CN110684236B - Hyperbranched starch modified zinc oxide and preparation method and application thereof - Google Patents
Hyperbranched starch modified zinc oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN110684236B CN110684236B CN201910952302.1A CN201910952302A CN110684236B CN 110684236 B CN110684236 B CN 110684236B CN 201910952302 A CN201910952302 A CN 201910952302A CN 110684236 B CN110684236 B CN 110684236B
- Authority
- CN
- China
- Prior art keywords
- starch
- zinc oxide
- hyperbranched
- stirring
- modified zinc
- 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.)
- Active
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 89
- 235000019698 starch Nutrition 0.000 title claims abstract description 89
- 239000008107 starch Substances 0.000 title claims abstract description 89
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011787 zinc oxide Substances 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 24
- 238000010057 rubber processing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000004382 Amylase Substances 0.000 claims description 9
- 108010065511 Amylases Proteins 0.000 claims description 9
- 102000013142 Amylases Human genes 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 235000019418 amylase Nutrition 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000003630 growth substance Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 240000003183 Manihot esculenta Species 0.000 claims description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 4
- 108090000637 alpha-Amylases Proteins 0.000 claims description 4
- 102000004139 alpha-Amylases Human genes 0.000 claims description 4
- 229940024171 alpha-amylase Drugs 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 108010019077 beta-Amylase Proteins 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000012936 vulcanization activator Substances 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000004922 Vigna radiata Species 0.000 claims description 2
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 2
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004073 vulcanization Methods 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 235000014692 zinc oxide Nutrition 0.000 description 37
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108010031186 Glycoside Hydrolases Proteins 0.000 description 1
- 102000005744 Glycoside Hydrolases Human genes 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber processing, in particular to hyperbranched starch modified zinc oxide and a preparation method and application thereof. The modified zinc oxide is modified by hyperbranched hydrophobic starch, and is in a nano form and uniformly and stably distributed on the surface of the hyperbranched hydrophobic starch. The zinc oxide can be uniformly dispersed in a rubber matrix, has stable property, does not have agglomeration phenomenon, solves the aeipathia of the traditional zinc oxide, and can better exert the effects of vulcanization activity, reinforcement and the like.
Description
Technical Field
The invention relates to the field of rubber processing, in particular to hyperbranched starch modified zinc oxide and a preparation method and application thereof.
Background
Zinc oxide is an oxide of zinc, is poorly soluble in water, and is soluble in acids and strong bases. Zinc oxide is a relatively common chemical additive, and can be widely applied to the fields of plastics, rubber, silicate products, lubricating oil, paint, ointment, adhesives, food, batteries, flame retardants and the like. The rubber industry is the first major user of zinc oxide, and during the vulcanization molding process of rubber products, zinc oxide is a good vulcanization activator, and zinc oxide has certain vulcanization and reinforcement effects on rubber. Because zinc oxide can be combined with rubber molecular chains at a molecular level, the service performance of the rubber material can be improved, and the characteristics of finished products such as: the zinc oxide can obviously improve the performances of the rubber product such as tensile strength, heat conductivity, tear resistance, wear resistance and the like; in the processing technology, the scorching time of the rubber compound can be prolonged, and the processing safety is also very favorable.
However, the zinc oxide particles have extremely high surface energy, are in a thermodynamically unstable state and are easy to agglomerate, so that the defect of agglomeration of particles in a rubber matrix is easily caused; and the surface of the zinc oxide is hydrophilic and oleophobic, has poor compatibility with an oily rubber matrix, has relatively poor dispersion performance and is easy to cause the defect of an interface. These properties all cause the problems of low performance, short service life and the like of the zinc oxide-rubber composite material.
Chinese invention patent (publication No. CN106380643A, published: 2017.02.08) discloses modified zinc oxide, a preparation method thereof and application thereof in rubber products. The modified zinc oxide comprises the following components in parts by weight: 8-15 parts of water, 0.01-0.1 part of sodium hydroxide, 2-6 parts of zinc oxide and 0.5-2 parts of tetraethyl orthosilicate; the modified oxidant is used for preparing rubber products. The modified zinc oxide promotes the uniform distribution of zinc oxide, carries out modification treatment on the surface of the zinc oxide, generates silicon dioxide by hydrolyzing tetraethyl orthosilicate in a solution, coats the silicon dioxide on the surface of the zinc oxide, avoids direct contact between latex and the zinc oxide, can be added, stirred, mixed and matured together with ingredients such as sulfur and the like during maturation, and enables the silicon dioxide on the outer layer of the zinc oxide to be corroded by alkali during high-temperature vulcanization so as to fully exert the vulcanization activation effect, and the preparation method and the application thereof in rubber products. The method adopts a wrapping method, but does not relate to the problem of particle agglomeration of zinc oxide in a rubber matrix.
