US20210253916A9 - Preparation Method Of Oxidized Anticoagulant Starch Adhesive - Google Patents
Preparation Method Of Oxidized Anticoagulant Starch Adhesive Download PDFInfo
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- US20210253916A9 US20210253916A9 US17/071,948 US202017071948A US2021253916A9 US 20210253916 A9 US20210253916 A9 US 20210253916A9 US 202017071948 A US202017071948 A US 202017071948A US 2021253916 A9 US2021253916 A9 US 2021253916A9
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- Prior art keywords
- starch
- anticoagulant
- oxidized
- preparation
- starch adhesive
- 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.)
- Abandoned
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- 229920002472 Starch Polymers 0.000 title claims abstract description 83
- 235000019698 starch Nutrition 0.000 title claims abstract description 80
- 239000008107 starch Substances 0.000 title claims abstract description 79
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 239000003146 anticoagulant agent Substances 0.000 title claims abstract description 22
- 229940127219 anticoagulant drug Drugs 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013530 defoamer Substances 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229920002261 Corn starch Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000008120 corn starch Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 230000008719 thickening Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000002429 anti-coagulating effect Effects 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- -1 tetrafluoroborate Chemical compound 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 239000001254 oxidized starch Substances 0.000 description 4
- 235000013808 oxidized starch Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RSNMDQAIHKTLRN-UHFFFAOYSA-M CCN1=CN(C)C=C1.FB(F)F.[F-] Chemical compound CCN1=CN(C)C=C1.FB(F)F.[F-] RSNMDQAIHKTLRN-UHFFFAOYSA-M 0.000 description 1
- TUQHUCNXLMYUAN-UHFFFAOYSA-M CN1C=CN(CC(=O)O)=C1.FB(F)F.[F-] Chemical compound CN1C=CN(CC(=O)O)=C1.FB(F)F.[F-] TUQHUCNXLMYUAN-UHFFFAOYSA-M 0.000 description 1
- BMEULUKRPADDOO-UHFFFAOYSA-L CN1C=CN(CCCCCCCCCCCC(=O)O)=C1.CN1C=CN(CCCCCCCCCCCC(=O)O)=C1.CN1C=CN=C1.CO.FB(F)(F)(F)[Na].FB(F)F.O.O=C(O)CCCCCCCCCCCBr.[Br-].[F-] Chemical compound CN1C=CN(CCCCCCCCCCCC(=O)O)=C1.CN1C=CN(CCCCCCCCCCCC(=O)O)=C1.CN1C=CN=C1.CO.FB(F)(F)(F)[Na].FB(F)F.O.O=C(O)CCCCCCCCCCCBr.[Br-].[F-] BMEULUKRPADDOO-UHFFFAOYSA-L 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Classifications
-
- 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
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
-
- 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
- C09J103/06—Esters
Definitions
- the invention relates to the technical field of adhesives, and in particular relates to a starch adhesive for carton.
- Corrugated box is made from corrugated cardboard by shearing, indentation, nailing box or gluing box. Corrugated box is one of the most widely used packaging products, and the amount has always been the first of all kinds of packaging products. At present, corrugated box has become the most widely used packaging containers in modern packaging, and is one of the most important packaging forms used all over the world.
- the food industry, electronic appliance industry, beverage industry, machinery industry, pharmaceutical industry, daily chemical industry and other industries closely related to people's lives constantly launches new products, thus the number and variety of exports increases day by day, which greatly promotes the production of corrugated boxes as outer packaging products.
- Adhesives are required for gluing corrugated boxes, the adhesives are viscous materials that connect the two separate materials by their adhesive properties.
- the present invention provides a preparation method of oxidized anticoagulant starch adhesive, and the specific technical solution is as follows:
- a method for preparing oxidized anticoagulant starch adhesive comprising the following steps:
- step (1) The starch granules obtained in step (1) are formulated into 40-50% starch emulsion, and the pH is adjusted to 6.5-7.5 after gelatinization, and an appropriate amount of dispersing agent, defoamer and water are added to form a starch adhesive.
