CN109233035A - A kind of rubber anti-recovery agent and its new synthetic method that partial size is 40-100 μm - Google Patents
A kind of rubber anti-recovery agent and its new synthetic method that partial size is 40-100 μm Download PDFInfo
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- CN109233035A CN109233035A CN201810962402.8A CN201810962402A CN109233035A CN 109233035 A CN109233035 A CN 109233035A CN 201810962402 A CN201810962402 A CN 201810962402A CN 109233035 A CN109233035 A CN 109233035A
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- sulphur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms
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Abstract
The present invention provides rubber anti-recovery agents and its new synthetic method that a kind of partial size is 40-100 μm, its synthesis step includes: first using green synthesis process water-soluble fluorine room temperature synthetic intermediate 1 under the action of phase transfer catalyst, bis- (the N of 6-, one sulphur of N '-bisbenzothiazole carbamyl)-hexane, obtained intermediate and sulfur reaction obtains first product 1, bis- (the N of 6-, two sulphur of N '-bisbenzothiazole carbamyl)-hexane, first product obtains 1 through recrystallization purifying process, bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane sterlings of 6-.Synthetic method solvent of the present invention can not generate waste water with recovery, and environmental protection and economy, the reaction time is short, and product purity is high, and high production efficiency, synthesis technology is simple, and low energy consumption；It prepares that rubber anti-recovery agent product granularity is big and particle diameter distribution is narrow, there is good processing performance.
Description
Technical field
The present invention relates to rubber processing aids synthesis technology field, specifically a kind of rubber anti-recovery agent
New synthetic method.
Background technique
1,6- bis- (N, N '-two sulphur of bisbenzothiazole carbamyl)-hexanes are that a kind of new and effective composite sulfur resisting reverts
Agent, anti-recovery mechanism: the sulphur sulfur bonds in its molecular structure during rubber vulcanization, intermediate C6 aliphatic chain together with
The sulphur atom at its both ends is connected in rubber molecule together, and the bond energy of carbon-carbon bond is greater than the sulphur that sulfur cross-linking is formed in C6 aliphatic chain
The bond energy of sulfide linkage, so that more stable vulcanization crosslinking network is formed, so that vulcanizate will not in production process and use process
Recovery phenomenon occurs, keeps preferable mechanical property and dynamic property.
The preparation method of dithiol derivatives is reported in patent CN 100522941C, which uses hexa-methylene-
1,6- bis- sodothiols and dibenzyl aminodithioformic acid sodium are that raw material passes through with water/toluene as reaction dissolvent
Investment sodium bicarbonate adjusts the pH value of reaction system, synthetic reaction finish after through the post-processings list such as extraction, reduced pressure, crystallization
Atom operation obtains product, which has the disadvantage in that 1) mass-transfer efficiency is lower in heterogeneous system water/toluene, leads
Cause reaction rate slower, industrial production campaign is longer, and Product industrialization production capacity is lower；2) a large amount of alkaline waste waters are generated (containing a small amount of
Organic solvent toluene), COD COD higher, i.e. biochemical treatment higher cost.
Chinese patent CN105503677B discloses a kind of environmentally friendly, (N, N- dibenzyl ammonia of high performance vulcanization crosslinking agent 1,6- bis-
Two sulphur of base formyl) hexane preparation method: first synthesize dibenzyl aminodithioformic acid sodium alcoholic solution, then with 1,6- bis-
Chlorohexane heating reflux reaction is filtered washing and obtains intermediate 1, and 6- bis- (one sulphur of N, N- dibenzyl amino formyl) hexane should
Intermediate is reacted with sulphur heating again generates product anti-recovery agent 1,6- bis- (two sulphur of N, N- dibenzyl amino formyl) hexane.
This synthetic method uses toxic volatile solvent methanol, and generates a large amount of waste water, pollutes environment, and back flow reaction energy
It consumes higher.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of 40-100 μm of rubber anti-recoveries
Agent and its new synthetic method, this method are anti-recovery agent 1, bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 6-
Industrialization new synthetic method, simple for process, easy to operate, solvent can with recovery and industrialization it is at low cost；System
Standby rubber is big with anti-recovery agent product granularity and particle diameter distribution is narrow, has good processing performance, adds in subsequent sizing material
Dust from flying can be efficiently reduced in work.
