CN115960469A - Preparation method and application of protective wax slow-release microcapsule - Google Patents
Preparation method and application of protective wax slow-release microcapsule Download PDFInfo
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- CN115960469A CN115960469A CN202211593019.2A CN202211593019A CN115960469A CN 115960469 A CN115960469 A CN 115960469A CN 202211593019 A CN202211593019 A CN 202211593019A CN 115960469 A CN115960469 A CN 115960469A
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- protective wax
- calcium
- wax
- rubber
- protective
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- 230000001681 protective effect Effects 0.000 title claims abstract description 137
- 239000003094 microcapsule Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 106
- 239000005060 rubber Substances 0.000 claims abstract description 106
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000007764 o/w emulsion Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000013268 sustained release Methods 0.000 claims abstract description 4
- 239000012730 sustained-release form Substances 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229960005069 calcium Drugs 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 hydrogen ions Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002775 capsule Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 claims description 2
- SIWNEELMSUHJGO-UHFFFAOYSA-N 2-(4-bromophenyl)-4,5,6,7-tetrahydro-[1,3]oxazolo[4,5-c]pyridine Chemical compound C1=CC(Br)=CC=C1C(O1)=NC2=C1CCNC2 SIWNEELMSUHJGO-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- 229940059251 calcium bromide Drugs 0.000 claims description 2
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 claims description 2
- 229960002713 calcium chloride Drugs 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 239000004227 calcium gluconate Substances 0.000 claims description 2
- 229960004494 calcium gluconate Drugs 0.000 claims description 2
- 235000013927 calcium gluconate Nutrition 0.000 claims description 2
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 2
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000013270 controlled release Methods 0.000 claims 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 16
- 230000005012 migration Effects 0.000 abstract description 16
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 119
- 238000007599 discharging Methods 0.000 description 36
- 238000004140 cleaning Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 4
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
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- 239000005662 Paraffin oil Substances 0.000 description 1
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- 239000010692 aromatic oil Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of tire auxiliary agents and rubber material production. Aiming at the problems of high migration speed and easiness in blooming of protective wax in rubber, the invention provides a preparation method and application of protective wax sustained-release microcapsules, wherein the protective wax which is solid at normal temperature and normal pressure is taken and heated to be melted into liquid; dropwise adding liquid protective wax into an anionic surfactant aqueous solution to obtain an oil-in-water emulsion; dropwise adding a calcium salt aqueous solution into the oil-in-water emulsion, and slowly dropwise adding a carbonate aqueous solution into the solution after dropwise adding is finished to obtain a protective wax-calcium carbonate microcapsule; adding protective wax microcapsules to H + Filtering in a low-concentration acid solution, washing with deionized water and drying to obtain the protective wax slow-release microcapsule. The protective wax is in a solid state at normal temperature, the protective wax is melted into a liquid state by heat absorption, and the liquid protective wax is migrated out through micropores on the surface of the calcium carbonate, so that the tread rubber composition with controllable migration speed of the protective wax can be obtained when the protective wax is applied to the rubber composition.
Description
Technical Field
The invention belongs to the field of tire auxiliary agent and rubber material production, and particularly relates to a preparation method and application of protective wax slow-release microcapsules.
Background
In the use process of rubber and rubber products, ozone in the environment can react with the ozone to degrade the physical and chemical properties of the rubber and influence the service life of the products, so that the rubber can be protected from ozone corrosion by adding protective wax in the preparation process of the rubber.
The protective effect of the protective wax on the rubber is mainly static protection, and when the tire is stored and is not used, the protective wax added into the rubber material can migrate to the surface of the rubber due to the low solubility of the protective wax in the rubber to form a micron-sized inert wax film to prevent ozone from contacting with the rubber, so that rubber macromolecules are protected from being attacked and aged by the ozone.
However, in the migration process of the protective wax, if the protective wax is excessively added or the migration speed of the wax is too high, the protective wax which migrates to the surface of the rubber is more, and a layer of white crystals appears when the wax film is thicker, so that the appearance of the product is seriously affected, especially in a pure carbon black tread with higher filling rate. In addition, as the amount of the protective wax added into the rubber material is fixed, the precipitation and the falling of a large amount of protective wax can cause the aging resistance of the finished tire to be reduced in later use. Therefore, how to effectively control the migration amount of the protective wax in the rubber becomes a relatively difficult problem.