The Chinese invention patent (publication No. CN107226927A, published: 2017.10.03) discloses a preparation method of modified nano zinc oxide for fatigue-resistant rubber, which comprises primary modification and coating of an antimony chloride film. The agglomeration degree of the modified nano zinc oxide prepared in the patent is reduced, the nano particles are uniform in size by controlling the conditions of all the steps, the compatibility of natural rubber and a filler can be improved, the carbon black is uniformly dispersed in the rubber, the microstructure of the natural rubber is changed, a uniformly distributed cross-linked network is formed, the stress borne by the rubber is uniformly distributed, stress concentration points are reduced, the tearing resistance and the dynamic fatigue resistance of a rubber material are improved, the thermal aging resistance of the rubber is improved to a certain extent, and the application range of the nano zinc oxide is expanded. However, antimony chloride is a dangerous product, and the production of the product is limited.
Disclosure of Invention
In order to solve the technical problems of low performance, short service life and the like of a zinc oxide-rubber composite material, the invention aims to provide modified zinc oxide, which can be uniformly dispersed in a rubber matrix, has stable property, does not have agglomeration phenomenon, solves the aeipathia of the traditional zinc oxide, and can better exert the effects of vulcanization activity, reinforcement and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified zinc oxide is modified by hyperbranched hydrophobic starch, and is in a nano form and uniformly and stably distributed on the surface of the hyperbranched hydrophobic starch.
Preferably, the mass ratio of the hyperbranched hydrophobic starch to the zinc oxide is 1: 1-20: 1, preferably 2: 1-10: 1.
Preferably, the starch of the hyperbranched hydrophobic starch is one or a mixture of corn starch, cassava starch, sweet potato starch or mung bean starch.
Preferably, the preparation method of the hyperbranched hydrophobic starch comprises the following steps: 1) performing enzymolysis on starch to obtain hyperbranched starch, and 2) adding a coupling agent and stearic acid into the hyperbranched starch and uniformly mixing; (ii) a Preferably, the amylase is alpha-amylase, beta-amylase or dehydrated glycosidase, and the dosage of the amylase is 0.01-0.03 percent of the mass of the starch; preferably, the coupling agent is one of KH550, KH570, tetraethyl titanate, tetrabutyl titanate and triisopropyl aluminate, and the dosage of the coupling agent is 0.8-1.6% of the mass of the starch.
It is another object of the present invention to provide a method for preparing the modified zinc oxide, which comprises the following steps:
1) adding a certain amount of starch into deionized water, heating to boil under reflux, and stirring at high speed to dissolve completely. After dissolving, adjusting the pH value to 3.5-4.5 by using a dilute hydrochloric acid solution, adding amylase, and continuously reacting for a period of time under a reflux state; after the reaction is finished, cooling the reactant to room temperature, filtering out precipitates, and drying to obtain hyperbranched starch;
2) heating the starch prepared in the step 1) to 65-75 ℃, performing ultrasonic treatment for 10-20min, then adding a certain amount of coupling agent, stirring for reaction for 10-20min, then adding stearic acid, continuing stirring for 15-25min, and finally drying in an oven to obtain hyperbranched hydrophobic starch;
3) dissolving inorganic zinc salt in absolute ethyl alcohol, then dripping absolute ethyl alcohol sodium hydroxide solution into the absolute ethyl alcohol sodium hydroxide solution, violently stirring the solution at normal temperature to form gel, adding a crystal growth regulator, and stirring the gel for later use;
4) adding the hyperbranched hydrophobic starch prepared in the step 2) into the gel in the step 3), stirring at a high speed at the temperature of 55-65 ℃ for reaction for 1-2h, and then carrying out vacuum filtration, drying and grinding to obtain the hyperbranched starch modified zinc oxide.
Preferably, the amylase in the step 1) is alpha-amylase, beta-amylase or anhydroglycosidase, and the dosage of the amylase is 0.01-0.03% of the mass of starch.
Preferably, the coupling agent in the step 2) is one of KH550, KH570, tetraethyl titanate, tetrabutyl titanate and triisopropyl aluminate, and the dosage of the coupling agent is 0.8-1.6% of the mass of the starch.
