CN104356424A - Preparation method of low-zinc vulcanizing activator - Google Patents
Preparation method of low-zinc vulcanizing activator Download PDFInfo
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- CN104356424A CN104356424A CN201410687791.XA CN201410687791A CN104356424A CN 104356424 A CN104356424 A CN 104356424A CN 201410687791 A CN201410687791 A CN 201410687791A CN 104356424 A CN104356424 A CN 104356424A
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Abstract
The invention discloses a preparation method of a low-zinc vulcanizing activator. The method comprises the following steps: adding a water-insoluble inert filler and zinc carbonate to water, and stirring so that the inert filler fully contacts the zinc carbonate; stirring and then standing; removing supernate; and burning the residues until no gas is generated, so as to obtain the low-zinc vulcanizing activator. The preparation method of the low-zinc vulcanizing activator disclosed by the invention is simple and fast, is free of pollution, energy-saving and environmentally friendly, and meets the national policy requirements of green chemical industry and clean production; water can be recycled in the preparation method; and the prepared low-zinc vulcanizing activator is a nanometer zinc oxide/inert filler mixture. The low-zinc vulcanizing activator has the characteristics that nanometer zinc oxide is evenly loaded on the surface of the inert filler; an application test in rubber shows that the low-zinc vulcanizing activator is equivalent to the same mass of nanometer zinc oxide in application effect; and the targets of reducing nanometer zinc oxide consumption and lowering zinc pollution are achieved.
Description
Technical field
The present invention relates to the preparation method of a kind of rubber with low zinc vulcanization leveller, belong to technical field of fine.
Background technology
In the sulfidization molding process of rubber, except will adding vulcanizing agent, vulcanization accelerator, scorch retarder, for improving vulcanization rate, generally also need to add vulcanization leveller, general conventional vulcanization leveller is zinc oxide, stearic acid etc., wherein zinc oxide not only can accelerate vulcanization rate, can also promote the cross-linking density of rubber, thus play strengthening action.For promoting the use properties of zinc oxide in rubber, use now more zinc oxide to be nano zine oxide, particle is thin, active high, very large at rubber industry consumption.But nano zine oxide due to particle thin, specific surface area is large, easily plays electrostatic, especially easily assembles conglomeration, particularly in compounding rubber, easily causes dispersion uneven, thus affects properties of rubber.In addition, nano zine oxide can along with the wearing and tearing of the rubber items such as tire, discarded and inevitably enter in water body, soil, cause zinc pollution, larger pollution hidden trouble is caused to ecotope, particularly larger to the procreative effect of animal, so rubber industry is also devoted to the new low zinc of exploitation or is carried out alternative nano zine oxide without the activating agent for rubber of zinc always, in the hope of reducing or stopping zinc pollution.
It take oyster shell whiting as the preparation method of the nano zine oxide of carrier that patent CN101352676A discloses a kind of, by soluble zinc salt wiring solution-forming, then oyster shell whiting is impregnated in solution, make zinc salts precipitate in oyster shell whiting by sodium hydroxide adjust ph, formed the nano zine oxide loaded in oyster shell whiting by calcining.Nano zine oxide loads in oyster shell whiting by the method, reduce the consumption of nano zine oxide in rubber, it also avoid the reunion of nano zine oxide, but the waste water containing sodium salt can be produced in zinc salts precipitate to the process of oyster shell whiting, environment-friendly type is poor, adds the cost of wastewater treatment.
Patent CN102382489A discloses a kind of method of method for preparing low-zinc vulcanized active agents by active carrier method, the method take clay as carrier, by organic modifiers, modification is carried out to clay, improve the charge capacity of clay to nano zine oxide, nano zine oxide is also by being impregnated into by clay in soluble Zn salt brine solution, then regulate pH by zinc salts precipitate, the method forming nano zine oxide finally by calcining obtains, can brine waste be produced equally, there is the problem that environment-friendly type is poor, cost for wastewater treatment is high.
Use soluble zinc salt as zinc source in prior art, the impact of granularity on performance about inert filler is not studied, and the granularity of each inert filler is all adopt the granularity (granularity that inert filler generally uses is 40-100 order) generally used.The present invention with inert filler and insoluble zinc carbonate for raw material, and the granularity of inert filler is studied, find through research, the granularity of inert filler is greater than 200 orders (such as 200-1200 order), most preferably be greater than 600 orders (such as 600-1200 order), the most preferably low zinc vulcanization leveller best results during 800-1200 order.The best results when granularity of zinc carbonate is 600-800 order.Select the inert filler of suitable particle size and zinc carbonate also can reduce the usage quantity of nano zine oxide.