The reasons for causing the protective wax in the rubber to be frosted are many, including internal factors and external environmental factors, on one hand, the migration speed of the protective wax can be influenced by the internal factors such as the variety and the dosage of the protective wax in the product formula, the variety and the dosage of the filler in the formula, the variety and the dosage of the polar micromolecules in the formula and the like. On the other hand, external factors such as the production process of the rubber product, the storage environment and the like are also main reasons for influencing the migration speed of the protective wax.
The main method for solving the problem of protective wax blooming at present is as follows: the blooming problem is solved by improving the formulation of the rubber composition, by using a combination of waxes, by using a modified protective wax or by improving the arrangement of wax molecules, mainly by improving the denseness of the wax film. CN108410036A combines two protective waxes with different carbon chain structure distributions, thereby avoiding the unstable migration speed in the sizing material caused by the unstable period structure of the protective wax using a single carbon chain structure. CN110437506A adopts novel modified protective wax HG72, modified protective wax HG72 is finer and denser than traditional protective wax crystallization, and the wax film compactness formed on the surface of rubber is high, so that the resistance received when the supersaturated protective wax inside the rubber continuously migrates out to the surface is larger, and the aims of resisting early-stage blooming and protecting the tire for a long time in a high-humidity and high-heat environment by greatly reducing the blooming and whitening of the rubber caused by excessive sprayed wax are fulfilled. CN110628228A discloses a production method of an anti-blooming rubber protective wax, after a prepared wax liquid is obtained, bubbles and impurities of low-component paraffin oil are removed under the condition of heating and vacuum, then the pressure is increased under the nitrogen atmosphere, the temperature is kept, so that the interaction force among molecules is increased, the wax molecules are changed from loose arrangement to tight arrangement, and after the wax liquid is applied to a rubber product, a wax film formed on the surface of the rubber product is uniform and compact, has strong adsorption force, and effectively prevents the protective wax from being excessively sprayed. The solutions all have certain improvement effects, but the problem of rubber wax spraying cannot be fundamentally solved, and particularly, under the conditions that the carbon black content in the formula of a rubber product is large, the consumption of flexible rubber macromolecules in a raw rubber system is large, and the content of polar substances is small, even if the consumption of the protective wax is reduced to the lower limit content, the phenomenon of surface whitening still occurs.
Disclosure of Invention
The invention aims to overcome the technical problems that the migration speed of protective wax in a rubber composition is uncontrollable and the surface of a rubber product is easy to frost, and provides a preparation method and application of a protective wax slow-release microcapsule.
The specific technical scheme is as follows:
the invention provides a preparation method of protective wax slow-release microcapsules, which comprises the following steps:
(1) Taking the protective wax which is solid at normal temperature and normal pressure, and heating and melting the protective wax to be liquid; preparing an anionic surfactant aqueous solution by using an anionic surfactant and deionized water; dropwise adding the liquid protective wax into an aqueous solution of an anionic surfactant, and stirring to obtain an oil-in-water emulsion;
the main principle of the step is that the protective wax is an oily substance, oil-soluble paraffin is added into an aqueous solution of an anionic surfactant dropwise, a hydrophobic group of the anionic surfactant points to the center of a liquid drop of the paraffin, a hydrophilic group points to an external aqueous solution, and the anionic surfactant is attached to the periphery of the protective wax liquid drop and is integrally in a sphere shape.
(2) Preparing a calcium salt aqueous solution by using soluble calcium salt and deionized water, dropwise adding the calcium salt aqueous solution into the oil-in-water emulsion while stirring, slowly dropwise adding a soluble carbonate aqueous solution into the solution after dropwise adding, continuously stirring for a period of time, performing suction filtration, washing and drying to obtain a protective wax-calcium carbonate microcapsule;
the main reaction principle of the step is that calcium ions can perform complex reaction with hydrophilic groups of anionic surfactants:
Ca 2+ +2RCOO - →ROOCCaCOOR
after the aqueous solution of soluble calcium salt is added into the emulsion in the step (1), calcium ions in the solution and the anionic surfactant are subjected to a complex reaction, and a large amount of calcium ions appear around the protective wax-anionic surfactant liquid drop. After the carbonate aqueous solution is added, calcium ions react with carbonate ions to generate calcium carbonate solid which is coated on the outer layer of the anionic surfactant to form the protective wax microcapsule.
