CN105017564A - Method for improving zinc oxide sulfuration activity - Google Patents
Method for improving zinc oxide sulfuration activity Download PDFInfo
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- CN105017564A CN105017564A CN201510426547.2A CN201510426547A CN105017564A CN 105017564 A CN105017564 A CN 105017564A CN 201510426547 A CN201510426547 A CN 201510426547A CN 105017564 A CN105017564 A CN 105017564A
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Abstract
The invention relates to a method for improving zinc oxide sulfuration activity and belongs to the technical field of natural rubber processing. The method comprises adding 0.5-10 parts of rare earth oxide into 100 parts of common zinc oxide and carrying out ball milling and high temperature sintering rare earth doping. According to inherent characteristics of rare earth, zinc oxide particle conformation structure and ion surface chemical properties are changed, sulfuration activity is improved, a use ratio of zinc oxide in the rubber formula is reduced from 5: 100 to 2: 100, sulfuration time is shortened, natural vulcanized rubber crosslinking density and mechanical properties are improved and reasonable utilization and saving of a zinc ore resource are realized.
Description
Technical field
The present invention relates to a kind of method improving zinc oxide sulfurate activity, belong to natural rubber processing technique field.
Background technology
The production of natural rubber products generally comprises the processing steps such as mixing, calendering, laminating, shaping, sizing, sulfuration, and wherein, the various performance and used lifes of sulfuration process remarkably influenced rubber item are one of processing steps of rubber item production most critical.The sulfuration of natural rubber is that Sulfur makes rubber molecular chain be cross-linked by monosulfidic bond or polysulfidic bond, forms the process of network structure, in vulcanization system design, must add promotor and promoting agent zinc oxide, to shorten curing time, improve the mechanical property of goods.
Zinc oxide is as the modal vulcanization leveller of caoutchouc vulcanization, be widely used in the production of natural rubber products, because caoutchouc vulcanization process is very complicated, up to now, still cannot specify promotor and by what mode, zinc oxide promotes that Sulfur is cross-linked natural rubber molecular chain, how particularly requisite zinc oxide in vulcanization system, play a role still unclear in caoutchouc vulcanization process.In some bibliographical informations, think that the effect of zinc oxide may be embodied in: (1), under stearic effect, generates zinc salt with booster response, improve the solubleness of promotor in rubber matrix; (2) by amine or lipid acid and promotor complexing, form the complex compound centered by zinc, impel the Sulfur molecule activation of octatomic ring; (3) by absorption induction, the reactive behavior of natural rubber molecular chain is improved.
Above-mentioned deduction lacks sufficient experimental evidence all the time, owing to lacking clear understanding to zinc oxide role in caoutchouc vulcanization process, causes reasonably to use zinc oxide in production application.At present, in the vulcanization system of nearly all natural rubber products, the consumption of zinc oxide is apparently higher than Sulfur and promotor, even up to 5 times in some systems, (ratio, zinc oxide dosage is higher), according to stoichiometry, most zinc oxide seems and has neither part nor lot in vulcanization reaction.Because the ratio of zinc oxide is great, fill more zinc oxide in formula and the density of sizing material certainly will be caused to increase, the heat-dissipating of sizing material is large, wear resisting property is poor, to work-ing life of goods and energy consumption all very unfavorable.
In addition, zinc oxide belongs to resource constraint product, and excessive use zinc oxide also must cause the wasting of resources.Although the explored zinc ore reserves of China more than 9,000 ten thousand tons, occupy third place in the world, the annual zinc oxide consumption of China reaches 1,200,000 tons, and wherein 1/3rd for rubber industry, and according to the estimation of current consumption, 10 Nian Hou China zinc resources are by approach exhaustion.Therefore, save zinc oxide and become one of key issue of the industry-by-industry urgent need solution comprising rubber industry.
At present, rubber industry field, mainly through reducing zinc oxide particles size, increases specific surface area, improves the activity of zinc oxide, to reduce the consumption of zinc oxide.Wherein, using wider is nano zine oxide, and it is mainly prepared by techniques such as chemical vapor infiltration, solvent-thermal method, electrochemical deposition method and sol-gel process.Because the particle diameter of nano zine oxide reduces, its surface tissue there occurs change, shows small-size effect, interfacial effect and quantum tunneling effect, therefore can significantly improve the strength and extension property of rubber, heat-dissipating in reducing, and formula consumption can reduce to 2 ~ 3 parts from original 5 parts.But, adding of nano zine oxide, disadvantageous effect is brought to the sulfuration of rubber, calendering process, shows: one is produce retarding action to the sulfuration of rubber; Two is the increases along with zinc oxide specific surface area, and interfacial effect is corresponding increase also, causes zinc oxide easily to be reunited in rubber matrix, difficult dispersion; In addition, due to nano zine oxide complicated process of preparation, production cost is higher, is also unfavorable for that it is applied.