Preferably, the ultrasonic power of the ultrasonic treatment in the step 2) is 100-300W.
Preferably, the crystal growth regulator in the step 3) is boron nitride, and the amount of the boron nitride is 0.1-0.6% of the mass of the inorganic zinc salt.
The invention also aims to provide the modified zinc oxide used as a vulcanization activator in rubber processing.
Another object of the present invention is to provide a rubber composition comprising the modified zinc oxide.
It is another object of the present invention to provide a tire comprising a vulcanizate of said rubber composition.
Compared with the prior art, the invention has the following technical beneficial effects:
(1) the invention controls the hydrolysis degree of the starch by controlling the reaction time, the enzyme dosage, the reaction pH and the like, so that more branched chains are generated on the molecular chain of the starch, and the hyperbranched starch is prepared. Then, the reaction of inorganic zinc salt and sodium hydroxide to generate zinc oxide is carried out on a micro water film adsorbed on the surface of the starch by utilizing polar groups such as a large number of hydroxyl groups on the surface of the starch, and the nano zinc oxide with uniform particles is generated under the action of boron nitride. The zinc oxide can be combined with active hydroxyl on the surface of the starch to form a covalent bond, so that the zinc oxide is uniformly and stably distributed on the surface of the starch to form the hyperbranched starch modified zinc oxide with stable structure. The higher the degree of branching of the starch, the more bound zinc oxide is formed on the starch surface.
(2) The hyperbranched starch modified zinc oxide is used for rubber processing, and because zinc oxide particles are uniformly distributed on the surface of the starch, and the starch can be rapidly and uniformly dispersed into the rubber matrix under the action of stearic acid and the like, the hyperbranched starch modified zinc oxide is equivalent to the situation that zinc oxide is uniformly dispersed into the rubber matrix, has stable property, can not generate agglomeration, solves the aeipathia of the traditional zinc oxide, and can better exert the effects of vulcanization activity, reinforcement and the like.
Drawings
FIG. 1 is a scanning electron micrograph of two zinc oxides, wherein FIG. 1A shows a common commercially available nano zinc oxide, and FIG. 1B shows a hyperbranched starch-modified zinc oxide prepared in example 1.
FIG. 2 is a sectional electron micrograph of each sample, A, example 1; B. example 2; C. comparative example.
Detailed Description
The invention is further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
A preparation method of hyperbranched starch modified zinc oxide comprises the following steps:
(1) 100kg of cassava starch is added into deionized water, heated to boiling under a reflux state, and stirred at a high speed until the cassava starch is completely dissolved. After dissolution, the pH was adjusted to about 4.0 with 0.1mol/L hydrochloric acid solution, and 15g of alpha-amylase was added, and the reaction was continued for 1.5 hours under reflux. After the reaction is finished, cooling the reactant to room temperature, filtering out precipitates, and drying to obtain the hyperbranched starch.
(2) Heating the starch prepared in the step (1) to about 70 ℃, carrying out ultrasonic treatment for 15min at the ultrasonic power of 100W, then adding 1.2kg of tetraethyl titanate, stirring for reaction for 15min, then adding 0.5kg of stearic acid, continuing stirring for 20min, and finally drying in an oven to obtain the hyperbranched hydrophobic starch.
(3) Dissolving 40kg of zinc acetate in absolute ethyl alcohol, then dripping 0.1mol/L of absolute ethyl alcohol sodium hydroxide solution into the zinc acetate, violently stirring the zinc acetate solution at normal temperature to form gel, adding 80g of boron nitride, and stirring the gel for later use;
(4) and (3) adding the hyperbranched hydrophobic starch prepared in the step (2) into the gel in the step (3), stirring at a high speed for reaction for 1.5h at a temperature of about 60 ℃, and then carrying out reduced pressure suction filtration, drying and grinding to obtain the hyperbranched starch modified zinc oxide.
The hyperbranched starch-modified zinc oxide prepared in example 1 was characterized by a scanning electron microscope, and the results are shown in fig. 1B, from which it can be seen that the zinc oxide particles are uniform in size and are distributed uniformly on the surface of the starch matrix. FIG. 1A shows a conventional commercially available nano zinc oxide, which is seen to be relatively non-uniform in particle size and to clump together.