In above-mentioned preparation method, water-fast inert filler and zinc carbonate are uniformly mixed at 40-50 DEG C of temperature.
In above-mentioned preparation method, water-fast inert filler and zinc carbonate mix under the stirring velocity of 120-150 r/min, preferred 130r/min.Under this stirring velocity, stir 2-3h and them can be made fully to contact.
In above-mentioned preparation method, water-fast inert filler and zinc carbonate are added to the water, and the consumption of water meets both dispersed.
In above-mentioned preparation method, calcining temperature is 550-600 DEG C.
The present invention has the following advantages:
1, the present invention's low zinc vulcanization leveller preparation method is simple and direct, water reusable edible, and pollution-free, energy-conserving and environment-protective, meet the policy requirements of national green chemical industry, cleanly production.
2, due to the existence of inert filler, nano zine oxide is conglomeration not easily, is very easy to dispersion, thus improves the use properties of zinc oxide in rubber.
3, obtained low zinc vulcanization leveller feature is nano zine oxide/inert filler mixture that nano zine oxide uniform loading is formed on inert filler surface, found by application test in rubber, low zinc vulcanization leveller containing 70% nano zine oxide with etc. the nano zine oxide effect of quality suitable, zinc consumption reduces 30%, reaches the object reducing nano zine oxide consumption, reduce zinc pollution.
Summary of the invention
The object of this invention is to provide a kind of preparation method of low zinc vulcanization leveller, the method is simple and easy to do, and pollution-free, energy-conserving and environment-protective, cost is low.
The concrete technical scheme of the present invention is as follows:
A preparation method for low zinc vulcanization leveller, step comprises: water-fast inert filler and zinc carbonate are added to the water, and makes them fully contact by stirring; Leave standstill after stirring, removing supernatant liquor, is fired to residuum till no longer producing gas, obtains low zinc vulcanization leveller.
The present invention adopts insoluble zinc carbonate as zinc source, with the inert filler with microvoid structure for carrier, finds that zinc carbonate is easy to when fully contacting with inert filler be attached to inert filler surface through test.Stir completely and by inert filler and zinc carbonate removing, not containing inorganic salt in remaining filtrate, can be reused, and can not exhaust emission be caused by filtration.
In above-mentioned preparation method, zinc carbonate in filter residue can be decomposed into nano zine oxide and carbonic acid gas when calcining, and inert filler can not change, the nano zine oxide be decomposed to form after having calcined can be dispersed in inert filler surface, form nano zine oxide/inert filler mixture, be low zinc vulcanization leveller by inert filler and load at the mixture that the nano zine oxide on inert filler surface is formed.
In above-mentioned preparation method, in the total mass of water-fast inert filler and zinc carbonate for 1, water-fast inert filler accounts for the 20-50% of total mass.
In above-mentioned preparation method, described water-fast inert filler is one or more in calcium carbonate, kaolin and activated clay.
embodiment
According to specific embodiment, the present invention will be further elaborated below.
In following embodiment, in low zinc vulcanization leveller, nano zine oxide cubage method is: (m1 × 81/125)/(m1 × 81/125+m2).Wherein: m1 is zinc carbonate quality, m2 is inert filler quality.
embodiment 1
Get 1200 object calcium carbonate powders 110g, 800 object zinc carbonate powder 400g, add in 2000mL water, at 40 DEG C, 130r/min stirring velocity stirs 120min, stir postprecipitation 30min, remove most of water, residuum adds in mini type high temperature rotary kiln, control temperature 550-600 DEG C, after calcination 2h, no longer produce gas, obtain shell core formula low zinc vulcanization activator 365g, calculating is learnt, nano oxidized Zn content is about 70.2%.
embodiment 2
Low zinc vulcanization leveller is prepared according to the method for embodiment 1, unlike: the granularity of calcium carbonate powders used is 800 orders.Final gained shell core formula low zinc vulcanization activator 365g, as calculated, nano oxidized Zn content is 70.2%.
embodiment 3
Low zinc vulcanization leveller is prepared according to the method for embodiment 1, unlike: the granularity of calcium carbonate powders used is 300 orders.Final gained shell core formula low zinc vulcanization activator 365g, as calculated, nano oxidized Zn content is 70.2%.
embodiment 4
Low zinc vulcanization leveller is prepared according to the method for embodiment 1, unlike: the granularity of calcium carbonate powders used is 600 orders.Final gained shell core formula low zinc vulcanization activator 365g, as calculated, nano oxidized Zn content is 70.2%.
