CN105504384A - Zinc oxide special for natural rubber and preparation method of zinc oxide - Google Patents
Zinc oxide special for natural rubber and preparation method of zinc oxide Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
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- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C08L7/00—Compositions of natural rubber
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- C08K3/20—Oxides; Hydroxides
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses zinc oxide special for natural rubber and a preparation method of the zinc oxide. The zinc oxide special for the natural rubber comprises, by weight, 50-70 parts of zinc oxide, 10-20 parts of zinc stearate, 15-25 parts of zinc p-toluate and 2-5 parts of dispersant. The preparation method of the zinc oxide comprises the following steps of 1, adding the dispersant to a zinc sulfate solution, and conducting stirring so that the dispersant can be uniformly dispersed in the solution; 2, adding p-toluylic acid and stearic acid to a sodium hydroxide solution, conducting stirring while the mixture is heated to 60 DEG C, and continuing with heat preservation and stirring till a reaction is conducted completely; 3, under the condition that stirring is conducted ceaselessly, adjusting the pH value of a mixed solution which is obtained in step 1 and step 2 after the reaction is conducted for a while with a sodium hydroxide solution, continuing stirring till the reaction is ended, and then conducting centrifugal separation; 4, drying filter cakes obtained after separation, so that the zinc oxide special for the natural rubber is obtained. The zinc oxide has the vulcanization activating function and can improve anti-vulcanization reversion performance of the natural rubber, and dispersibility of the zinc oxide in a rubber material is good.
Description
Technical field
The invention belongs to Field of Fine Chemicals, relate to a kind of high dispersive zinc oxide and preparation method thereof.
Background technology
Natural rubber (NR), as a kind of conventional rubber, has good elasticity and mechanical property, obtains a wide range of applications at each department of national economy.But NR there will be reversion phenomenon in various degree in sulfur cross-linking system, which greatly limits the application of NR, in particular for thick products such as engineering tyres.Reversion refers to that polysulfidic bond thermal destruction causes cross-linking density to decline, and crosslinking bond type distribution changes, backbone modification.Reversion can cause vulcanizating glue physical performance decline, Young's modulus reduces, viscous modulus increases, havoc sizing material dynamic property.The reversion of sizing material mainly causes due to the over cure in sulfuration and use procedure.
Cryogenic vulcanization improves the simplest and method of widespread use of reversion, but cryogenic vulcanization causes curing time to extend, as sizing material sulfuration at 170 DEG C arrive time of plateau cure be 130 DEG C at sulfuration 1/16, and the method thoroughly can not solve product phenomenon of reverting in use, what produce because crosslinked is polysulfidic bond, lacks thermostability.Effectively or SE curing system, the generation quantity of polysulfidic bond can be reduced, improve reversion resistance, but this scorch safety to sizing material, flexing fatigue and tear resistance have negative impact.And efficient vulcanization system vulcanization rate is fast, total sulfur content is low, is unsuitable for the bonding of sizing material and metal or fabric.The C-C cross-link bond bond energy that peroxide vulcanizing system produces is high, and resistance toheat is good, but the physical and mechanical properties of gained cross-linked rubber is poor, poor with the bond properties of metal or fabric, and is not suitable for using in a dynamic condition.A few class anti-recovery agents in the market, as dual-citraconic imide class, the two Sulfothiorine classes of hexamethylene and organic zinc soap class, can anti-recovery, do not affect again other mechanical properties of cross-linked rubber, but the price of these recovery agent costlinesses has become the pain of injury of rubber molding plant, in order to control cost, it can only be the least possible use anti-recovery agent when meeting properties of rubber, general addition can not exceed 0.6% of rubber unvulcanizate gross weight, so low interpolation number, thus be difficult to it is dispersed in sizing material, closely affect the performance of its whole structure.
