CN104356424B - A kind of preparation method of low zinc vulcanizing activator - Google Patents
A kind of preparation method of low zinc vulcanizing activator Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of low zinc vulcanizing activator, step includes：Inert filler and zinc carbonate not soluble in water are added to the water, them is fully contacted by stirring；Stood after stirring, remove supernatant, residue is fired to untill no longer producing gas, produce low zinc vulcanizing activator.The present invention is low, and zinc vulcanizing activator preparation method is simple and direct, water reusable edible, pollution-free, energy-conserving and environment-protective, meets the policy requirements of national green chemical industry, cleanly production.Obtained low zinc vulcanizing activator is nano zine oxide/inert filler mixture, it is characterized in that nano zine oxide is uniformly supported on inert filler surface, by in rubber application test find, the low zinc vulcanizing activator with etc. quality nano zine oxide application effect it is suitable, reached the purpose for reducing nano zine oxide dosage, reducing zinc pollution.
Description
Technical field
A kind of preparation method the present invention relates to rubber with low zinc vulcanizing activator, belongs to technical field of fine.
Background technology
During the sulfidization molding of rubber, in addition to vulcanizing agent to be added, vulcanization accelerator, antiscorching agent, to improve sulphur
Change speed, typically also need to add vulcanizing activator, typically conventional vulcanizing activator is zinc oxide, stearic acid etc., wherein oxygen
Curingprocess rate can not only be accelerated by changing zinc, the crosslink density of rubber can also be lifted, so as to play strengthening action.Aoxidized for lifting
Performance of the zinc in rubber, the use of more zinc oxide is nano zine oxide now, particle is thin, and activity is high, in rubber
Industry dosage is very big.But for nano zine oxide because particle is thin, specific surface area is big, easily plays electrostatic, it is particularly easy to assemble conglomeration, it is special
Be not in compounding rubber, easily cause it is scattered uneven, so as to influence properties of rubber.In addition, nano zine oxide can be with wheel
Wearing, discarding and inevitably enter in water body, soil for the rubbers such as tire, causes zinc pollution, ecological environment is caused
Larger pollution hidden trouble, it is particularly larger to the procreative effect of animal, so rubber industry is also directed to developing newly low always
Zinc or activating agent for rubber without zinc substitute nano zine oxide, in the hope of reducing or preventing zinc pollution.
Patent CN101352676A discloses a kind of preparation method using oyster shell whiting as the nano zine oxide of carrier, will be solvable
Property zinc salt wiring solution-forming, then oyster shell whiting is impregnated into solution, with sodium hydroxide regulation pH value make zinc salts precipitate to oyster shell whiting
In, form the nano zine oxide loaded in oyster shell whiting by calcining.This method loads to nano zine oxide in oyster shell whiting, drop
Low dosage of the nano zine oxide in rubber, it also avoid the reunion of nano zine oxide, but zinc salts precipitate is to oyster shell whiting
During can produce the waste water containing sodium salt, 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, this method with
Clay is carrier, and clay is modified by organic modifiers, improves load capacity of the clay to nano zine oxide, nano oxygen
It is also by the way that clay is impregnated into soluble Zn saline solution to change zinc, pH is then adjusted by zinc salts precipitate, finally by calcining
The method for forming nano zine oxide is made, and can equally produce brine waste, there is that environment-friendly type is poor, cost for wastewater treatment is high asks
Topic.
The content of the invention
It is an object of the invention to provide a kind of preparation method of low zinc vulcanizing activator, this method is simple and easy to do, pollution-free,
Energy-conserving and environment-protective, cost are low.
Concrete technical scheme of the present invention is as follows：
A kind of preparation method of low zinc vulcanizing activator, step include：Inert filler and zinc carbonate not soluble in water are added
Enter in water, them is fully contacted by stirring；Stood after stirring, remove supernatant, residue is fired to and no longer produces gas
Untill body, low zinc vulcanizing activator is produced.
The present invention uses insoluble zinc carbonate as zinc source, using the inert filler with microcellular structure as carrier, through experiment
It was found that zinc carbonate is easy to be attached to inert filler surface in the case where fully contacting with inert filler.Passed through after stirring completely
Filter can remove inert filler and zinc carbonate, be free of inorganic salts in remaining filtrate, can reuse, and will not the row of causing
Put pollution.