- the original starch comprises at least one of corn starch, wheat starch, tapioca starch or potato starch;
- the oxidant used in the oxidation reaction includes at least one of hydrogen peroxide, sodium hypochlorite, and potassium permanganate;
- the reductant is at least one of sodium hydrogen sulfite, sodium sulfite, sodium sulfate, or ferrous sulfate;
- the esterifying agent is composed of an anion and a cation, wherein the cation is a methylimidazole substituted by a carboxyl-functionalized long-chain and the anion is tetrafluoroborate.
- the carboxyl functional group in the structure can be esterified with a hydroxyl group in corn starch to form a hydrophobic long-chain ester-based compound, and the ionic structure has a certain hydrophilic property, and the amphipathic property makes it have a good emulsifying property;
- tetrafluoroborate anion also has complexation property, can complex with oxygen-containing groups in starch, acts as a thickener, and also reduces complexation of starch molecules and tendency to agglomerate, thus increases its anticoagulant effect.
- the acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid;
- the dispersing agent is at least one of a non-ionic surfactant PE-6200, a surfactant Dyno160, and a wetting and dispersing agent CF-10;
- the defoamer is a mixture of an aqueous silicone defoamer (Q-119) and an oily silicone defoamer (DF-886), the mass ratio of the two is 1:1.
- the invention has the beneficial effects of using a self-made ionic compound functionalized with carboxylic acid as an esterifying agent, which significantly improves anticoagulant effect of the starch adhesive.
- the starch adhesive prepared by the method has long storage period and good anticoagulant effect, and is particularly suitable for corrugated box adhesives.
- starch adhesive is commonly used.
- Starch adhesive is a renewable natural polymer binder, which has been widely promoted because of its wide source, low price, non-toxic, odorless, environment-friendly and strong adhesion.
- Natural starches have better properties after physical or chemical modification and are widely used in the production of paper, labels and corrugated cardboard.
- oxidized starch adhesives occupy a considerable proportion.
- Natural starch is a high polymer with glucose its a structural unit, and has the disadvantages of high paste viscosity, poor fluidity and poor stability.
- Oxidized starch improves the disadvantages of low strength, short storage period and slow drying speed of gelatinized starch adhesives.
- the existing oxidized starch adhesive still has a problem of low capability of anti-coagulation and poor storage stability.
- the present invention provides a preparation method of oxidized anticoagulant starch adhesive, and is further described below in conjunction with the embodiments, which are merely a part of the embodiments of the present invention. It is within the scope of the present invention to make equivalent substitutions or improvements by those skilled in the art based on the embodiments of the present invention without creative efforts.
- the esterifying agent is synthesized by the inventors, and the specific synthetic route includes a substitution reaction and an ion exchange reaction, take 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate as an example, the specific scheme is as follows:
- a method for preparing an oxidized anticoagulant starch adhesive comprising the following steps:
- step (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of surfactant Dyno 160, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- surfactant Dyno 160 a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- a method for preparing an oxidized anticoagulant starch adhesive comprising the following steps:
- step (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- PE-6200 non-ionic surfactant PE-6200
- a mixture of aqueous silicone defoamer Q-119, 20 g
- oily silicone defoamer DF-886, 20 g
- a method for preparing an oxidized anticoagulant starch adhesive comprising the following steps:
- step (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- PE-6200 non-ionic surfactant PE-6200
- a mixture of aqueous silicone defoamer Q-119, 20 g
- oily silicone defoamer DF-886, 20 g
- a method for preparing an oxidized anticoagulant starch adhesive comprising the following steps:
- step (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- PE-6200 non-ionic surfactant PE-6200
- a mixture of aqueous silicone defoamer Q-119, 20 g
- oily silicone defoamer DF-886, 20 g
- Embodiment 1 Comparative Example 1
- Embodiment 4 Comparative Example 2
- starch paste was prepared under the same formulation system with the esterifying agent prepared in present invention was replaced by common esterifying agent vinyl acetate, and the anticoagulant effect was compared.
- the relevant data is as described in Table 1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
- This application claims priority of the Chinese Patent Application filed on Aug. 16, 2019, with the application number of 201910759465.8, and the title of “Preparation Method of Oxidized Anticoagulant Starch Adhesive”, the entire contents of which are fully incorporated herein by reference.