(3) Adding the protective wax microcapsules to H + Stirring for a period of time in an acid solution with the concentration of 0.01mol/L-0.1mol/L, filtering, washing with deionized water and drying to obtain the protective wax slow-release microcapsule.
The main reaction principle of the step is that in a low-concentration acid solution, a small amount of hydrogen ions react with calcium carbonate on the surface of the microcapsule, a small amount of calcium carbonate is dissolved, so that fine micropores are formed on the compact calcium carbonate capsule wall, and finally, through washing with deionized water for multiple times, an anionic surfactant is dissolved in water, and after filtration and drying, the protective wax-calcium carbonate microcapsule with a microporous structure, namely the protective wax sustained-release microcapsule, is finally formed.
The anionic surfactant can be selected from fatty acid salt type, sulfonate type, sulfate salt type or phosphate salt type, such as: sodium dodecylbenzenesulfonate, sulfonates of ethoxylated fatty acid methyl esters, sodium stearate, sodium laureth-11 carboxylate, and the like, and sodium dodecylbenzenesulfonate is preferred.
The aqueous anionic surfactant solution is preferably maintained at a temperature of between 10 ℃ and 45 ℃, more preferably at room temperature.
The soluble calcium salt can be at least one of calcium chloride, calcium gluconate, calcium dihydrogen phosphate, calcium nitrate, calcium bicarbonate, calcium hydrogen sulfate, calcium hydrogen sulfite, calcium hypochlorite, calcium bromide, calcium iodide, calcium chlorate, calcium perchlorate and calcium permanganate, and preferably is calcium chloride.
The soluble carbonate can be at least one of sodium carbonate, potassium carbonate or ammonium carbonate, and is preferably sodium carbonate.
The melting point of the protective wax is preferably 50-70 ℃. Common paraffin wax and microcrystalline wax products can be selected.
The acid solution can be prepared from inorganic strong acid, and preferably hydrochloric acid solution.
In the above-mentioned methods, the stirring speed is low, preferably 100rpm to 200rpm.
The invention also provides an application of the protective wax sustained-release microcapsule. The protective wax-calcium carbonate microcapsule with the micropore structure is added in the processing process of the sizing material, the characteristic that the protective wax is solid at normal temperature and melts into liquid when the environmental temperature reaches the melting point of the protective wax is utilized, and the migration speed of the protective wax can be dynamically controlled by combining the structure of the microcapsule with the micropore.
Preferably, the protective wax slow-release microcapsules and other protective wax are simultaneously present in the rubber. The other protective wax is protective wax except the protective wax, and comprises products such as paraffin wax, microcrystalline wax and the like which are commonly used at present.
Preferably, the protective wax microcapsules with micropores are added into the tread rubber composition to prepare the tread rubber with controllable migration speed of the protective wax.
The calcium carbonate-protective wax microcapsule with micropores is added into the rubber composition, on one hand, the calcium carbonate is added into the rubber composition to have a certain reinforcing effect, the tensile property of rubber materials can be improved, on the other hand, the calcium carbonate-protective wax microcapsule can effectively control the migration speed of the protective wax, the protective wax is in a solid state at normal temperature, the protective wax cannot migrate out of the calcium carbonate capsule, the tread temperature of an automobile can reach more than 60 ℃ in the driving process, the protective wax absorbs heat and is melted to be in a liquid state, at the moment, part of the liquid protective wax can migrate out through the micropores on the surface of the calcium carbonate, and after a certain time, the liquid protective wax can migrate to the surface of the tread rubber, so that the controllable protective effect is achieved.
Preferably, the tread rubber composition with the controllable migration speed of the protective wax comprises, by weight, 100 parts of rubber, 10-70 parts of carbon black, 0.1-5 parts of an active agent, 0.1-3 parts of the protective wax, 0.1-5 parts of an anti-aging agent, 0.1-5 parts of a plasticizer, 0.1-5 parts of a crosslinking agent, 0.1-3 parts of a crosslinking accelerator and 1-5 parts of the calcium carbonate-protective wax microcapsule with micropores.