In above-mentioned preparation method, the zinc carbonate in filter residue can be decomposed into nano zine oxide and carbon dioxide in calcining, and
Inert filler will not change, and the nano zine oxide being decomposed to form after the completion of calcining can be dispersed in inert filler surface,
Nano zine oxide/inert filler compound is formed, is formed by inert filler and the nano zine oxide for being supported on inert filler surface
Compound be low zinc vulcanizing activator.
In above-mentioned preparation method, counted using the gross mass of inert filler and zinc carbonate not soluble in water as 1, not soluble in water is lazy
Property filler accounts for the 20-50% of gross mass.
In above-mentioned preparation method, the inert filler not soluble in water is one in calcium carbonate, kaolin and activated clay
Kind is several.
Using soluble zinc salt in the prior art, influence of the granularity to performance on inert filler is not ground as zinc source
Study carefully, the granularity of each inert filler is all using the granularity generally used（The granularity that inert filler generally uses is 40-100 mesh）.
The present invention is studied the granularity of inert filler using inert filler and insoluble zinc carbonate as raw material, by grinding
Study carefully discovery, the granularity of inert filler is more than 200 mesh（Such as 200-1200 mesh）, most preferably greater than 600 mesh（Such as 600-1200
Mesh）, the most preferably 800-1200 mesh when low zinc vulcanizing activator best results.The granularity of zinc carbonate is 600-800 mesh timeliness
Fruit is optimal.The inert filler of suitable particle size and zinc carbonate is selected also to reduce the usage amount of nano zine oxide.
In above-mentioned preparation method, inert filler not soluble in water and zinc carbonate are stirred mixing at a temperature of 40-50 DEG C.
In above-mentioned preparation method, inert filler not soluble in water and zinc carbonate are under 120-150 r/min mixing speed
Mixing, preferably 130r/min.Under this mixing speed, stirring 2-3h can be such that they fully contact.
In above-mentioned preparation method, inert filler not soluble in water and zinc carbonate are added to the water, the dosage of water meet by this two
Person is dispersed.
In above-mentioned preparation method, calcining heat is 550-600 DEG C.
The present invention has advantages below：
1st, the low zinc vulcanizing activator preparation method of the present invention is simple and direct, water reusable edible, pollution-free, energy-conserving and environment-protective, meets
The policy requirements of national green chemical industry, cleanly production.
2nd, due to the presence of inert filler, nano zine oxide not easy to knot groups, be very easy in rubber it is scattered, so as to be lifted
The performance of zinc oxide.
3rd, obtained low zinc vulcanizing activator feature is that nano zine oxide uniform load is received what inert filler surface was formed
Rice zinc oxide/inert filler compound, by rubber application test finds that low zinc containing 70% nano zine oxide vulcanizes
Activating agent with etc. quality nano zine oxide application effect it is suitable, zinc dosage reduces 30%, reached reduction nano zine oxide use
Amount, the purpose for reducing zinc pollution.
Embodiment
Below according to specific embodiment, the present invention will be further elaborated.
In following embodiments, nano zine oxide cubage method is in low zinc vulcanizing activator：(m1×81/125)/
(m1×81/125+m2).Wherein：M1 is zinc carbonate quality, and m2 is inert filler quality.
Embodiment 1
The calcium carbonate powder 110g of 1200 mesh, the zinc carbonate powder 400g of 800 mesh are taken, is added in 2000mL water, at 40 DEG C
130r/min mixing speeds stir 120min, and 30min is precipitated after stirring, remove most of water, and residue adds mini type high temperature and returned
In converter, control 550-600 DEG C of temperature, after calcination 2h, no longer produce gas, obtain the low zinc vulcanizing activator 365g of shell core formula,
Calculating learns that nano oxidized Zn content is about 70.2%.
Embodiment 2
Method according to embodiment 1 prepares low zinc vulcanizing activator, unlike：The granularity of calcium carbonate powder used is
800 mesh.The low zinc vulcanizing activator 365g of shell core formula obtained by final, is computed, and nano oxidized Zn content is 70.2%.
Embodiment 3
Method according to embodiment 1 prepares low zinc vulcanizing activator, unlike：The granularity of calcium carbonate powder used is
300 mesh.The low zinc vulcanizing activator 365g of shell core formula obtained by final, is computed, and nano oxidized Zn content is 70.2%.