Therefore, be necessary to invent a kind of method improving common zinc oxide sulfurate activity, effectively can not only promote zinc oxide in the activity participating in vulcanization reaction, can also significantly reduce zinc oxide adds number in formula simultaneously, its number in formula is down to less than 2 parts, thus reaches the object of the zinc resource of Appropriate application and saving China.
At present, rubber industry also increases the research of this respect.Chinese invention " vulcanization acceralator for rare earth rubber and preparation method thereof ", application number 97105303.0, disclose a kind of rare earth and organic group chemical combination, develop vulcanization rate fast, the Novel vulcanization accelerator of excellent property, but use this Novel vulcanization accelerator, the consumption of zinc oxide at least also needs more than 5 parts.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method improving common zinc oxide sulfurate activity is provided, present method has abundant energy level, 5d unoccupied orbital and 4f transition of electron characteristic based on rare earth element, the features such as easy generation polyelectrons configuration, by rare earth oxide, common zinc oxide is adulterated, utilize some characteristics that rare earth is intrinsic, improve zinc oxide particles crystal habit structure and ion surface chemical property etc., improve the activity that zinc oxide participates in vulcanization reaction, reduce the usage quantity of zinc oxide in rubber compounding.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
Improve a method for zinc oxide sulfurate activity, comprise the steps:
(1) mixing of materials: in 100 parts of common zinc oxides, adds the rare earth oxide of 0.5 ~ 10 part, mixes;
(2) ball milling: be put in by mixture with the speed ball grinding stirring of 250 ~ 300r/min in planetary type ball-milling instrument PM100, Ball-milling Time is 2 ~ 8 hours, then takes out material for subsequent use;
(3) high temperature sintering: the material that ball milling is good is placed in retort furnace high temperature sintering 1 ~ 1.5 hour, the temperature of sintering is 150 ~ 800 DEG C, namely obtains the product that can improve zinc oxide sulfurate activity---the zinc oxide of doped with rare-earth oxide.
Described rare earth oxide is the one of lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide.
Described common zinc oxide is that rubber industry produces conventional indirect process zinc oxide, purity 99.7%.
The invention has the beneficial effects as follows: the method for raising common zinc oxide sulfurate activity of the present invention, simple to operate, successful, in the cross-linking density situation guaranteeing vulcanized rubber, the vulcanization rate of natural rubber can be significantly improved, reduce the usage quantity of zinc oxide in formula, minimum use number can be down to 2 parts from original 5 parts.
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention;
Embodiment 1
Improve a method for zinc oxide sulfurate activity, comprise the steps:
Take 2.5 parts of rare earth lanthanum oxides, 100 parts of common zinc oxides, ball milling 2 hours in planetary type ball-milling instrument PM100, then at 150 DEG C of temperature, 1 hour is sintered, carry out mixing and sulfuration by following rubber compounding, and carry out the test of rubber unvulcanizate vulcanization characteristics and mechanical property of vulcanized rubber: natural rubber 100 parts, stearic acid 1 part, 2.5 parts, zinc oxide, promotor 1.4 parts, 2 parts, sulphur, filler 30 parts.
Embodiment 2
Improve a method for zinc oxide sulfurate activity, comprise the steps:
Take 5 parts of rare earth cerium oxides, 100 parts of common zinc oxides, ball milling 4 hours in planetary type ball-milling instrument PM100, then at 300 DEG C of temperature, 1 hour is sintered, carry out mixing and sulfuration by following rubber compounding, and carry out the test of rubber unvulcanizate vulcanization characteristics and mechanical property of vulcanized rubber: natural rubber 100 parts, stearic acid 1 part, 2.5 parts, zinc oxide, promotor 1.4 parts, 2 parts, sulphur, filler 30 parts.
Embodiment 3
Improve a method for zinc oxide sulfurate activity, comprise the steps:
Take 7.5 parts of rare earth cerium oxides, 100 parts of common zinc oxides, ball milling 6 hours in planetary type ball-milling instrument PM100, then at 600 DEG C of temperature, 1 hour is sintered, carry out mixing and sulfuration by following rubber compounding, and carry out the test of rubber unvulcanizate vulcanization characteristics and mechanical property of vulcanized rubber: natural rubber 100 parts, stearic acid 1 part, 2.5 parts, zinc oxide, promotor 1.4 parts, 2 parts, sulphur, filler 30 parts.
Embodiment 4
Improve a method for zinc oxide sulfurate activity, comprise the steps:
Take 10 parts of rare earth lanthanum oxides, 100 parts of common zinc oxides, ball milling 4 hours in planetary type ball-milling instrument PM100, then at 800 DEG C of temperature, 1 hour is sintered, carry out mixing and sulfuration by following rubber compounding, and carry out the test of rubber unvulcanizate vulcanization characteristics and mechanical property of vulcanized rubber: natural rubber 100 parts, stearic acid 1 part, 2.5 parts, zinc oxide, promotor 1.4 parts, 2 parts, sulphur, filler 30 parts.
