayed in the mixture, the oxidation initiating reaction lasts for 0.5 to 1 hour, then 2 to 4 weight portions of monomer methyl methacrylate and 8 to 10 weight portions of esterifying agent vinyl acetate are sprayed, stirring is performed for 0.5 to 1 h, the temperature is increased to 60 to 80 DEGC in 1 to 2 h, and heat preservation reaction lasts for 2 to 4 h; and after the reaction, the temperature is reduced to normal temperature, dehumidification by using residual heat is performed for 1 to 2 h, and then pulverizing, screening and packaging are performed. The nano grafting starch prepared by using the method provided by the invention has an excellent film forming performance and a strong cohesive force, can completely replace synthetic latex to achieve the same effect, and is safe and environment-friendly.
Description
Technical field
The invention belongs to technical field of modified starch, be specifically related to a kind of preparation method of nanometer graft starch.
Background technology
Along with printing industry improving constantly printing paper and cardboard requirement, the paper motor speed is when improving constantly, coating also becomes the scraper coating by the coating of vapour cutter, chemosynthesis latex is also substituted by the Starch Adhesive of excellent property on coating adhesive, because, not only require bond properties good as coating with Starch Adhesive, also good to the transmission performance of printing ink, and can also adapt to the processing request of high-speed paper machine, therefore, very high to the requirement of Starch Adhesive.The coating starch that can partly substitute synthetic latex in the prior art has Sumstar 190, esterification starch, graft modified starch etc.Wherein, the modified starch of routine such as Sumstar 190 and esterification starch is as auxiliary binder, and the ratio of instead of chemical synthetic latex is lower, and its fatal shortcoming is that serous coat is crisp hard, and humidification is poor, and water-retentivity is not good, and printability is poor.Graft starch has increased the viscosifying power of tackiness agent because inserting vinyl acetate or acrylic acid or the like material at starch molecular chain, in use can improve the ratio of instead of chemical synthetic latex, but also can't reach the purpose that substitutes fully.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can substitute the traditional chemical tackiness agent fully, the coating that is used for paper is gluing, not the preparation method of the nanometer graft starch that can pollute environment.
Technical scheme of the present invention:
Tapioca (flour) and acid are carried out the reaction of acidolysis nanometer in microwave environment, and then carry out graft reaction.
Preferably:
Tapioca (flour) and phosphoric acid are carried out the reaction of acidolysis nanometer in microwave environment.
Described microwave environment is 2450 ± 50MHz microwave environment.
With 100 weight part tapioca (flour)s and 5-10 weight part industrial phosphoric acids, the mass concentration of industrial phosphoric acid is 85%, carries out the reaction of acidolysis nanometer in microwave environment.Describedly carry out acidolysis nanometer reaction be in microwave environment: radiation is 0.5-1 hour in 2450 ± 50MHz microwave environment, carries out the reaction of acidolysis nanometer.
Further preferably made by following steps:
⑴. in 100 weight part tapioca (flour)s, spray into 5-10 weight part industrial phosphoric acids, the mass concentration of industrial phosphoric acid is 85%;
. with step ⑴ make thing through microwave powder equipment, radiation is 0.5-1 hour in 2450 ± 50MHz microwave environment, carries out acidolysis nanometer reaction;
⑶ enter reactor again with the thing that makes of step ⑵, vacuumize, spray into 1-3 weight part initiators, oxidation initiation reaction 0.5-1 hour, spray 2-4 weight parts monomers methyl methacrylates again, 8-10 weight part esterifying agents stirred 0.5-1 hour, heated up insulation reaction 2-4 hour 1-2 hours to 60-80 ℃;
⑷ after step ⑶ reaction is finished, be cooled to normal temperature, utilize waste heat hydrofuge 1-2 hours, pulverize the packing of sieving.
Described initiator is ammonium persulphate, and esterifying agent is vinyl acetate.
Best selection process is:
The mass ratio of each raw material is: tapioca (flour): mass concentration is 85% phosphoric acid: vinyl acetate: monomers methyl methacrylate: ammonium persulphate=100:7:3:9:2.
Tapioca (flour) is made up of amylose starch and amylopectin two portions among the present invention, amylose starch be by glucose with α-1, the chain compound of 4-glycosidic link be combined into can be maltose by amylorrhexis, the content in starch is about 10-20%.In the amylopectin between the glucose molecule divided by α-1, outside the 4-glycosidic link links to each other, also have with α-1, the 6-glycosidic link links to each other.