Embodiment 4
Method according to embodiment 1 prepares low zinc vulcanizing activator, unlike：The granularity of calcium carbonate powder used is
600 mesh.The low zinc vulcanizing activator 365g of shell core formula obtained by final, is computed, and nano oxidized Zn content is 70.2%.
Embodiment 5
Method according to embodiment 1 prepares low zinc vulcanizing activator, unlike：The granularity of calcium carbonate powder used is
1400 mesh.The low zinc vulcanizing activator 365g of shell core formula obtained by final, is computed, and nano oxidized Zn content is 70.2%.
Embodiment 6
The activated clay powder 170g of 600 mesh, the zinc carbonate powder 400g of 800 mesh are taken, is added in 2000mL water, 40 DEG C
Lower 130r/min mixing speeds stir 120min, precipitate 30min, remove most of water, and residue adds mini type high temperature rotary furnace
In, control 550-600 DEG C of temperature, after calcination 2h, no longer produce gas, obtain the low zinc activator 426g of shell core formula, calculating is learnt,
Nano oxidized Zn content is about 60.4%.
Embodiment 7
The activated clay 266.7g of 1000 mesh, the zinc carbonate powder 400g of 600 mesh are taken, is added in 2000mL water, at 50 DEG C
150r/min mixing speeds stir 120min, and 30min is precipitated after stirring, remove most of water, and residue adds mini type high temperature and returned
In converter, control 550-600 DEG C of temperature, after calcination 2h, no longer produce gas, obtain the low zinc vulcanizing activator of shell core formula
525.5g, calculating learns, nano oxidized Zn content 49.3%.
Embodiment 8
The kaolin 400g of 1000 mesh, the zinc carbonate powder 400g of 600 mesh are taken, is added in 2000mL water, 120r/ at 50 DEG C
Min mixing speeds stir 180min, and 30min is precipitated after stirring, remove most of water, and residue adds mini type high temperature rotary furnace
In, control 550-600 DEG C of temperature, after calcination 2h, no longer produce gas, obtain the low zinc vulcanizing activator 659g of shell core formula, calculate
Learn, nano oxidized Zn content 39.3%.
Embodiment 9
Method according to embodiment 8 prepares low zinc vulcanizing activator, unlike：Kaolinic granularity is 200 mesh.Finally
The low zinc vulcanizing activator 658g of gained shell core formula, calculating learns, nano oxidized Zn content 39.3%.
Comparative example
The zinc acetate 400g of 800 mesh is taken, is added in 2000mL water, stirring is to dissolving, then by the Paris white of 1200 mesh
Last 110g is added in the aqueous solution, is stirred, and is added sodium hydroxide solution and is adjusted pH to 8,130r/min stirrings are fast at 40 DEG C
Degree stirring 120min, 30min is precipitated after stirring, removes most of water, and residue is added in mini type high temperature rotary furnace, controls temperature
550-600 DEG C, calcination 3-4h, the low zinc vulcanizing activator 280g of shell core formula is obtained, calculating learns that nano oxidized Zn content is about
61.6%。
In order to embody the advantage of the present invention, the low zinc vulcanizing activator obtained by above-described embodiment and comparative example is carried in all steel
Used in baryon conductivity of radial tire tread material, to evaluate its application effect, method is as follows：
1st, all-steel radial tyre tread glue formula is in parts by weight：5# natural rubbers, 100 parts；Carbon black N234,45
Part；White carbon, 15 parts；Rubber plastizing agent A, 2 parts；Embodiment and the low zinc vulcanizing activator of comparative example or pure nano zine oxide, 3
Part；Stearic acid, 2 parts；Silane coupler si69,3 parts；Anti-aging agent RD, 1.5 parts；Antioxidant 4020,2 parts；Sulfur, 1.2 parts；Promote
Enter agent CZ, 1.5 parts.
2nd, tread rubber calendering process（According to material rate in above-mentioned tread glue formula）：Mixed using two sections of calendering process
Refining, one section of mixing are carried out in 1.5L banburies, rotor speed 80rmin-1, charging sequence is：Rubber → small powder → hard charcoal
Black, carbon black → dumping（140℃）；Two-stage mixing is carried out in XK-160 mills, charging sequence be one section of elastomeric compound → Sulfur,
Accelerant CZ → thin logical 3 times → bottom sheet.