Example 2
A preparation method of hyperbranched starch modified zinc oxide comprises the following steps:
(1) 120kg of corn starch was added to deionized water, heated to boiling under reflux, and stirred at high speed until completely dissolved. After dissolution, the pH was adjusted to about 4.0 with 0.1mol/L hydrochloric acid solution, and 24g of anhydroglycosidase was added to continue the reaction under reflux for 1.2 hours. After the reaction is finished, cooling the reactant to room temperature, filtering out precipitates, and drying to obtain the hyperbranched starch.
(2) Heating the starch prepared in the step (1) to about 70 ℃, carrying out ultrasonic treatment for 15min at the ultrasonic power of 120W, then adding 2kg of tetraethyl titanate, stirring for reaction for 15min, then adding 0.8kg of stearic acid, continuing stirring for 20min, and finally drying in an oven to obtain the hyperbranched hydrophobic starch.
(3) Dissolving 60kg of zinc nitrate in absolute ethyl alcohol, then dripping 0.1mol/L absolute ethyl alcohol sodium hydroxide solution into the absolute ethyl alcohol sodium hydroxide solution, violently stirring the solution at normal temperature to form gel, then adding 160g of boron nitride, and stirring the gel for later use;
(4) and (3) adding the hyperbranched hydrophobic starch prepared in the step (2) into the gel in the step (3), stirring at a high speed for reaction for 1.5h at a temperature of about 60 ℃, and then carrying out reduced pressure suction filtration, drying and grinding to obtain the hyperbranched starch modified zinc oxide.
To compare the effects of the invention, a test was conducted using a commercially available nano zinc oxide (shown in FIG. 1A) as a comparative example. 5g of the rubber prepared in each of examples 1 and 2 and comparative examples was added to 100g of rubber, and a predetermined amount of carbon black, sulfur, an accelerator, stearic acid, an antioxidant and the like was added thereto, and the mixture was kneaded in a torque rheometer for 12 minutes, followed by rubber discharge. And (3) preparing the vulcanized rubber from the prepared rubber compound in a flat vulcanizing machine under the vulcanization condition of 160 ℃ for 30 min. The mechanical properties of the vulcanized rubber were tested according to the national standard GB/T528-2009, and the test results are shown in Table 1.
TABLE 1 mechanical Properties of the vulcanizates
| Sample numbering | Tensile strength/MPa | Elongation at break/% | Tear Strength/kN.m-1 |
| Example 1 | 28.8 | 661 | 22.7 |
| Example 2 | 27.3 | 632 | 21.3 |
| Comparative example | 24.6 | 512 | 17.8 |
As can be seen from Table 1, the mechanical properties of the vulcanized rubber using the hyperbranched starch-modified zinc oxide of the present invention are much better than those of the commercially available nano zinc oxide vulcanized rubber. In the above comparative test, all the test conditions were identical except for the zinc oxide, and the difference in mechanical properties was only zinc oxide. The hyperbranched starch modified zinc oxide provided by the invention has uniform particle size distribution, uniform dispersion in a rubber matrix, no agglomeration, few microscopic defects caused in the rubber matrix, and strong anti-damage capability of vulcanized rubber under stress, so that the hyperbranched starch modified zinc oxide has good mechanical properties.
The vulcanized sample prepared above was sliced and sampled at low temperature with liquid nitrogen, and the cut of the sample was observed by scanning electron microscope, the specific electron microscope photograph is shown in fig. 2. The rubber sample materials using the hyperbranched starch-modified zinc oxide prepared in examples 1 and 2 were uniformly distributed without significant agglomerated particles, whereas the rubber samples using ordinary commercially available nano-zinc oxide had many agglomerated particles as shown in the figure.
Claims (13)
1. The modified zinc oxide is characterized in that hyperbranched hydrophobic starch modified zinc oxide is adopted as the modified zinc oxide, and the zinc oxide is in a nano form and uniformly and stably distributed on the surface of the hyperbranched hydrophobic starch;
the method for modifying zinc oxide by hyperbranched hydrophobic starch comprises the following steps:
1) adding a certain amount of starch into deionized water, heating to boil under reflux, stirring at high speed until the starch is completely dissolved, adjusting pH to 3.5-4.5 with dilute hydrochloric acid solution after the starch is dissolved, adding amylase, and continuously reacting for a period of time under reflux; after the reaction is finished, cooling the reactant to room temperature, filtering out precipitates, and drying to obtain hyperbranched starch;
2) heating the starch prepared in the step 1) to 65-75 ℃, performing ultrasonic treatment for 10-20min, then adding a coupling agent, stirring for reaction for 10-20min, then adding stearic acid, continuing stirring for 15-25min, and finally drying in an oven to obtain hyperbranched hydrophobic starch;
3) dissolving inorganic zinc salt in absolute ethyl alcohol, then dripping absolute ethyl alcohol sodium hydroxide solution into the absolute ethyl alcohol sodium hydroxide solution, violently stirring the solution at normal temperature to form gel, adding a crystal growth regulator, and stirring the gel for later use;
4) adding the hyperbranched hydrophobic starch prepared in the step 2) into the gel in the step 3), stirring at a high speed at the temperature of 55-65 ℃ for reaction for 1-2h, and then carrying out vacuum filtration, drying and grinding to obtain the hyperbranched starch modified zinc oxide.