The different doping process of table 1 is on the impact of caoutchouc vulcanization characteristic
| Project | Control sample | Example 1 | Example 2 | Example 3 | Example 4 |
| T 10/min | 2.44 | 2.42 | 2.38 | 2.26 | 2.19 |
| T 90/min | 5.19 | 5.14 | 4.75 | 4.51 | 4.37 |
| M L/dN.m | 0.32 | 0.33 | 0.57 | 0.63 | 0.65 |
| M H/dN.m | 8.53 | 8.62 | 8.73 | 9.60 | 9.89 |
The formula mechanical property of vulcanized rubber of the zinc oxide of the different doping process of table 2
| Project | Control sample | Example 1 | Example 2 | Example 3 | Example 4 |
| Tensile yield | 694.00 | 636.64 | 645.20 | 649.64 | 666.80 |
| Tensile strength | 30.72 | 25.68 | 27.52 | 29.30 | 31.79 |
| Tear strength | 30.56 | 32.34 | 31.93 | 35.14 | 32.94 |
| 500% stretches surely | 10.00 | 11.32 | 11.50 | 12.20 | 11.67 |
Can be found out by above embodiment, in zinc oxide after rare earth doped oxide compound, reduce the usage quantity of zinc oxide in rubber compounding, curing time can not only be shortened, improve vulcanization rate, cross-linking density and the mechanical property of natural rubber vulcanized rubber can also be improved, Be very effective.
Claims (4)
1. improve a method for zinc oxide sulfurate activity, it is characterized in that: comprise the steps:
(1) mixing of materials: in 100 parts of common zinc oxides, adds the rare earth oxide of 0.5 ~ 10 part, mixes;
(2) ball milling: mixture to be put in ball milling instrument with the speed ball grinding stirring of 250 ~ 300r/min, to take out material after ball milling for subsequent use;
(3) high temperature sintering: the material that ball milling is good is placed in retort furnace high temperature sintering 1 ~ 1.5 hour, namely obtains the product that can improve zinc oxide sulfurate activity---the zinc oxide of doped with rare-earth oxide.
2. a kind of method improving zinc oxide sulfurate activity according to claim 1, is characterized in that: the rare earth oxide described in step (1) is the one of lanthanum trioxide, cerium oxide, rubidium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide.
3. a kind of method improving zinc oxide sulfurate activity according to claim 1, is characterized in that: the described ball milling instrument of step (2) adopts planetary type ball-milling instrument PM100, and Ball-milling Time is 2 ~ 8 hours.
4. a kind of method improving zinc oxide sulfurate activity according to claim 1, is characterized in that: the temperature of step (3) described high temperature sintering is 150 ~ 800 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903455A (en) * | 2017-11-08 | 2018-04-13 | 广西融辰建设工程有限公司 | A kind of radiation resistant rubber and preparation method thereof |
| CN109133151A (en) * | 2018-10-31 | 2019-01-04 | 江苏伊顿航天材料股份有限公司 | A method of preparing sealing ring zinc oxide |
| CN109251364A (en) * | 2018-08-14 | 2019-01-22 | 含山县胜发塑料制品有限公司 | Heat stabilizer is used in a kind of production and processing of PVC plastic |
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| CN1219553A (en) * | 1997-06-12 | 1999-06-16 | 江西师范大学 | Vulcanization acceralator for rare earth rubber and its preparation method |
| CN101962452A (en) * | 2010-09-26 | 2011-02-02 | 华南理工大学 | Rare earth rubber vulcanization accelerator, and preparation method and application thereof |
| CN103537664A (en) * | 2013-10-11 | 2014-01-29 | 芜湖市鸿坤汽车零部件有限公司 | Powder metallurgy composite material and manufacturing method thereof |
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Patent Citations (3)
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| CN1219553A (en) * | 1997-06-12 | 1999-06-16 | 江西师范大学 | Vulcanization acceralator for rare earth rubber and its preparation method |
| CN101962452A (en) * | 2010-09-26 | 2011-02-02 | 华南理工大学 | Rare earth rubber vulcanization accelerator, and preparation method and application thereof |
| CN103537664A (en) * | 2013-10-11 | 2014-01-29 | 芜湖市鸿坤汽车零部件有限公司 | Powder metallurgy composite material and manufacturing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903455A (en) * | 2017-11-08 | 2018-04-13 | 广西融辰建设工程有限公司 | A kind of radiation resistant rubber and preparation method thereof |
| CN109251364A (en) * | 2018-08-14 | 2019-01-22 | 含山县胜发塑料制品有限公司 | Heat stabilizer is used in a kind of production and processing of PVC plastic |
| CN109133151A (en) * | 2018-10-31 | 2019-01-04 | 江苏伊顿航天材料股份有限公司 | A method of preparing sealing ring zinc oxide |
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