3rd, Tread Compound Property is as shown in table 1：
Note：（MH-ML）Value can characterize the size of crosslink density, it is ensured that the acquisition of physical properties；(t90-t10) can table
The speed of curingprocess rate is levied, numerical value is smaller, and curingprocess rate is faster.
4th, conclusion
4.1 zinc oxide are mainly used as vulcanizing activator in rubber, can not only accelerate curingprocess rate by adding zinc oxide,
The raising of rubber size density can also be promoted.By contrast as can be seen that being using nano oxidized Zn content produced by the present invention
70.2% low zinc vulcanizing activator compared with pure nano zine oxide,（MH-ML）It is worth slightly higher or suitable, curingprocess rate（t90-
t10）Numerical value is suitable.And when preparing the calcium carbonate powder mesh number of low zinc vulcanizing activator in 800 ~ 1200 mesh, the crosslinking of sizing material
Density is maximum, and curingprocess rate is fast.Except having for the low zinc activating agent using produced by the present invention 70.2 nano oxidized Zn contents
Outside compression heat generation advantageously reduces, other physical and mechanical properties of sizing material are suitable with pure nano zine oxide effect.
4.2 can be seen that the high low zinc of the nano oxidized Zn content of the present invention by the contrast between various embodiments of the present invention
The using effect of vulcanizing activator is better than the low low zinc vulcanizing activator of nano oxidized Zn content, and works as nano oxidized Zn content
It is suitable with the using effect of pure nano zine oxide when reaching 70.2%.
4.3 use the similar nature of zinc carbonate and the low zinc vulcanizing activator obtained by soluble zinc salt, without notable difference.
The performance shown using vulcanizing activator during varigrained inert filler has certain difference, using the sulphur of preferred size
Change activating agent performance more preferably.It can thus be seen that the low zinc vulcanizing activator of the present invention can replace nano zine oxide, can both drop
The content of zinc in low sizing material, the cost of raw material of sizing material can be reduced again, and the performance of sizing material will not be a greater impact.
Claims (5)
1. a kind of preparation method of low zinc vulcanizing activator, it is characterized in that：Inert filler not soluble in water and zinc carbonate are distinguished
It is added to the water, them is fully contacted by stirring；Stood after stirring, remove supernatant, residue is fired to and no longer produced
Untill gas, low zinc vulcanizing activator is produced；
The inert filler not soluble in water is calcium carbonate, and inert filler granularity not soluble in water is 300-1400 mesh, zinc carbonate
Granularity be 600-800 mesh；
Inert filler not soluble in water accounts for the 11/51 of inert filler not soluble in water and zinc carbonate gross mass；
Inert filler not soluble in water and zinc carbonate are stirred mixing at a temperature of 40-50 DEG C, and mixing speed is 130 r/
Min, mixing time 2-3h.
2. preparation method according to claim 1, it is characterized in that：The low zinc vulcanizing activator is inertia not soluble in water
Filler and the nano zine oxide for being supported on inert filler surface.
3. preparation method according to claim 1, it is characterized in that：The granularity of the inert filler not soluble in water is more than
600 mesh.
4. preparation method according to claim 3, it is characterized in that：The granularity of the inert filler not soluble in water is 800-
1200 mesh.
5. preparation method according to claim 1, it is characterized in that：Calcining heat is 550-600 DEG C.
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| JP6926629B2 (en) * | 2017-04-24 | 2021-08-25 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tires |
| 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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| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN1994892A (en) * | 2006-11-27 | 2007-07-11 | 华南理工大学 | Microwave method for preparing nanometer zinc oxide |
| CN102898681A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Loaded type nano-zinc oxide composite material |
| CN103360628A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof |
| CN103818945A (en) * | 2013-11-15 | 2014-05-28 | 洛阳市蓝天化工科技有限公司 | Production method of efficient zinc oxide |
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Patent Citations (5)
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|---|---|---|---|---|
| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN1994892A (en) * | 2006-11-27 | 2007-07-11 | 华南理工大学 | Microwave method for preparing nanometer zinc oxide |
| CN102898681A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Loaded type nano-zinc oxide composite material |
| CN103360628A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof |
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