Zinc oxide is conventional vulcanization activator, generally coordinates sulphur, promotor jointly to form sulfur cross-linking system, plays a role in sulfidation, the performance shortening curing time, improve cross-linking density, improve cross-linked rubber.But use the NR system of sulfur cross-linking all can there is phenomenon of reverting.In addition, zinc oxide is inorganics, be doomed poor compatibility therebetween, and zinc oxide is also urgently to be resolved hurrily at the scattering problem of rubber materials with the difference of rubber polymer solubility parameter aspect.
At present, lack the special zinc oxide of a kind of natural gum, it has good dispersiveness in natural rubber, and can improve the anti-problem of reverting of sizing material, closely improves the physical and mechanical properties of rubber item (especially thick product).
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of special zinc oxide of natural rubber having both anti-recovery effect and preparation method thereof.
To achieve these goals, the present invention is achieved through the following technical solutions: the special zinc oxide of a kind of natural rubber of the present invention, and the special zinc oxide of described natural rubber comprises the following component by mass percentage:
Zinc oxide 50 ~ 70
Zinic stearas 10 ~ 20
P-methylbenzoic acid zinc 15 ~ 25
Dispersion agent 2 ~ 5
The preparation method of the special zinc oxide of natural rubber of the present invention, comprises the steps:
(1) add in solution of zinc sulfate by dispersion agent, stir and make it in the solution dispersed, the mass percentage that dispersion agent accounts for solution is 0.27% ~ 1.5%, and the mass percentage that zinc sulfate accounts for solution is 20% ~ 35%;
(2) under the rotating speed of 100 ~ 800r/min, p-methylbenzoic acid and stearic acid are added in sodium hydroxide solution, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 5.5% ~ 29%, and the mass percentage that sodium stearate accounts for solution is 4.5% ~ 20%;
(3) under the rotating speed of 100 ~ 800r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 30 ~ 120min, the pH value of hydro-oxidation sodium solution regulation system is 7 ~ 8, after continuing stirring reaction 30 ~ 120min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained.
Further, in step (1), described dispersion agent is: the mixture of one or both and above arbitrary proportion in Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, trisodium phosphate, sodium oleate, sodium polyacrylate, cetyl trimethylammonium bromide, polyoxyethylene octylphenol ether, Arlacel-20, Arlacel-40, Arlacel-60, Tween-60.
In step (2), the concentration of described sodium hydroxide solution is 2% ~ 10%.
In step (3), described concentration of sodium hydroxide solution is 25% ~ 33%.
Beneficial effect: the present invention is by simple, easy and the solution methods of gentleness prepares a kind of special zinc oxide of natural rubber having both anti-recovery effect.The introducing of dispersion agent solves the agglomeration traits between zinc oxide primary particles, improves its dispersiveness in macromolecular material; The introducing of organic carboxyl acid zinc salt improves the consistency between zinc oxide and rubber molecule, and improves the processing characteristics of rubber size to a certain extent.Synergy between zinc oxide, phenyl carboxylic acid's zinc and Zinic stearas, make it existing vulcanization of rubber active function, the compression deformation rate under the anti-recovery problem of sizing material, reduction high temperature and dynamic heat build up can also be improved simultaneously, also contribute to promoting the bond properties between sizing material and steel wire cord.In addition, the composition that this product is special, makes each component all can disperse well in sizing material, is the rubber vulcanization system auxiliary agent that a comprehensive cost performance is very high.
Accompanying drawing explanation
Fig. 1 is that the special zinc oxide of natural rubber of embodiments of the invention 1 gained is added in sizing material, the photo of the amplification 400 times using separating apparatus to collect.
Fig. 2 is that the indirect process zinc oxide of comparative example gained of the present invention is added in sizing material, the photo of the amplification 400 times using separating apparatus to collect.
Fig. 3 is the photo that the scanning electronic microscope in the special zinc oxide of natural rubber of embodiments of the invention 1 gained and the tension fracture face of rubber composite amplifies 1000 times.
Fig. 4 is the photo that the scanning electronic microscope in the tension fracture face of comparative example gained indirect process zinc oxide of the present invention and rubber composite amplifies 1000 times.