2. The modified zinc oxide of claim 1, wherein the mass ratio of the hyperbranched hydrophobic starch to the zinc oxide is 1: 1-20: 1.
3. The modified zinc oxide according to claim 2, wherein the mass ratio of the hyperbranched hydrophobic starch to the zinc oxide is 2: 1-10: 1.
4. The modified zinc oxide according to claim 1, wherein the starch of the hyperbranched hydrophobic starch is selected from one or more of corn starch, tapioca starch, sweet potato starch or mung bean starch.
5. The modified zinc oxide according to claim 1, wherein the preparation method of the hyperbranched hydrophobic starch comprises the following steps: 1) hydrolyzing starch into hyperbranched starch, and 2) adding a coupling agent and stearic acid into the hyperbranched starch and mixing uniformly.
6. The modified zinc oxide according to claim 5, wherein the amylase is alpha-amylase, beta-amylase or anhydroglycosidase, and the amount of the amylase is 0.01-0.03% of the mass of the starch.
7. The modified zinc oxide according to claim 5, wherein the coupling agent is one of KH550, KH570, tetraethyl titanate, tetrabutyl titanate and triisopropyl aluminate, and the amount of the coupling agent is 0.8-1.6% of the mass of the starch.
8. A process for preparing the modified zinc oxide of any one of claims 1 to 7, comprising the steps of:
1) adding a certain amount of starch into deionized water, heating to boil under reflux, stirring at high speed until the starch is completely dissolved, adjusting pH to 3.5-4.5 with dilute hydrochloric acid solution after the starch is dissolved, adding amylase, and continuously reacting for a period of time under reflux; after the reaction is finished, cooling the reactant to room temperature, filtering out precipitates, and drying to obtain hyperbranched starch;
2) heating the starch prepared in the step 1) to 65-75 ℃, performing ultrasonic treatment for 10-20min, then adding a coupling agent, stirring for reaction for 10-20min, then adding stearic acid, continuing stirring for 15-25min, and finally drying in an oven to obtain hyperbranched hydrophobic starch;
3) dissolving inorganic zinc salt in absolute ethyl alcohol, then dripping absolute ethyl alcohol sodium hydroxide solution into the absolute ethyl alcohol sodium hydroxide solution, violently stirring the solution at normal temperature to form gel, adding a crystal growth regulator, and stirring the gel for later use;
4) adding the hyperbranched hydrophobic starch prepared in the step 2) into the gel in the step 3), stirring at a high speed at the temperature of 55-65 ℃ for reaction for 1-2h, and then carrying out vacuum filtration, drying and grinding to obtain the hyperbranched starch modified zinc oxide.
9. The method as claimed in claim 8, wherein the ultrasonic power of the ultrasonic treatment in step 2) is 100-300W.
10. The method as claimed in claim 8, wherein the crystal growth regulator in step 3) is boron nitride, and the amount of boron nitride is 0.1-0.6% of the inorganic zinc salt.