Embodiment 5
Low zinc vulcanization leveller is prepared according to the method for embodiment 1, unlike: the granularity of calcium carbonate powders used is 1400 orders.Final gained shell core formula low zinc vulcanization activator 365g, as calculated, nano oxidized Zn content is 70.2%.
embodiment 6
Get 600 object activated clay powder 170g, 800 object zinc carbonate powder 400g, add in 2000mL water, at 40 DEG C, 130r/min stirring velocity stirs 120min, precipitation 30min, remove most of water, residuum adds in mini type high temperature rotary kiln, control temperature 550-600 DEG C, after calcination 2h, no longer produce gas, obtain shell core formula low zinc activator 426g, calculating is learnt, nano oxidized Zn content is about 60.4%.
embodiment 7
Get 1000 object activated clay 266.7g, 600 object zinc carbonate powder 400g, add in 2000mL water, at 50 DEG C, 150r/min stirring velocity stirs 120min, stir postprecipitation 30min, remove most of water, residuum adds in mini type high temperature rotary kiln, control temperature 550-600 DEG C, after calcination 2h, no longer produce gas, obtain shell core formula low zinc vulcanization activator 525.5g, calculating is learnt, nano oxidized Zn content 49.3%.
embodiment 8
Get 1000 object kaolin 400g, 600 object zinc carbonate powder 400g, add in 2000mL water, at 50 DEG C, 120r/min stirring velocity stirs 180min, stir postprecipitation 30min, remove most of water, residuum adds in mini type high temperature rotary kiln, control temperature 550-600 DEG C, after calcination 2h, no longer produce gas, obtain shell core formula low zinc vulcanization activator 659g, calculating is learnt, nano oxidized Zn content 39.3%.
embodiment 9
Low zinc vulcanization leveller is prepared according to the method for embodiment 8, unlike: kaolinic granularity is 200 orders.Final gained shell core formula low zinc vulcanization activator 658g, calculating is learnt, nano oxidized Zn content 39.3%.
comparative example
Get 800 object zinc acetate 400g, add in 2000mL water, be stirred to dissolving, then 1200 object calcium carbonate powders 110g are added in the aqueous solution, be uniformly mixed, add sodium hydroxide solution again and regulate pH to 8, at 40 DEG C, 130r/min stirring velocity stirs 120min, stirs postprecipitation 30min, removes most of water, residuum adds in mini type high temperature rotary kiln, control temperature 550-600 DEG C, calcination 3-4h, obtain shell core formula low zinc vulcanization activator 280g, calculating is learnt, nano oxidized Zn content is about 61.6%.
In order to embody advantage of the present invention, used in TBR tire tread material by the low zinc vulcanization leveller of above-described embodiment and comparative example gained, to evaluate its effect, method is as follows:
1, all-steel radial tyre tread glue formula with parts by weight is: 5# natural rubber, 100 parts; Carbon black N234,45 parts; White carbon black, 15 parts; Rubber plastizing agent A, 2 parts; The low zinc vulcanization leveller of embodiment and comparative example or pure nano zine oxide, 3 parts; Stearic acid, 2 parts; Silane coupling agent si69,3 parts; Anti-aging agent RD, 1.5 parts; Antioxidant 4020,2 parts; Sulfur, 1.2 parts; Accelerant CZ, 1.5 parts.
2, tread rubber calendering process (according to above-mentioned tread glue formula Raw ratio): adopt two sections of calendering process to carry out mixing, one section mixing carries out in 1.5L Banbury mixer, and rotor speed is 80rmin
-1, order of addition(of ingredients) is: rubber → small powder → white carbon black, carbon black → binder removal (140 DEG C); Two-stage mixing carries out in XK-160 mill, and order of addition(of ingredients) is one section of rubber unvulcanizate → Sulfur, accelerant CZ → thin-pass 3 times → bottom sheet.
3, Tread Compound Property is as shown in table 1:
Note: (MH-ML) value can characterize the size of cross-linking density, guarantees the acquisition of physical properties; (t90-t10) can characterize the speed of vulcanization rate, numerical value is less, and vulcanization rate is faster.