Embodiment
Further illustrate the present invention by the following examples.It should be understood that these embodiments are explaination of the present invention and citing, do not limit the scope of the invention in any form.
Embodiment 1
The special zinc oxide of a kind of natural rubber of the present invention, the special zinc oxide of described natural rubber comprises following component by weight:
Zinc oxide 50
Zinic stearas 20
P-methylbenzoic acid zinc 25
Dispersion agent (Zinc dodecylbenzenesulphonate) 5
The preparation method of the special zinc oxide of natural rubber of the present invention, comprises the steps:
(1) add in solution of zinc sulfate by Sodium dodecylbenzene sulfonate, stir and make it in the solution dispersed, the mass percentage that Sodium dodecylbenzene sulfonate accounts for solution is 1.5%, and the mass percentage that zinc sulfate accounts for solution is 35%;
(2) under the rotating speed of 100r/min, p-methylbenzoic acid and stearic acid being added concentration is in the sodium hydroxide solution of 2%, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 5.5%, and the mass percentage that sodium stearate accounts for solution is 4.5%;
(3) under the rotating speed of 100r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 30min, to add concentration be the pH value of the sodium hydroxide solution regulation system of 25% is 7, after continuing stirring reaction 30min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained.
Embodiment 2
The special zinc oxide of a kind of natural rubber of the present invention, the special zinc oxide of described natural rubber comprises the following component by mass percentage:
Zinc oxide 70
Zinic stearas 10
P-methylbenzoic acid zinc 15
Dispersion agent (hexa metaphosphoric acid zinc) 5
The preparation method of the special zinc oxide of natural rubber of the present invention, comprises the steps:
(1) add in solution of zinc sulfate by Sodium hexametaphosphate 99, stir and make it in the solution dispersed, the mass percentage that Sodium hexametaphosphate 99 accounts for solution is 0.65%, and the mass percentage that zinc sulfate accounts for solution is 20%;
(2) under the rotating speed of 800r/min, p-methylbenzoic acid and stearic acid being added concentration is in the sodium hydroxide solution of 10%, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 29%, and the mass percentage that sodium stearate accounts for solution is 20%;
(3) under the rotating speed of 800r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 120min, to add concentration be the pH value of the sodium hydroxide solution regulation system of 33% is 8, after continuing stirring reaction 120min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained.
Embodiment 3
The special zinc oxide of a kind of natural rubber of the present invention, the special zinc oxide of described natural rubber comprises the following component by mass percentage:
Zinc oxide 60
Zinic stearas 15
P-methylbenzoic acid zinc 23
Dispersion agent (zinc oleate) 2
The preparation method of the special zinc oxide of natural rubber of the present invention, comprises the steps:
(1) add in solution of zinc sulfate by sodium oleate, stir and make it in the solution dispersed, the mass percentage that sodium oleate accounts for solution is 0.4%, and the mass percentage that zinc sulfate accounts for solution is 28%;
(2) under the rotating speed of 600r/min, p-methylbenzoic acid and stearic acid being added concentration is in the sodium hydroxide solution of 6%, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 17.6%, and the mass percentage that sodium stearate accounts for solution is 11.8%;
(3) under the rotating speed of 500r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 90min, to add concentration be the pH value of the sodium hydroxide solution regulation system of 32% is 7.5, after continuing stirring reaction 120min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained.
Embodiment 4
The special zinc oxide of a kind of natural rubber of the present invention, the special zinc oxide of described natural rubber comprises the following component by mass percentage:
Zinc oxide 70
Zinic stearas 10
P-methylbenzoic acid zinc 18
Dispersion agent (polyacrylic acid zinc) 2
The preparation method of the special zinc oxide of natural rubber of the present invention, comprises the steps:
(1) add in solution of zinc sulfate by sodium polyacrylate, stir and make it in the solution dispersed, the mass percentage that sodium polyacrylate accounts for solution is 0.27%, and the mass percentage that zinc sulfate accounts for solution is 20%;
(2) under the rotating speed of 500r/min, p-methylbenzoic acid and stearic acid being added concentration is in the sodium hydroxide solution of 8%, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 24.5%, and the mass percentage that sodium stearate accounts for solution is 14%;
(3) under the rotating speed of 600r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 110min, to add concentration be the pH value of the sodium hydroxide solution regulation system of 28% is 7, after continuing stirring reaction 95min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained.