Preferably, the tread rubber composition with the controllable migration speed of the protective wax comprises, by weight, 50-70 parts of natural rubber, 30-50 parts of butadiene rubber, 40-70 parts of carbon black, 1-5 parts of zinc oxide, 0.1-2 parts of stearic acid, 0.1-1 part of protective wax, 0.1-2 parts of anti-aging agent RD, 0.1-2 parts of anti-aging agent 4020.1-2 parts, 0.1-5 parts of environment-friendly aromatic oil, 0.1-2 parts of accelerator NS, 1-5 parts of sulfur and 1-5 parts of calcium carbonate-protective wax microcapsules.
The invention also provides a preparation method of the tread rubber composition, and the calcium carbonate-protective wax microcapsule with micropores is added during two-stage mixing.
Preferably, the preparation method of the tread rubber composition comprises the following steps:
first-stage mixing: putting rubber, carbon black, an active agent, protective wax and an anti-aging agent into an internal mixer, pressing a top plug at the rotating speed of 70rpm for mixing for 30-35s, raising the top plug, adding a plasticizer, mixing for 50s at the rotating speed of 70rpm, cleaning the top plug, controlling the mixing temperature to be 160-180 ℃, continuously mixing for 50s, opening a discharging door, discharging rubber materials, and discharging rubber materials by using an open mill;
and (3) second-stage mixing: putting the first-stage rubber compound into an internal mixer, mixing for 30s at the rotating speed of 45rpm, adding the calcium carbonate-protective wax microcapsules with micropores, mixing for 60s at the rotating speed of 65rpm, cleaning the upper top plug, continuously mixing for 30s, discharging rubber, and discharging sheets by using an open mill;
and (3) final refining: and (2) putting the two-stage rubber compound, the cross-linking agent and the cross-linking accelerator into an internal mixer, mixing for 30s at the rotating speed of 45rpm, cleaning the internal mixer after a ram is arranged, mixing for 30s, discharging rubber, discharging the rubber by an open mill, and controlling the rotating speed of the internal mixer during the mixing process to ensure that the rubber discharging temperature is 50-100 ℃.
The invention has the beneficial effects that:
(1) The calcium carbonate-protective wax microcapsule prepared by the invention has the particle size distribution range of 0.5-5 mu m, can be rapidly dispersed in rubber, and has good processability; the micropore size is 0.1nm-10nm, the migration speed of protective wax molecules can be controlled, the accumulation amount of the protective wax can be controlled, and the phenomenon of blooming is avoided. In addition, the content of the protective wax in the calcium carbonate-protective wax microcapsule particle reaches more than 40 percent.
(2) As a commonly used inorganic reinforcing filler, the addition of calcium carbonate can enhance the tensile property of the rubber compound. Secondly, at normal temperature, the protective wax is wrapped in a solid state and is filled in the calcium carbonate capsule, so that the condition that the protective wax migrates out in large quantity due to the problems of environmental temperature, humidity and the like in the storage process can be effectively avoided. In addition, during the period from tire production to installation, the static ozone protection of the rubber material mainly depends on a part of protective wax added in a mixing process, after the tire is installed and runs on a road, most of the protective wax on the surface of the tread is reduced due to friction, and meanwhile, as the temperature of the tire can reach more than 60 ℃ during the running process, the protective wax wrapped in calcium carbonate is melted into liquid and slowly migrates out to the surface of tread rubber through micropores on the bag wall, so that the state of controllable migration speed is achieved.
Drawings
FIG. 1 shows the results of the weathering test of tread compounds with and without the addition of the slow-release microcapsules of protective wax.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
1. Preparation of protective wax slow-release microcapsule
Example 1
(1) Putting a certain volume fraction of protective wax into a beaker, heating in a water bath to melt the protective wax into a liquid state, dropwise adding the liquid protective wax into an aqueous solution of SDBS (sodium dodecyl benzene sulfonate) and stirring at the speed of 150rpm to obtain a light milky oil-in-water emulsion;
(2) Dissolving calcium chloride with a certain mass fraction in deionized water to prepare a calcium chloride solution, dropwise adding the calcium chloride solution into the emulsion prepared in the step (1), stirring at the speed of 150rpm for a period of time, slowly dropwise adding a sodium carbonate aqueous solution with a certain concentration into the solution, continuously stirring for a period of time, performing suction filtration, washing and drying to obtain the protective wax microcapsule;
(3) Adding the protective wax microcapsule into H + Stirring the mixture for 2 hours at the speed of 150rpm in a hydrochloric acid solution with the concentration of 0.05mol/L, filtering, washing with deionized water and drying to obtain the protective wax-calcium carbonate microcapsule with a microporous structure.