- The invention relates to the technical field of adhesives, and in particular relates to a starch adhesive for carton.
- Corrugated box is made from corrugated cardboard by shearing, indentation, nailing box or gluing box. Corrugated box is one of the most widely used packaging products, and the amount has always been the first of all kinds of packaging products. At present, corrugated box has become the most widely used packaging containers in modern packaging, and is one of the most important packaging forms used all over the world. The food industry, electronic appliance industry, beverage industry, machinery industry, pharmaceutical industry, daily chemical industry and other industries closely related to people's lives constantly launches new products, thus the number and variety of exports increases day by day, which greatly promotes the production of corrugated boxes as outer packaging products. These industry users not only have a large increase in the demand for cartons, but also put forward higher requirements for the moisture resistance, aesthetics, environmental protection and anti-wear of the carton. Adhesives are required for gluing corrugated boxes, the adhesives are viscous materials that connect the two separate materials by their adhesive properties.
- The present invention provides a preparation method of oxidized anticoagulant starch adhesive, and the specific technical solution is as follows:
- A method for preparing oxidized anticoagulant starch adhesive, comprising the following steps:
- (1) an original starch and deionized water are mixed to form a 40-45% starch emulsion, then the pH is adjusted to 7-11 with sodium hydroxide, and oxidation reaction is carried out at 40-60° C.; after the oxidation reaction is completed, a reductant is added to react with the unreacted oxidant; after the reaction is completed, sodium bicarbonate is added to adjust the pH to 7-11, and an esterifying agent is added for esterification reaction; after the esterification, a product is neutralized with acid, washed with water, suction filtrated and dried to obtain starch granules.
- (2) The starch granules obtained in step (1) are formulated into 40-50% starch emulsion, and the pH is adjusted to 6.5-7.5 after gelatinization, and an appropriate amount of dispersing agent, defoamer and water are added to form a starch adhesive.
- Further, the original starch comprises at least one of corn starch, wheat starch, tapioca starch or potato starch;
- Further, the oxidant used in the oxidation reaction includes at least one of hydrogen peroxide, sodium hypochlorite, and potassium permanganate;
- Further, the reductant is at least one of sodium hydrogen sulfite, sodium sulfite, sodium sulfate, or ferrous sulfate;
- Further, the formula of the esterifying agent is as follows,
- The esterifying agent is composed of an anion and a cation, wherein the cation is a methylimidazole substituted by a carboxyl-functionalized long-chain and the anion is tetrafluoroborate. On the one hand, the carboxyl functional group in the structure can be esterified with a hydroxyl group in corn starch to form a hydrophobic long-chain ester-based compound, and the ionic structure has a certain hydrophilic property, and the amphipathic property makes it have a good emulsifying property; on the other hand, tetrafluoroborate anion also has complexation property, can complex with oxygen-containing groups in starch, acts as a thickener, and also reduces complexation of starch molecules and tendency to agglomerate, thus increases its anticoagulant effect.
- Further, the acid is at least one of hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid;
- Further, the dispersing agent is at least one of a non-ionic surfactant PE-6200, a surfactant Dyno160, and a wetting and dispersing agent CF-10;
- Further, the defoamer is a mixture of an aqueous silicone defoamer (Q-119) and an oily silicone defoamer (DF-886), the mass ratio of the two is 1:1.
- The invention has the beneficial effects of using a self-made ionic compound functionalized with carboxylic acid as an esterifying agent, which significantly improves anticoagulant effect of the starch adhesive. The starch adhesive prepared by the method has long storage period and good anticoagulant effect, and is particularly suitable for corrugated box adhesives.