4, conclusion
4.1 zinc oxide are main in rubber is used as vulcanization leveller, can not only accelerate vulcanization rate, can also promote the raising of rubber size density by adding zinc oxide.Can be found out by contrast, use the nano oxidized Zn content that obtains of the present invention be the low zinc vulcanization leveller of 70.2% compared with pure nano zine oxide, (MH-ML) value is slightly high or suitable, and vulcanization rate (t90-t10) numerical value is suitable.And when the calcium carbonate powders order number of the low zinc vulcanization leveller of preparation is at 800 ~ 1200 order, the cross-linking density of sizing material is maximum, and vulcanization rate is fast.Except the compression heat generation had advantageously of the low zinc promoting agent of 70.2 nano oxidized Zn content adopting the present invention to obtain reduces, other physical and mechanical propertiess of sizing material are suitable with pure nano zine oxide effect.
4.2 can be found out by the contrast between various embodiments of the present invention, the result of use of the low zinc vulcanization leveller that the nano oxidized Zn content of the present invention is high is better than the low low zinc vulcanization leveller of nano oxidized Zn content, and when nano oxidized Zn content reaches 70.2%, suitable with the result of use of pure nano zine oxide.
The similar nature of the low zinc vulcanization leveller of 4.3 use zinc carbonates and soluble zinc salt gained, does not have notable difference.The performance that when adopting varigrained inert filler, vulcanization leveller shows has certain difference, adopts the vulcanization leveller performance of preferred size better.This shows, the present invention is low, and zinc vulcanization leveller can replace nano zine oxide, both can reduce the content of zinc in sizing material, can reduce again the material cost of sizing material, and the performance of sizing material can not be a greater impact.
Claims (10)
1. a preparation method for low zinc vulcanization leveller, is characterized in that: water-fast inert filler and zinc carbonate are added to the water, and makes them fully contact by stirring; Leave standstill after stirring, removing supernatant liquor, is fired to residuum till no longer producing gas, obtains low zinc vulcanization leveller.
2. preparation method according to claim 1, is characterized in that: described low zinc vulcanization leveller is water-fast inert filler and the nano zine oxide of load on inert filler surface.
3. preparation method according to claim 1, is characterized in that: water-fast inert filler accounts for the 20-50% of water-fast inert filler and zinc carbonate total mass.
4. preparation method according to claim 1, is characterized in that: described water-fast inert filler is one or more in calcium carbonate, kaolin and activated clay.
5. preparation method according to claim 1, is characterized in that: described water-fast inert filler granularity is greater than 200 orders, is preferably greater than 600 orders, is more preferably 800-1200 order.
6. preparation method according to claim 1, is characterized in that: the granularity of zinc carbonate is 600-800 order.
7. preparation method according to claim 1, is characterized in that: water-fast inert filler and zinc carbonate are uniformly mixed at 40-50 DEG C of temperature.
8. preparation method according to claim 1, is characterized in that: stirring velocity is 120-150 r/min, preferred 130r/min.
9. preparation method according to claim 1, is characterized in that: churning time is 2-3h.
10. preparation method according to claim 1, is characterized in that: calcining temperature is 550-600 DEG C.
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Cited By (4)
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| CN107216501A (en) * | 2017-07-18 | 2017-09-29 | 利辛县正大化工原料有限公司 | The formula and preparation method of a kind of water base latices for transmission belt infantees soaking paste |
| CN108752651A (en) * | 2017-04-24 | 2018-11-06 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
| CN111607127A (en) * | 2020-06-09 | 2020-09-01 | 江西宝弘纳米科技有限公司 | Rubber vulcanization activator and preparation method and application thereof |
| CN115678317A (en) * | 2022-10-21 | 2023-02-03 | 科迈特新材料有限公司 | Preparation method and application of low-zinc composite vulcanization activator |
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| CN108752651A (en) * | 2017-04-24 | 2018-11-06 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
| CN108752651B (en) * | 2017-04-24 | 2022-02-18 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
| CN107216501A (en) * | 2017-07-18 | 2017-09-29 | 利辛县正大化工原料有限公司 | The formula and preparation method of a kind of water base latices for transmission belt infantees soaking paste |
| CN111607127A (en) * | 2020-06-09 | 2020-09-01 | 江西宝弘纳米科技有限公司 | Rubber vulcanization activator and preparation method and application thereof |
| CN115678317A (en) * | 2022-10-21 | 2023-02-03 | 科迈特新材料有限公司 | Preparation method and application of low-zinc composite vulcanization activator |
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