In one embodiment of the invention, a kind of rubber anti-recovery agent 1, bis- (N, the N '-hexichol of 6- are provided
And two sulphur of thiazoleamino formyl)-hexane, wherein at least 90% grain diameter is 40-100 μm；
A kind of new synthetic method of rubber anti-recovery agent is also provided in another embodiment of the invention, it is special
Sign is to comprise the steps of:
(1) synthesis of bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexane intermediates of 1,6-
With dibenzylamine, carbon disulfide, sodium hydroxide solution, 1,6- dichloro hexane for raw material, phase transfer catalyst is catalysis
Agent is added to containing water or is applied in the reaction kettle of mother liquor, after the reaction was completed, obtains 1,6- after centrifugation, washing, filter cake drying
Bis- (N, N '-one sulphur of bisbenzothiazole carbamyl)-hexanes, washing mother liquor A collect reuse；
(2) synthesis of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6-
In bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- synthesized to step (1), sulphur is successively put into
Sulphur and organic solvent, are reacted, and after reaction, vacuum distillation removing organic solvent obtains bis- (N, the N '-dibenzo of 1,6-
Two sulphur of thiazoleamino formyl)-hexane first product；
(3) purification of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6-
To in step (2) in bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6- obtained, investment
Ethyl acetate dissolves by heating, and cools to lower than 10 DEG C, and blowing is centrifugally separating to obtain white powder, and mother liquor B collects reuse；
Then dry by the white powder, oil spout crushes, and packaging is got product.
Further, a kind of new synthetic method of rubber anti-recovery agent is provided, comprising the following steps:
(1) first by aqueous solvent or mother liquor investment reaction kettle is applied, then successively puts into dibenzylamine and phase transfer catalyst,
It cools to 0-5 DEG C, starts that carbon disulfide is added dropwise, 1-2h is added dropwise, and continues that 32% sodium hydrate aqueous solution, drop is added dropwise
Heating degree is no more than 10 DEG C, is added dropwise and 1,6- dichloro hexane is and then slowly added dropwise, 0-5 DEG C of dropping temperature, room is added dropwise
2.5-6h is stirred to react under temperature, after completion of the reaction, be centrifuged, washing, mother liquor A collect reuse, filter cake drying after obtain 1,6- it is bis- (N,
One sulphur of N '-bisbenzothiazole carbamyl)-hexane；
(2) it into bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- made from step (1), successively puts into
Sulphur and organic solvent react 6-8h at 80-100 DEG C of temperature, and after reaction, vacuum distillation removing organic solvent obtains
Bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6-；
(3) into bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- made from step (2), acetic acid is put into
Ethyl ester dissolves by heating reflux 30min, cools to lower than 10 DEG C, blowing is centrifugally separating to obtain white powder product, mother liquor B
Collect reuse；
(4) product drying that obtains above-mentioned steps (3), oil spout, crushing, packaging, obtain finished product anti-recovery agent 1,
Bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 6-.
Two sections of the subsequent refining glue of-hexane of anti-recovery agent 1,6- bis- (N, N '-two sulphur of bisbenzothiazole carbamyl) processing
Technique: the condition of one section of calendering process is (80 DEG C of roller temperature, rod revolving speed 60rpm), calendering process are as follows: by load weighted 100 parts
Natural gum, 25 parts of N234 carbon blacks, 4.4 parts of zinc oxide, 2 parts of SA stearic acid, 1.5 part of 4020 anti-aging agent, 1 part of 9332F preventing rubber
Wax, 25 parts of N234 carbon blacks, which sequentially add, is kneaded 260S in mixer, cleans, dumping, after sizing material is put into mill mixing 5min
It is placed in natural cooling 4h in air, obtains masterbatch；Two-stage mixing process condition is (60 DEG C of roller temperature, rod revolving speed 40rpm), is mixed
Sweetening process are as follows: by one section of masterbatch, load weighted 0.6 part of Sulfur, 1 part of promotor and bis- (N, the N '-dibenzo thiophenes of 1.5 parts of 1,6-
Two sulphur of azoles carbamyl)-hexane sequentially add in mixer be kneaded 100S back glue obtain finished composition, it is wrapped on a mill
Roller is tapped rubber slice after turning refining 5 times.