The know-why of institute of the present invention foundation is as follows:
The present invention adopts microwave radiation and acidolysis that starch is carried out nanometer and handles, and is that raw material carries out grafting, oxidative esterification reaction again with the nano-starch.This nanometer graft starch is applied in following several advantage on the coating binder: good film-forming properties, cohesive force are strong, substitute synthetic latex fully with the 1:2 ratio, can reach same effect, the product safety environmental protection; Over-all properties is strong during use, only needs to use the nanometer graft starch, does not need to add synthetic latex and PVA etc., can reduce the water-holding agent addition.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 1.
Fig. 2 is the nanometer graft starch of the embodiment of the invention 1 is observed 50000 times of amplifications under transmission electron microscope picture.
Fig. 3 is the nanometer graft starch of the embodiment of the invention 1 is observed 200000 times of amplifications under transmission electron microscope picture.
Embodiment
The present invention is by the following examples can the invention will be further described, yet scope of the present invention is not limited to following embodiment.
Embodiment 1: in the double centner tapioca (flour), spray into 7 kilograms of industrial phosphoric acids (mass concentration 85%), through microwave powder equipment, stopped 0.5 hour at 2450 ± 50MHz microwave environment, carry out the reaction of acidolysis nanometer.
Enter reactor again, vacuumize, sprayed into 2 kilograms of initiator ammonium persulfates 0.5 hour, carry out oxidation and cause.
Spray 3 kilograms of monomers methyl methacrylate (MMA) again, 9 kilograms of esterifying agent vinyl acetates (VAC) stirred 1 hour, heated up insulation reaction 3 hours 1.5 hours to 80 ℃.
After reaction is finished, be cooled to normal temperature, utilized the waste heat hydrofuge 1.5 hours, pulverize, cross 100 mesh sieves, packing.
The nanometer graft starch of embodiment 1 preparation is through the test of Jiangxi Province Institute of Analysis, and every index all meets company standard Q/JBH04-2012, and test result is listed as follows:
| Project | Technical indicator | Measured result |
| Outward appearance | White powder does not have mechanical impurity | White powder |
| Moisture (%) | ≤14.0 | 8.08 |
| PH value | 6.0±1 | 6.1 |
| Viscosity (30%, 60 ℃, NDJ-1) mPa.s | 100-300 | 120 |
| Whiteness (%) | ≥85.0 | 89.2 |
| Percentage of grafting (%) | ≥6.0 | 6.6 |
| Spot (individual/cm2): | ≤4.0 | 1.0 |
Product is given birth to the test of ring test center through Zhejiang University's farming, its conclusion is as follows: submitted sample disperses through ethanol, under the Japanese JEOL JEM-1230 of company type transmission electron microscope, observe, be the irregular particle aggregate, high power lens is observed the single particle particle diameter and is distributed in below the 100nm more, the rare above particle of 100nm is seen Fig. 2 and Fig. 3.
The comparison of embodiment 1 nanometer graft starch main performance index and similar products at home and abroad
| The sample title | Whiteness | Viscosity (mPas) | Film-forming properties | The serous coat snappiness | Water-retentivity |
| The nanometer graft starch | 89 | 120 | Fine | Pliable and tough | Good |
| National coating | 90 | 265 | Better | Generally | Generally |
| Bright sun coating | 93 | 411 | Better | Crisp hard | Generally |
The coating effect relatively under the equal conditions
From last table coating effect as can be seen, the coating effect of nanometer graft starch is two class kind of starch head and shoulders above, it with the starch granules nanometer after, introduce polymer side chain in skeletal chain again, the character that had both had natural adhesive, be with the high molecular polymer characteristic again, remedied many deficiencies of starch derivative, be well suited for the substituted chemistry synthetic latex and be used for high-speed paper machine coating use.
Graft starch coating and chemosynthesis latex paint ink absorption are relatively
| Starch/latex | Dope viscosity mpa.s | K﹠N value 1% |
| 0/10 | 890 | 18.1 |
| 2.5/5 | 912 | 20.7 |
| 5/0 | 975 | 22.8 |
Learn that from last table along with the increase of nanometer graft starch ratio in the binders for coatings, dope viscosity slightly rises, rheological is more or less the same, and ink absorption significantly strengthens.After the starch pasting coating, produce the coatingsurface open than latex, guaranteeing that nano and micro relief does not reduce under the too many situation, improve the White Board Gas permeability, make K﹠amp; The N value has a bigger raising.Owing to introduce the polymer side chain gene, to do, wet picking strength is on the whole suitable with chemosynthesis latex, and becoming the wear resistance of paper is that print surface intensity is unaffected substantially.