Comparative example
Indirect process zinc oxide is raw material with zinc ingot metal, in plumbago crucible, be converted into zinc fume under the high temperature of 1000 DEG C, generated zinc oxide subsequently by the atmospheric oxidation blasted, and collect after cooling tube and obtain.
Test 1
Be applied in buffering adhesive formula by indirect process zinc oxide prepared by the special zinc oxide of natural rubber obtained for embodiment 1 and comparative example, formula used is as shown in table 1 below.
Table 1
In two roller mill, first natural rubber is plasticated, then add various auxiliary agent, obtain rubber unvulcanizate, then on vulcanizing press, carry out sulfuration, obtain vulcanized rubber.Test by national standard, gained performance is as shown in table 2.Note: the test stroke of compression fatigue temperature rise is 5.08 ± 0.03X, testing the prestress born is 1.00 ± 0.03MPa; Reversion resistance conservation rate refers to the ratio with performance under 145 DEG C × 45min condition under 175 DEG C × 45min condition.
Data analysis in his-and-hers watches 2: the comparison of 1) fill a prescription 1 and formula 2: after adding anti-recovery agent HTS, compound modulus increases, and fatigue temperature rise reduces, and anti-reversion behaviour promotes; 2) formula 3 and formula 1 compare: after using the special zinc oxide of natural rubber, and processing characteristics is improved, compound modulus lifting, and fatigue temperature rise reduces, and the bond properties of sizing material and steel wire cord improves, and anti-reversion behaviour improves; 3) to fill a prescription the comparison of 2 and formula 3: the physical and mechanical properties of the two sizing material and antireversion energy difference are little, but formula 3 is comparatively filled a prescription and 2 is had more excellent processing characteristics.As fully visible: the special zinc oxide of natural rubber prepared by 6 parts of embodiments 1 can substitute 5 parts of indirect process zinc oxides and 0.6 part of HTS completely to promote the antireversion energy of sizing material, and the special zinc oxide market price the same with indirect process zinc oxide and HTS exceed the price more than 5 times compared with indirect process zinc oxide, make the target product of present specification have more excellent comprehensive cost performance.
Separating apparatus is used to observe the cross section of rubber unvulcanizate: Fig. 1 is that after the special zinc oxide of natural rubber of embodiment 1 preparation is added on sizing material, rubber unvulcanizate cross section is exaggerated the photo of 400 times; Fig. 2 is that after indirect process zinc oxide prepared by comparative example is added on sizing material, rubber unvulcanizate cross section is exaggerated the photo of 400 times.Vulcanized rubber, after low-temperature brittle fracture, uses sem observation section situation: Fig. 3 is the section picture of the cross-linked rubber adding the special zinc oxide of natural rubber prepared by embodiment 1; Fig. 4 is the section picture of the cross-linked rubber of the indirect process zinc oxide using comparative example to prepare.
Find out from the comparison of Fig. 1 and Fig. 2: the special zinc oxide of the natural rubber Fig. 1 has better dispersiveness compared with the indirect process zinc oxide in Fig. 2.The comparison of Fig. 3 and Fig. 4: the indirect process zinc oxide agglomerate grain in Fig. 4, and have part indirect process zinc oxide exposed; And the consistency of the special zinc oxide of natural rubber that embodiment 1 obtains and rubber matrix is good, Fig. 3 shows the special zinc oxide of natural rubber and is all coated in rubber matrix, rarely expose, from Fig. 3, it can also be seen that the special zinc oxide of natural rubber is dispersed in rubber.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (4)
1. the special zinc oxide of natural rubber, is characterized in that: the special zinc oxide of described natural rubber comprises following component by weight:
Zinc oxide 50 ~ 70,
Zinic stearas 10 ~ 20,
P-methylbenzoic acid zinc 15 ~ 25,
Dispersion agent 2 ~ 5.