Wherein, carbon disulfide in step (1), 1,6- dichloro hexane, sodium hydroxide solution, dibenzylamine, aqueous solvent weight
Than for 1:(0.8-2.0): (1.0-2.0): (1.0-3.0): (10-15), preferably 1:(1-1.5): (1.0-1.5): (1.0-
2.5): (12-15), further preferred 1:(1-1.2): (1.2-1.5): (1.2-2.3): (12.5-13.5).
It is 3-5 DEG C that carbon disulfide temperature is preferably added dropwise in step (1), and the preferred sodium hydrate aqueous solution temperature that is added dropwise is
8-10 DEG C, preferably it is added dropwise 3-5 DEG C of temperature of 1,6- dichloro hexane.
Phase transfer catalyst used is tetrabutylammonium bromide or chlorination triethyl group benzyl ammonium in step (1), preferred catalyst
Dosage is the 6-8% of dibenzylamine quality.
Rear reaction time 3-6h is added dropwise in preferred 1,6- dichloro hexane in step (1).
Preferred organic solvent is toluene, dimethylbenzene or chlorobenzene in step (2).
The molar ratio of preferred 1,6-, bis- (N, N '-one sulphur of dibenzyl amino formyl) hexane and sulphur is 1 in step (2):
The mass ratio of (2.0-2.5), 1,6- bis- (N, N '-one sulphur of bisbenzothiazole carbamyl)-hexanes and organic solvent is 1:(2-
5)。
The mass ratio of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- and ethyl acetate is in step (3)
1:(1.0-2.0), preferably 1:(1.5-2.0).
Specifically, synthetic route of the invention is as follows:
Step (1) route of synthesis
Step (2) route of synthesis
Compared with prior art, beneficial effects of the present invention are as follows:
1) mother liquor can not generate waste water, green, environmental protection, economy with recovery after reaction.
2) synthesis technology of bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexanes of intermediate 1,6- adopts water as molten
Agent, it is environmentally protective, it is used cooperatively phase transfer catalyst, oil/water two-phase mass-transfer efficiency can be improved in phase transfer catalyst, accelerates anti-
Rate is answered, yield is improved.
3) synthetic reaction of bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexanes of intermediate 1,6- at room temperature into
Row, required energy consumption is lower, easy to operation.
4) synthetic method uses crystallization processes, and the product purity made is high, and application value is wide.
5) the product cut size narrowly distributing and granularity that the synthetic method obtains are big, and material has in the process of downstream sizing material
There is good mobility, and dust concentration is lower in actual processing production process, reduces the extent of injury of occupational disease.
Detailed description of the invention
Fig. 1 is production technological process of the invention.
Specific embodiment
Present invention is further elaborated in following combination specific embodiment, but institute's protection scope of the present invention is without being limited thereto,
All deformations that he directly exports or associate from the content of present invention, are considered as protection scope of the present invention.
The partial size of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of anti-recovery agent 1,6- described herein is used
BT-9300S laser fineness gage is as obtained by Mie scattering principle progress particle size distribution measurement.Sedimentation medium is deionization
Water, dispersing agent are the aqueous solution of calgon.
Embodiment 1
A kind of new synthetic method of rubber anti-recovery agent, preparation step are as follows:
(1) 1670kg deionized water, 315.2kg dibenzylamine and 19kg catalyst four are successively put into 5000L reaction kettle
Butylammonium bromide, logical chilled brine cooling and stirring are cooled to 5 DEG C, 133.6kg bis- are slowly added dropwise into reaction kettle by head tank
Nitric sulfid, dropping temperature are no more than 5 DEG C, after being added dropwise in 2h, continue that 32% sodium hydroxide solution 199kg is added dropwise, temperature is added dropwise
Degree is no more than 10 DEG C, is added dropwise and 125kg 1 is and then slowly added dropwise into aforesaid reaction vessel, 6- dichloro hexane, dropping temperature
It no more than 5 DEG C, is added dropwise and stirs 3h at room temperature, after completion of the reaction, obtain intermediate 1,6- after centrifugation, washing, filtration cakes torrefaction
Bis- (N, N '-one sulphur of bisbenzothiazole carbamyl)-hexanes, mother liquor A collect reuse.