Example 2
Sodium stearate was used as an anionic surfactant in addition to example 1, and other conditions were not changed.
Example 3
On the basis of example 1, potassium carbonate was used instead of sodium carbonate, the other conditions being unchanged.
Example 4
On the basis of example 1, H is used + In 0.1mol/L hydrochloric acid solution, stirring at 150rpm for 10min, and keeping the other conditions unchanged.
The particle size distribution range of the protective wax slow-release microcapsule prepared by the embodiment is 0.5-5 μm; micropore size range: 0.1nm-10nm; the content of the protective wax reaches more than 40 percent. The following application experiments were carried out with the protective wax slow release minigels prepared in example 1.
2. Application of protective wax microcapsule in rubber
Comparative example:
first-stage mixing: putting 60 parts of natural rubber, 40 parts of butadiene rubber, 60 parts of carbon black N330, 1 part of stearic acid, 0.5 part of protective wax, 3 parts of zinc oxide, 1 part of antioxidant RD and 1.5 parts of antioxidant 4020 into an internal mixer, pressing a top plug, mixing for 30-35s at a rotating speed of 70r, lifting the top plug, adding 3 parts of TDAE, mixing for 50s at a rotating speed of 70rpm, cleaning the top plug, controlling the mixing temperature to be 160-180 ℃, continuously mixing for 50s, then opening a discharging door, discharging rubber materials, and discharging sheets by using an open mill.
And (3) second-stage mixing: and (3) putting the first-stage rubber compound into an internal mixer, mixing for 30s at the rotation speed of 45rpm, mixing for 60s at the rotation speed of 65rpm, cleaning a top plug, continuously mixing for 30s, discharging rubber, and discharging pieces by using an open mixer.
And (3) final refining: and (2) putting the two-stage rubber compound, 3 parts of sulfur and 1 part of an accelerant NS into an internal mixer, mixing for 30s at the rotating speed of 45rpm, cleaning the top plug, mixing for 30s, discharging rubber after the top plug is lifted, continuously mixing for 30s, discharging rubber from an open mixer, and controlling the rotating speed of the internal mixer during the mixing process to ensure that the rubber discharging temperature is 50-100 ℃.
Example 1:
first-stage mixing: putting 60 parts of natural rubber, 40 parts of butadiene rubber, 60 parts of carbon black N330, 1 part of stearic acid, 0.5 part of protective wax, 3 parts of zinc oxide, 1 part of antioxidant RD and 1.5 parts of antioxidant 4020 into an internal mixer, pressing a top plug, mixing for 30-35s at a rotating speed of 70r, lifting the top plug, adding 3 parts of TDAE, mixing for 50s at a rotating speed of 70rpm, cleaning the top plug, controlling the mixing temperature to be 160-180 ℃, continuously mixing for 50s, then opening a discharging door, discharging rubber materials, and discharging sheets by using an open mill.
And (3) second-stage mixing: and (3) putting the first-stage rubber compound into an internal mixer, mixing for 30s at the rotation speed of 45rpm, adding 3 parts of calcium carbonate-protective wax microcapsules, mixing for 60s at the rotation speed of 65rpm, cleaning a top plug, continuously mixing for 30s, discharging rubber, and discharging pieces by using an open mill.
And (3) final refining: and (2) putting the two-stage rubber compound, 3 parts of sulfur and 1 part of an accelerator NS into an internal mixer, mixing for 30s at the rotating speed of 45rpm, cleaning a ram, mixing for 30s, discharging rubber after continuing mixing for 30s after lifting the ram, discharging rubber by using an open mill, and controlling the rotating speed of the internal mixer in the mixing process to ensure that the rubber discharging temperature is 50-100 ℃.
Example 2
First-stage mixing: 60 parts of natural rubber, 40 parts of butadiene rubber, 60 parts of carbon black N330, 1 part of stearic acid, 0.5 part of protective wax, 3 parts of zinc oxide, 1 part of antioxidant RD, and 1.5 parts of antioxidant 4020 are put into an internal mixer, a ram is pressed on, the rotating speed is 70r, the mixture is mixed for 30-35s, the ram is lifted up, 3 parts of TDAE are added, the mixture is mixed for 50s at the rotating speed of 70rpm, the mixing temperature is controlled to be 160-180 ℃ after the ram is cleaned, the mixing is continued for 50s, a discharging door is opened, the rubber material is discharged, and the sheet is discharged by using an open mill.