2. the special zinc oxide of natural rubber according to claim 1, is characterized in that comprising the steps:
(1) dispersion agent adds in solution of zinc sulfate, and stir and make it in the solution dispersed, the mass percentage that dispersion agent accounts for solution is 0.27% ~ 1.5%, and the mass percentage that zinc sulfate accounts for solution is 20% ~ 35%;
(2) under the rotating speed of 100 ~ 800r/min, p-methylbenzoic acid and stearic acid are added in sodium hydroxide solution, be heated to 60 DEG C while stirring, continue insulated and stirred to reacting completely, obtain the mixing solutions of p-methylbenzoic acid sodium and sodium stearate, the mass percentage that p-methylbenzoic acid sodium accounts for solution is 5.5% ~ 29%, and the mass percentage that sodium stearate accounts for solution is 4.5% ~ 20%;
(3) under the rotating speed of 100 ~ 800r/min, by two kinds of solution short mix of step (1) and step (2), after continuing stirring reaction 30 ~ 120min, the pH value of hydro-oxidation sodium solution regulation system is 7 ~ 8, after continuing stirring reaction 30 ~ 120min, carry out centrifugation;
(4), after isolated filter cake drying, the special zinc oxide of natural rubber can be obtained;
Further, in step (1), described dispersion agent is: the mixture of one or both and above arbitrary proportion in Sodium hexametaphosphate 99, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, trisodium phosphate, sodium oleate, sodium polyacrylate, cetyl trimethylammonium bromide, polyoxyethylene octylphenol ether, Arlacel-20, Arlacel-40, Arlacel-60, Tween-60.
3. the preparation method of the special zinc oxide of natural rubber according to claim 2, is characterized in that: in step (2), and the concentration of described sodium hydroxide solution is 2% ~ 10%.
4. the preparation method of the special zinc oxide of natural rubber according to claim 2, is characterized in that: in step (3), and described concentration of sodium hydroxide solution is 25% ~ 33%.
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| CN113214547A (en) * | 2021-06-24 | 2021-08-06 | 四川川东电缆有限责任公司 | Rubber for cable and preparation method thereof |
| CN114316448A (en) * | 2021-12-28 | 2022-04-12 | 仝国磊 | Melting and chemically modified ethylene propylene rubber sealing element material and preparation method thereof |
| CN115353664A (en) * | 2022-09-02 | 2022-11-18 | 常州市五洲环保科技有限公司 | Modified zinc oxide vulcanizing agent and preparation method thereof |
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| CN106366701B (en) * | 2016-08-24 | 2018-02-27 | 江苏爱特恩高分子材料有限公司 | A kind of preparation method of high dispersive zinc oxide |
| CN107935024A (en) * | 2018-01-17 | 2018-04-20 | 盐城科迈特新材料有限公司 | A kind of preparation method of high-activity nano zinc oxide |
| CN107935024B (en) * | 2018-01-17 | 2019-12-03 | 科迈特新材料有限公司 | A kind of preparation method of high-activity nano zinc oxide |
| CN113214547A (en) * | 2021-06-24 | 2021-08-06 | 四川川东电缆有限责任公司 | Rubber for cable and preparation method thereof |
| CN114316448A (en) * | 2021-12-28 | 2022-04-12 | 仝国磊 | Melting and chemically modified ethylene propylene rubber sealing element material and preparation method thereof |
| CN115353664A (en) * | 2022-09-02 | 2022-11-18 | 常州市五洲环保科技有限公司 | Modified zinc oxide vulcanizing agent and preparation method thereof |
| CN115650196A (en) * | 2022-09-09 | 2023-01-31 | 株洲冶炼集团股份有限公司 | Synthesis method of zinc metaphosphate and application of zinc metaphosphate in thallium removal of zinc sulfate solution |
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