- There are many types of adhesives for adhesion of corrugated box, but starch adhesive is commonly used. Starch adhesive is a renewable natural polymer binder, which has been widely promoted because of its wide source, low price, non-toxic, odorless, environment-friendly and strong adhesion. Natural starches have better properties after physical or chemical modification and are widely used in the production of paper, labels and corrugated cardboard. Among the modified starches, oxidized starch adhesives occupy a considerable proportion. Natural starch is a high polymer with glucose its a structural unit, and has the disadvantages of high paste viscosity, poor fluidity and poor stability. After slight oxidation by the oxidizing agent, the hydroxyl group on the glucose structural unit is oxidized to the aldehyde group and the carboxyl group, and at the same time, the glycosidic bond between the molecular rings is partially broken, thus becomes an oxidized starch with a low degree of polymerization. Oxidized starch improves the disadvantages of low strength, short storage period and slow drying speed of gelatinized starch adhesives. However, the existing oxidized starch adhesive still has a problem of low capability of anti-coagulation and poor storage stability.
- The present invention provides a preparation method of oxidized anticoagulant starch adhesive, and is further described below in conjunction with the embodiments, which are merely a part of the embodiments of the present invention. It is within the scope of the present invention to make equivalent substitutions or improvements by those skilled in the art based on the embodiments of the present invention without creative efforts.
- Preparation of an Esterifying Agent:
- In present invention, the esterifying agent is synthesized by the inventors, and the specific synthetic route includes a substitution reaction and an ion exchange reaction, take 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate as an example, the specific scheme is as follows:
- (1) 1-methylimidazole was mixed with 12-bromosodecanoic acid in a methanol solvent with a mole ratio of 1:1, the mixture reacted for 12 hours under reflux condition, the solvent was then evaporated to obtain 3-dodecanoic acid-1-methylimidazolium bromide;
- (2) The bromide prepared in the step 1 was reacted with sodium tetrafluoroborate in an aqueous solution at room temperature for 24 hours, and then extracted with dichloromethane to obtain 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate.
- The 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate prepared was analyzed by H NMR, and the results were as follows: 1H NMR (600 MHz, DMSO) δ=1.3-2.2 (10×CH2) 3.72 (CH3), 5.1 (CH2), 7.75 (CH), 7.92 (CH), 8.92 (CH), 11.87 ppm (OH).
- A method for preparing an oxidized anticoagulant starch adhesive, comprising the following steps:
- (1) corn starch and deionized water were mixed to form 40% starch emulsion 5 kg, then the pH was adjusted to 7-11 with sodium hydroxide, 120 g of 30% hydrogen peroxide was added at 45° C., an oxidation reaction was carried out under vigorously stirring, the pH value was maintained at 7-11 during oxidation process; after 30 minutes of the oxidation reaction, a reductant sodium hydrogen sulfite was added, the amount of the reductant added is to ensure that the reaction solution will not make color change of the starch potassium iodide test paper as the end point; after the reaction is completed, sodium bicarbonate was added to adjust the pH to 7-11, and 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate was added for esterification reaction; after the esterification, the pH of product was adjusted with hydrochloric acid to neutral, and washed with water, suction filtered and dried to obtain starch granules.
- (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of surfactant Dyno 160, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- A method for preparing an oxidized anticoagulant starch adhesive, comprising the following steps:
- (1) corn starch and deionized water were mixed to form 40% starch emulsion 5 kg, then the pH was adjusted to 7-11 with sodium hydroxide, 40 g of sodium hypochlorite was added at 45° C., an oxidation reaction was carried out under vigorously stirring, the pH value was maintained at 7-11 during oxidation process; after 30 minutes of the oxidation reaction, a reductant ferrous sulfate was added, the amount of the reductant added is to ensure that the reaction solution will not make color change of the starch potassium iodide test paper as the end point; after the reaction is completed, sodium bicarbonate was added to adjust the pH to 7-11, and 3-tetradecanoic acid-1-methylimidazolium tetrafluoroborate was added for esterification reaction; after the esterification, the pH of product was adjusted with hydrochloric acid to neutral, and washed with water, suction filtered and dried to obtain starch granules.