And (3) second-stage mixing: and (3) putting the first-stage rubber compound into an internal mixer, mixing for 30s at the rotating speed of 45rpm, adding 4 parts of calcium carbonate-protective wax microcapsules, mixing for 60s at the rotating speed of 65rpm, cleaning the upper top plug, continuously mixing for 30s, discharging rubber, and discharging pieces by using an open mixer.
And (3) final refining: and (2) putting the two-stage rubber compound, 3 parts of sulfur and 1 part of an accelerant NS into an internal mixer, mixing for 30s at the rotating speed of 45rpm, cleaning the top plug, mixing for 30s, discharging rubber after the top plug is lifted, continuously mixing for 30s, discharging rubber from an open mixer, and controlling the rotating speed of the internal mixer during the mixing process to ensure that the rubber discharging temperature is 50-100 ℃.
Example 3
First-stage mixing: 60 parts of natural rubber, 40 parts of butadiene rubber, 60 parts of carbon black N330, 1 part of stearic acid, 0.5 part of protective wax, 3 parts of zinc oxide, 1 part of antioxidant RD, and 1.5 parts of antioxidant 4020 are put into an internal mixer, a ram is pressed on, the rotating speed is 70r, the mixture is mixed for 30-35s, the ram is lifted up, 3 parts of TDAE are added, the mixture is mixed for 50s at the rotating speed of 70rpm, the mixing temperature is controlled to be 160-180 ℃ after the ram is cleaned, the mixing is continued for 50s, a discharging door is opened, the rubber material is discharged, and the sheet is discharged by using an open mill.
And (3) second-stage mixing: and (3) putting the first-stage rubber compound into an internal mixer, mixing for 30s at the rotation speed of 45rpm, adding 5 parts of calcium carbonate-protective wax microcapsules, mixing for 60s at the rotation speed of 65rpm, cleaning the upper top plug, continuously mixing for 30s, discharging rubber, and discharging pieces by using an open mixer.
And (3) final refining: and (2) putting the two-stage rubber compound, 3 parts of sulfur and 1 part of an accelerant NS into an internal mixer, mixing for 30s at the rotating speed of 45rpm, cleaning the top plug, mixing for 30s, discharging rubber after the top plug is lifted, continuously mixing for 30s, discharging rubber from an open mixer, and controlling the rotating speed of the internal mixer during the mixing process to ensure that the rubber discharging temperature is 50-100 ℃.
TABLE 1 formulation of rubber compositions for comparative and example
The rubber compositions prepared in comparative examples, examples 1 to 3 in Table 1 were subjected to the tests for basic properties, surface protective wax precipitation, static ozone, weathering test, and the test results are shown in Table 2.
As can be seen from the physical property data before and after aging in Table 2, compared with the comparative example, the tensile strength and the stress at definite elongation of the rubber material after the protective wax slow-release microcapsules are added are improved to a certain extent, and are obviously improved along with the increase of the addition amount of the protective wax slow-release microcapsules, in addition, the elongation at break of the rubber material is slightly reduced, and the difference of the other basic physical property data is not large.
From the test result of the precipitation amount of the protective wax, the precipitation amount of the protective wax of the test glue is obviously lower than that of the comparative example in each test stage.
From the static ozone aging data, the degree of cracking of the rubber mixture surface was comparable to the comparative example.
From the results of the weathering test, the surfaces of the comparative examples and examples were not significantly changed and no weathering cracks were observed after 5 months of the weathering test (FIG. 1).
In conclusion, after the protective wax slow-release microcapsule prepared by the invention is added into a tread rubber material to prepare the tread rubber composition, the precipitation amount of the protective wax can be effectively controlled on the premise of ensuring that the rubber material slows down ozone aging, so that the problem of tire appearance pollution caused by the precipitation of the protective wax on the tire tread is pertinently solved.
TABLE 2 results of sample testing
The related test method comprises the following steps:
hardness before and after aging: [ GB/T531.1 ] vulcanized rubber or thermoplastic rubber indentation hardness test method the first part of the Shore durometer method.
Tensile strength, stress at definite elongation, elongation at break before and after aging: [ GB/T528 ] determination of tensile Properties of vulcanized rubber and thermoplastic rubber.