11. The modified zinc oxide of any one of claims 1 to 7 for use as a vulcanization activator in rubber processing.
12. A rubber composition comprising the modified zinc oxide according to any one of claims 1 to 7.
13. A tire comprising a vulcanizate of the rubber composition of claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952302.1A CN110684236B (en) | 2019-10-09 | 2019-10-09 | Hyperbranched starch modified zinc oxide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952302.1A CN110684236B (en) | 2019-10-09 | 2019-10-09 | Hyperbranched starch modified zinc oxide and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110684236A CN110684236A (en) | 2020-01-14 |
| CN110684236B true CN110684236B (en) | 2021-06-04 |
Family
ID=69111661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910952302.1A Active CN110684236B (en) | 2019-10-09 | 2019-10-09 | Hyperbranched starch modified zinc oxide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110684236B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068067A (en) * | 2020-02-25 | 2020-04-28 | 广东卫康有害生物防制有限公司 | Pharmaceutical composition for preventing and treating dengue fever virus and preparation method thereof |
| CN112592619A (en) * | 2020-12-22 | 2021-04-02 | 闫明亮 | Antibacterial and mildew-proof putty powder and preparation method thereof |
| CN119264282A (en) * | 2024-10-18 | 2025-01-07 | 华南理工大学 | A high-cavity nano starch and a high-aging-resistant rubber material based thereon and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE250634T1 (en) * | 1999-01-15 | 2003-10-15 | Avebe Coop Verkoop Prod | HYDROPHOBIC STARCH DERIVATIVES |
| CN101230151B (en) * | 2007-12-28 | 2011-04-06 | 北京航空航天大学 | High-fluidity and strong-hydrophobicity starch and preparation method thereof |
| CN101519543A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for preparing coupling agent modified nanometer zinc oxide with reaction groups |
| CN102199639B (en) * | 2011-04-11 | 2014-08-13 | 江南大学 | Carboxymethyl starch stearate and its preparation method |
| CN109912889B (en) * | 2019-03-25 | 2021-07-06 | 深圳市广信达环保材料有限公司 | Method for improving thermal stability of starch-based biodegradable plastic |
-
2019
- 2019-10-09 CN CN201910952302.1A patent/CN110684236B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110684236A (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110684236B (en) | Hyperbranched starch modified zinc oxide and preparation method and application thereof | |
| CN105802032A (en) | High temperature-resistant ethylene-propylene rubber / silicone rubber blended rubber compound and preparation method thereof | |
| CN103627055A (en) | Method for preparing tire tread rubber by use of modified microcrystalline cellulose | |
| CN102952295B (en) | Ozone-resistant and heat-resistant natural mixed rubber | |
| CN117736517A (en) | Ageing-resistant ethylene propylene diene monomer product and preparation method thereof | |
| CN113861511A (en) | Modified pyrolysis carbon black, preparation method thereof and aging-resistant rubber compound | |
| CN101165105B (en) | Chemical coating method for modifying surface of magnesium hydroxide whisker material | |
| EP0555737B1 (en) | Chitosan reinforced tires and method of incorporating chitosan into an elastomer | |
| CN112321909A (en) | High-strength wear-resistant natural rubber composite material and preparation method thereof | |
| CN108250475A (en) | A kind of PVDC coating materials with high obstructing performance and preparation method thereof | |
| CN112458568B (en) | Preparation method of functionalized graphene intercalation in-situ polymerization polyester composite fiber | |
| CN116332157B (en) | A kind of preparation method of nitrogen-metal doped carbon material and its application in rubber | |
| CN109971047B (en) | Natural rubber-white carbon black composite material and preparation method and application thereof | |
| JPH07309956A (en) | Polymers that can be extruded at high casting speeds and their production | |
| CN104725947A (en) | Method for preparing novel polyvinyl alcohol based coating | |
| CN113462042B (en) | Amino modified sepiolite/graphene oxide/natural rubber composite latex and preparation method thereof | |
| CN114031874A (en) | Manufacturing method of CPVC cable protection pipe | |
| CN110734593B (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| CN119081412A (en) | Environmentally friendly rubber composite material of polydopamine/KH550 modified carbon nanotubes and preparation method thereof | |
| CN118852804A (en) | A composite plastic hose and its preparation method and application | |
| CN111807373B (en) | Inorganic nano material with polymer performance and preparation method thereof | |
| CN118344666A (en) | Low-temperature compression permanent deformation resistant rubber material and preparation method thereof | |
| CN1906231A (en) | Method for producing composition containing polymer from liquid containing polymer component and drying apparatus for same | |
| CN108342132A (en) | A kind of PVDC coating materials and preparation method thereof with high obstructing performance | |
| CN117362760A (en) | Starch-based biodegradable film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 310018 No. 1, No. 1 Street, Qiantang District, Hangzhou, Zhejiang Patentee after: Zhongce Rubber Group Co.,Ltd. Address before: 310018 No.2, 10th Street, economic and Technological Development Zone, Jianggan District, Hangzhou City, Zhejiang Province Patentee before: ZHONGCE RUBBER GROUP Co.,Ltd. |