(2) bis- (N, the N '-bisbenzothiazole amino of 1,6- made from above-mentioned steps (1) are successively put into aforesaid reaction vessel
One sulphur of formyl)-hexane, 52kg sulphur and 1000kg toluene solvant, after reacting 6h at 80 DEG C, vacuum distillation removing toluene is obtained
To bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6-, fraction collection reuse.
(3) into bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6- made from step (2), investment
760kg ethyl acetate dissolves by heating 30min, cools to lower than 10 DEG C, and blowing is centrifugally separating to obtain white powder product,
Mother liquor B collects reuse.
(4) vacuum bipyramid dries 5h at 70 DEG C of the filter cake product obtained, and oil spout, crushing, packaging obtain finished product sulfuration resistant and return
Former agent 1, bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 6-, can be calculated gross production rate 91.3%, through testing and analyzing
Product content 98.8%, 91.7 DEG C of fusing point, ash content 0.05%, oil content 7.2%, (90) 59.26 μm of partial size d.
In the finished composition machining process of downstream, above-mentioned conjunction is measured by JC-1000 handheld-type intelligent dust detector
At anti-recovery agent 1,6- bis- (N, N '-two sulphur of bisbenzothiazole carbamyl)-hexanes investment mixers during it is existing
Field dust concentration is 88.5mg/m3。
Embodiment 2,3,4, the step of repeating embodiment 1, the difference is that: step (1) reaction time is respectively 4,5,
6h.Analysis the results are shown in Table 1.
The embodiment of 1 step of table (1) differential responses time
Embodiment 5
The step of repeating embodiment 1, the difference is that: step (1) used catalyst is 19kg chlorination triethyl group benzyl ammonium,
Finally can be calculated gross production rate 92.3%, through test and analyze product content 98.2%, 91.5 DEG C of fusing point, ash content 0.03%, oil-containing
Amount 6.7%, (90) 72.33 μm of partial size d, live dust concentration is 85.1mg/m3。
Embodiment 6
The step of repeating embodiment 1, the difference is that: solvent is 1000kg chlorobenzene in step (2), finally be can be calculated
Gross production rate 91.3%, through test and analyze product content 98.2%, 92.0 DEG C of fusing point, ash content 0.07%, oil content 6.5%, partial size d
(90) 71.33 μm, live dust concentration is 86.1mg/m3。
Embodiment 7
Step (1) centrifugation recycling filtrate 2292kg direct reuse in embodiment 1 is worked as into solvent, other steps with embodiment 1,
Obtained product, which is computed, can obtain gross production rate 90.7%, through test and analyze product content 96.1%, 91.2 DEG C of fusing point, ash content
0.04%, oil content 6.9%, (90) 58.13 μm of partial size d, live dust concentration is 89.1mg/m3。
Case of comparative examples:
One group of confirmatory experiment is completed according to the example of the preparation method of patent CN100522941C dithiol derivatives, is obtained
Bis- (N, N '-two sulphur of bisbenzothiazole carbamyl) (90) the 12.99 μm of-hexane partial size d of 1, the 6- arrived, it is hand-held by JC-1000
Formula intelligence dust detector measures the process of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane investment mixers of 1,6-
Live dust concentration is 150.2mg/m3。
Claims (11)
1. a kind of rubber anti-recovery agent 1, bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 6-, wherein at least
90% grain diameter is 40-100 μm.
2. the new synthetic method of rubber anti-recovery agent described in claim 1, it is characterised in that comprise the steps of:
(1) synthesis of bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexane intermediates of 1,6-
With dibenzylamine, carbon disulfide, sodium hydroxide solution, 1,6- dichloro hexane for raw material, phase transfer catalyst is catalyst, is added
Enter to water or apply in the reaction kettle of mother liquor, after the reaction was completed, be centrifuged, washing, obtained after filter cake drying 1,6- it is bis- (N, N '-
One sulphur of bisbenzothiazole carbamyl)-hexane, washing mother liquor A collection reuse；
(2) synthesis of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6-
To step (1) synthesize bis- (N, N '-one sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- in, successively put into sulphur with
Organic solvent is reacted, and after reaction, vacuum distillation removing organic solvent obtains bis- (N, the N '-bisbenzothiazoles of 1,6-
Two sulphur of carbamyl)-hexane first product；
(3) purification of bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6-
To in step (2) in bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexane first products of 1,6- obtained, acetic acid is put into
Ethyl ester dissolves by heating, and cools to lower than 10 DEG C, and blowing is centrifugally separating to obtain white powder, and mother liquor B collects reuse；Then
Dry by the white powder, oil spout crushes, and packaging is got product.