Static ozone aging: [ GB/T7762 ] static tensile test method for ozone aging resistance test of vulcanized rubber.
The amount of the protective wax precipitated out was determined using the method established in the following literature: li Jianmin, wangyuang, zijuan, sunyuan, li Linglili, zhang Caiyun and high temperature gas chromatography are used for measuring the carbon number distribution of the rubber protective wax, namely [ J ]. Henan Petroleum, 2005 (03): 79-80+102.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (9)
1. A preparation method of a protective wax slow-release microcapsule is characterized by comprising the following steps:
(1) Taking the protective wax which is solid at normal temperature and normal pressure, and heating and melting the protective wax to be liquid; preparing an anionic surfactant aqueous solution by using an anionic surfactant and deionized water; dropwise adding the liquid protective wax into an aqueous solution of an anionic surfactant, and stirring to obtain an oil-in-water emulsion;
(2) Preparing a calcium salt aqueous solution by using soluble calcium salt and deionized water, dropwise adding the calcium salt aqueous solution into the oil-in-water emulsion obtained in the step (1) while stirring, allowing calcium ions in the solution to perform a complexing reaction with an anionic surfactant, slowly dropwise adding a soluble carbonate aqueous solution after dropwise adding is finished, and stirring, wherein Ca is added 2+ With CO 3 2- Reaction to produce CaCO 3 Coating the solid outside the anionic surfactant, stirring for a period of time, filtering, washing and drying to obtain the protective wax-calcium carbonate microcapsule;
(3) Adding the protective wax-calcium carbonate microcapsule to H + Stirring for a period of time in an acid solution with the concentration of 0.01-0.1 mol/L, reacting a small amount of hydrogen ions with calcium carbonate on the surface of the microcapsule, dissolving a small amount of calcium carbonate, so that fine micropores are formed on the compact calcium carbonate capsule wall, filtering, washing with deionized water, and drying to obtain the protective wax slow-release microcapsule with a microporous structure.
2. The process for preparing wax-protected microcapsules of claim 1, wherein the anionic surfactant is a fatty acid salt type, a sulfonate type, a sulfate type or a phosphate type.
3. The method for preparing the protective wax slow-release microcapsule according to claim 1, wherein the soluble calcium salt can be at least one of calcium chloride, calcium gluconate, calcium dihydrogen phosphate, calcium nitrate, calcium bicarbonate, calcium hydrogen sulfate, calcium hydrogen sulfite, calcium hypochlorite, calcium bromide, calcium iodide, calcium chlorate, calcium perchlorate and calcium permanganate; the soluble carbonate is at least one of sodium carbonate, potassium carbonate or ammonium carbonate.
4. The method for preparing the protective wax sustained-release microcapsule according to claim 1, wherein the melting point of the protective wax at normal temperature and normal pressure is 50-70 ℃.
5. The method for preparing the protective wax slow-release microcapsule according to claim 1, wherein the stirring is performed at a rotation speed of 100rpm to 200rpm.
6. The use of the protective wax slow-release microcapsules prepared according to claim 1 in rubber, characterized in that the protective wax slow-release microcapsules with a microporous structure are added in the process of rubber material processing, the protective wax is in a solid state at normal temperature, the protective wax is melted into a liquid state by heat absorption, and the liquid protective wax migrates out through micropores on the surface of calcium carbonate.
7. Use of the protective wax controlled-release microcapsules prepared according to claim 1 in rubber, characterized in that the protective wax controlled-release microcapsules are added to a tread rubber composition, the protective wax controlled-release microcapsules and the other protective wax being present in the rubber at the same time.
8. The application of the protective wax slow-release microcapsule prepared by the method of claim 7 in rubber is characterized in that the tread rubber composition comprises, by weight, 100 parts of rubber, 10-70 parts of carbon black, 0.1-5 parts of an active agent, 0.1-3 parts of protective wax, 0.1-5 parts of an anti-aging agent, 0.1-5 parts of a plasticizer, 0.1-5 parts of a cross-linking agent, 0.1-3 parts of a cross-linking accelerator and 1-5 parts of the calcium carbonate-protective wax microcapsule with micropores.
9. Use of the wax-protected slow-release microcapsules prepared according to claim 8 in rubber, characterized in that the calcium carbonate-wax-protected microcapsules with micropores are added during the two-stage mixing.
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