Embodiment 2:
⑴. in the double centner tapioca (flour), spray into 6 kilograms of industrial phosphoric acids, the mass concentration of industrial phosphoric acid is 85%;
. with step ⑴ make thing through microwave powder equipment, radiation is 0.5 hour in 2450 ± 50MHz microwave environment, carries out acidolysis nanometer reaction;
⑶ enter reactor again with the thing that makes of step ⑵, and vacuumizes, and sprays into 3 kilograms of ammonium persulphates, 2 kilograms of monomers methyl methacrylate are sprayed in oxidation initiation reaction 0.5 hour again, 8 kilograms of vinyl acetates, stirred 1 hour, and heated up 2 hours to 60-80 ℃ insulation reaction 2 hours;
⑷ after step ⑶ reaction is finished, be cooled to normal temperature, utilize waste heat hydrofuge hour, pulverize the packing of sieving.
Embodiment 3:
⑴. in the double centner tapioca (flour), spray into 8 kilograms of industrial phosphoric acids, the mass concentration of industrial phosphoric acid is 85%;
. with step ⑴ make thing through microwave powder equipment, radiation is 0.5 hour in 2450 ± 50MHz microwave environment, carries out acidolysis nanometer reaction;
⑶ enter reactor again with the thing that makes of step ⑵, and vacuumizes, and sprays into 1.5 kilograms of ammonium persulphates, 4 kilograms of monomers methyl methacrylate are sprayed in oxidation initiation reaction 0.5 hour again, 9 kilograms of vinyl acetates, stirred 1 hour, and heated up 2 hours to 60-80 ℃ insulation reaction 3 hours;
⑷ after step ⑶ reaction is finished, be cooled to normal temperature, utilized the waste heat hydrofuge 1.5 hours, pulverize the packing of sieving.
Claims (5)
1. the preparation method of a nanometer graft starch is characterized in that tapioca (flour) and phosphoric acid are carried out the reaction of acidolysis nanometer in 2450 ± 50MHz microwave environment, and then carries out graft reaction.
2. the preparation method of a kind of nanometer graft starch according to claim 1 is characterized in that the mass concentration of industrial phosphoric acid is 85% with 100 weight part tapioca (flour)s and 5-10 weight part industrial phosphoric acids, carries out the reaction of acidolysis nanometer in microwave environment.
3. the preparation method of a kind of nanometer graft starch according to claim 2, it is characterized in that describedly carrying out the reaction of acidolysis nanometer be in microwave environment: radiation is 0.5-1 hour in 2450 ± 50MHz microwave environment, carries out the reaction of acidolysis nanometer.
4.1 the preparation method of the described a kind of nanometer graft starch of-3 arbitrary claims is characterized in that being made by following steps:
⑴. in 100 weight part tapioca (flour)s, spray into 5-10 weight part industrial phosphoric acids, the mass concentration of industrial phosphoric acid is 85%;
. with step ⑴ make thing through microwave powder equipment, radiation is 0.5-1 hour in 2450 ± 50MHz microwave environment, carries out acidolysis nanometer reaction;
⑶ enter reactor again with the thing that makes of step ⑵, vacuumize, spray into 1-3 weight part initiators, oxidation initiation reaction 0.5-1 hour, spray 2-4 weight parts monomers methyl methacrylates again, 8-10 weight part esterifying agents stirred 0.5-1 hour, heated up insulation reaction 2-4 hour 1-2 hours to 60-80 ℃;
⑷ after step ⑶ reaction is finished, be cooled to normal temperature, utilize waste heat hydrofuge 1-2 hours, pulverize the packing of sieving.