3. according to the described in any item methods of claim 2, it is characterised in that: the carbon disulfide, 1,6- dichloro hexane, hydrogen-oxygen
Change sodium solution, dibenzylamine, aqueous solvent weight ratio be 1:(0.8-2.0): (1.0-2.0): (1.0-3.0): (10-15).
4. according to the described in any item methods of claim 2-3, it is characterised in that: bis- (N, the N '-dibenzo of 1,6- in step (2)
One sulphur of thiazoleamino formyl) molar ratio of-hexane and sulphur is 1:(2.0-2.5), 1,6- bis- (N, N '-bisbenzothiazole amino
One sulphur of formyl) mass ratio of-hexane and organic solvent is 1:(2-5).
5. according to the described in any item methods of claim 2-4, it is characterised in that: bis- (N, the N '-dibenzo of 1,6- in step (3)
Two sulphur of thiazoleamino formyl) mass ratio of-hexane and ethyl acetate is 1:(1.0-2.0).
6. according to any one of claim 2-5 the method, it is characterised in that: step (1) specific preparation step are as follows:
First by aqueous solvent or mother liquor investment reaction kettle is applied, then successively puts into dibenzylamine and phase transfer catalyst, cooling drop
Temperature to 0-5 DEG C starts that carbon disulfide is added dropwise, and 1-2h is added dropwise, and continues that 32% sodium hydrate aqueous solution, dropping temperature is added dropwise
No more than 10 DEG C, it is added dropwise and 1,6- dichloro hexane is and then slowly added dropwise, 0-5 DEG C of dropping temperature, be added dropwise and stir at room temperature
Mix reaction 2.5-6h, after completion of the reaction, be centrifuged, washing, mother liquor A collects reuse, obtain intermediate 1 after filter cake drying, 6- it is bis- (N,
One sulphur of N '-bisbenzothiazole carbamyl)-hexane.
7. according to the described in any item methods of claim 2-6, it is characterised in that: the phase transfer catalyst is tetrabutyl phosphonium bromide
Ammonium or chlorination triethyl group benzyl ammonium, the dosage of catalyst are the 6-8% of dibenzylamine quality.
8. the method according to claim 2, it is characterised in that: reaction temperature is 80-100 DEG C in step (2),
Time is 6-8h, and the organic solvent is toluene, dimethylbenzene or chlorobenzene.
9. according to the described in any item methods of claim 2-8, which is characterized in that carbon disulfide temperature is added dropwise in step (1) is
3-5 DEG C, it is 8-10 DEG C that sodium hydrate aqueous solution temperature, which is added dropwise,.
10. according to the described in any item methods of claim 5-8, which is characterized in that temperature is added dropwise in 1,6- dichloro hexane in step (1)
3-5 DEG C of degree, is added dropwise rear reaction time 3-6h.
11. bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of anti-recovery agent 1,6- described in claim 1 or
Bis- (N, N '-two sulphur of bisbenzothiazole the carbamyl)-hexanes of 1,6- of the described in any item method preparations of claim 2-10 are made
For the application of rubber anti-recovery agent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810962402.8A CN109233035B (en) | 2018-08-22 | 2018-08-22 | Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof |
| PCT/CN2018/113797 WO2020037831A1 (en) | 2018-08-22 | 2018-11-02 | ANTI-VULCANISATION REVERSION AGENT FOR RUBBER HAVING PARTICLE DIAMETER OF 40-100 μM AND NEW SYNTHESIS METHOD THEREFOR |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810962402.8A CN109233035B (en) | 2018-08-22 | 2018-08-22 | Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof |
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| CN109233035B CN109233035B (en) | 2020-10-23 |
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| CN109233035B (en) | 2020-10-23 |
| WO2020037831A1 (en) | 2020-02-27 |
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