- (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- A method for preparing an oxidized anticoagulant starch adhesive, comprising the following steps:
- (1) wheat starch and deionized water were mixed to form 45% starch emulsion 5 kg, then the pH was adjusted to 7-11 with sodium hydroxide, 120 g of 30% hydrogen peroxide was added at 50° C., an oxidation reaction was carried out under vigorously stirring, the pH value was maintained at 7-11 during oxidation process; after 45 minutes of the oxidation reaction, a reductant sodium sulfite was added, the amount of the reductant added is to ensure that the reaction solution will not make color change of the starch potassium iodide test paper as the end point; after the reaction is completed, sodium bicarbonate was added to adjust the pH to 7-11, and 3-dodecanoic acid-1-methylimidazolium tetrafluoroborate was added for esterification reaction; after the esterification, the pH of product was adjusted with hydrochloric acid to neutral, and washed with water, suction filtered and dried to obtain starch granules.
- (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- A method for preparing an oxidized anticoagulant starch adhesive, comprising the following steps:
- (1) tapioca starch and deionized water were mixed to form 40% starch emulsion 5 kg, then the pH was adjusted to 7-11 with sodium hydroxide, 50 g of potassium permanganate was added at 50° C., an oxidation reaction was carried out under vigorously stirring, the pH value was maintained at 7-11 during oxidation process; after 30 minutes of the oxidation reaction, a reductant ferrous sulfate was added, the amount of the reductant added is to ensure that the reaction solution will not make color change of the starch potassium iodide test paper as the end point; after the reaction is completed, sodium bicarbonate was added to adjust the pH to 7-11, and 3-hexadecanoic acid-1-methylimidazolium tetrafluoroborate was added for esterification reaction; after the esterification, the pH of product was adjusted with hydrochloric acid to neutral, and washed with water, suction filtered and dried to obtain starch granules.
- (2) The starch granules obtained in step (1) were formulated into 4 kg of 45% starch emulsion, and after gelatinization, the pH was adjusted to 6.5-7.5; then 60 g of non-ionic surfactant PE-6200, a mixture of aqueous silicone defoamer (Q-119, 20 g) and oily silicone defoamer (DF-886, 20 g) were added, the reaction solution was stirred at 55° C. to obtain an anticoagulant starch adhesive.
- To demonstrate the effects of the present invention, for the above Embodiment 1 (Comparative Example 1), Embodiment 4 (Comparative Example 2), starch paste was prepared under the same formulation system with the esterifying agent prepared in present invention was replaced by common esterifying agent vinyl acetate, and the anticoagulant effect was compared. The relevant data is as described in Table 1.
-
TABLE 1 Comparison of anticoagulant properties of starch paste Serum Serum Serum Serum Serum volume volume volume volume volume ratio, ratio, ratio, ratio, ratio, Samples 12 h 24 h 48 h 72 h 96 h Embodiment 1 13 20 27 32 36 Embodiment 2 14 21 27 33 37 Embodiment 3 13 19 26 30 35 Embodiment 4 12 18 25 30 34 Comparative 16 26 42 53 61 Example 1 Comparative 15 24 41 50 59 Example 2 - It can be seen from the data in Table 1 that the starch paste formulated by the starch adhesive of the present invention has a good anticoagulant effect.
- The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection scope of the present invention.
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US5716441A (en) * | 1996-09-27 | 1998-02-10 | National Starch And Chemical Investment Holding Corporation | Starch-based, water resistant adhesives |
US5789570A (en) * | 1994-11-30 | 1998-08-04 | Degussa Aktiengesellschaft | Swellable starch ester and methods of its production and use |
CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
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JP4540229B2 (en) * | 1998-07-23 | 2010-09-08 | コオペラティ・アヴェベ・ユー・エイ | Adhesive composition |
CN108864986A (en) * | 2017-05-11 | 2018-11-23 | 淄博市思瑞颖胶粘剂有限公司 | Starch phosphate adhesive |
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US5789570A (en) * | 1994-11-30 | 1998-08-04 | Degussa Aktiengesellschaft | Swellable starch ester and methods of its production and use |
US5716441A (en) * | 1996-09-27 | 1998-02-10 | National Starch And Chemical Investment Holding Corporation | Starch-based, water resistant adhesives |
CN108018739A (en) * | 2017-12-14 | 2018-05-11 | 广东省造纸研究所 | A kind of nano-starch adhesive and preparation method thereof |
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