5. the preparation method of a kind of nanometer graft starch according to claim 4 is characterized in that described initiator is ammonium persulphate, and esterifying agent is vinyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210103807 CN102617797B (en) | 2012-04-11 | 2012-04-11 | Preparation method of nano grafting starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210103807 CN102617797B (en) | 2012-04-11 | 2012-04-11 | Preparation method of nano grafting starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102617797A CN102617797A (en) | 2012-08-01 |
| CN102617797B true CN102617797B (en) | 2013-09-18 |
Family
ID=46558038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210103807 Expired - Fee Related CN102617797B (en) | 2012-04-11 | 2012-04-11 | Preparation method of nano grafting starch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617797B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152085A (en) * | 2013-05-14 | 2014-11-19 | 金东纸业（江苏）股份有限公司 | Adhesive and preparation method |
| CN104804136A (en) * | 2015-01-30 | 2015-07-29 | 武汉纺织大学 | Synthetic method of degradable adhesive |
| CN105885111A (en) * | 2016-05-30 | 2016-08-24 | 蚌埠市维光塑胶制品有限公司 | Plastic bag easy to degrade |
| CN108148526A (en) * | 2017-04-10 | 2018-06-12 | 滁州卷烟材料厂 | A kind of corrugated case of the stupefied shape difficulty stripping of environment-friendly type |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749279A (en) * | 2005-10-12 | 2006-03-22 | 江南大学 | Process for preparing modified composite denatured starch by microwave acidiolysis and esterification |
| CN101864035A (en) * | 2010-06-18 | 2010-10-20 | 罗代洪 | Method for preparing grafted starch by microwave |
| CN102050922A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Methyl acrylate grafted starch size synthesized with ultrasonic microwave method |
-
2012
- 2012-04-11 CN CN 201210103807 patent/CN102617797B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1749279A (en) * | 2005-10-12 | 2006-03-22 | 江南大学 | Process for preparing modified composite denatured starch by microwave acidiolysis and esterification |
| CN102050922A (en) * | 2009-10-30 | 2011-05-11 | 成都海旺科技有限责任公司 | Methyl acrylate grafted starch size synthesized with ultrasonic microwave method |
| CN101864035A (en) * | 2010-06-18 | 2010-10-20 | 罗代洪 | Method for preparing grafted starch by microwave |
Non-Patent Citations (2)
| Title |
|---|
| 淀粉的预处理方法对其接枝共聚的影响;钱维金等;《化工科技》;20061231;第14卷(第3期);p49-53 * |
| 钱维金等.淀粉的预处理方法对其接枝共聚的影响.《化工科技》.2006,第14卷(第3期),p49-53. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102617797A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Bonding strength and water resistance of starch-based wood adhesive improved by silica nanoparticles | |
| CN102086360B (en) | Modified starch-based wood adhesive as well as preparation method and application thereof | |
| CN102732186B (en) | Modified starch adhesive and method for preparing same | |
| CN102617797B (en) | Preparation method of nano grafting starch | |
| CN103627352B (en) | Emulsion type wood starch adhesive and preparation method thereof | |
| CN102391797B (en) | Corn starch adhesive for building and preparation method thereof | |
| CN104327787B (en) | A kind of carton processing adhesive | |
| EP2744837B1 (en) | Method for producing an aqueous binder system | |
| CN110760040A (en) | Aluminum strip for cigarette packet printing ink and preparation method thereof | |
| CN107868627A (en) | Timber industry vegetable adhesive and preparation method thereof | |
| EP2694580A1 (en) | Aqueous binder for granular and/or fibrous substrates | |
| CN107502229A (en) | A kind of nanocrystal cellulose enhancing maize-starch adhesive modified with oxidizing for making-cigarette and preparation method | |
| CN103102663A (en) | Sumac seed shell fiber-reinforced polylactic acid composite material and preparation method as well as application thereof | |
| CN102533182A (en) | Method for preparing starch-based water-resistant adhesive for corrugated board production | |
| CN102719208A (en) | High polymer binder and preparation method thereof | |
| CN106280517A (en) | A kind of environment-protection ground plate substrate | |
| CN106272843A (en) | A kind of Eucalyptus floor base material | |
| US20130046055A1 (en) | Process for producing an aqueous binder system | |
| CN116180487A (en) | Waterproof paper bag adhesive with high bursting strength and preparation method thereof | |
| CN114108368A (en) | Environment-friendly coating, preparation method and application | |
| CN101979452B (en) | Method for preparing waterproof adhesive for corrugated paper production | |
| KR101452698B1 (en) | Starch-based polymer particle emulsion, manufacturing method thereof and use of thereof | |
| CN108358513A (en) | A kind of Environment-friendlywear-resistant wear-resistant heat-insulating and fire-proof composite board and preparation method thereof | |
| CN114574126A (en) | Raw material composition of hemicellulose-based bobbin adhesive and preparation method thereof | |
| CN104312502A (en) | Novel starch-based quebracho tannin extract aldehyde-free wood adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130918 Termination date: 20160411 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |