CN104860829B - A kind for the treatment of of rubber vulcanizing accelerator CBS mother liquor and using method - Google Patents
A kind for the treatment of of rubber vulcanizing accelerator CBS mother liquor and using method Download PDFInfo
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Abstract
Treatment and using method the invention discloses a kind of rubber vulcanizing accelerator CBS mother liquor, including：By CBS mother liquors in 20~35 DEG C of standings, 0~15 DEG C of standing is cooled to again after mother liquor is tentatively divided into three layers, until each interlayer boundary line of CBS mother liquors is clear；Extract the CBS mother liquors positioned at middle part, it is designated as intermediate layer mother liquor, it is stood at normal temperatures, the upper strata of intermediate layer mother liquor is carried out into rectifying after standing reclaims cyclohexylamine, is directly covered the lower floor of intermediate layer mother liquor as recovery mother liquor in the synthetic method for rubber vulcanizing accelerator CBS.Process of the present invention is simple, easily operated, has reclaimed the CBS for being dissolved in and reclaiming in mother liquor, saved water consumption and later stage mother liquor rectifying needed for the energy, reduce production cost, reduce the discharge of sewage and waste residue, meet national environmental protection policy.
Description
Technical field
Treatment and using method the present invention relates to a kind of rubber vulcanizing accelerator CBS mother liquor, belong to vulcanization of rubber promotion
Agent CBS production technical fields.
Background technology
Rubber vulcanizing accelerator CBS（Chemical name is N- cyclohexyl-2-benzothiazole sulfonamides, and molecular formula is
C13H16N2S2）It is a kind of late effect property thiofide conventional both at home and abroad, is remarkably improved the physical of rubber
Energy and ageing-resistant performance, scorching quality are excellent, and process safety, cure time is short, it is adaptable to various rubber, and discoloration is slight, no
Bloom, vulcanizate is ageing-resistant, tensile strength, and it is preferable to stretch ability surely, mainly for the manufacture of tire, sebific duct, rubber overshoes, the work such as electric wire
Industry rubber.Because it is in the absence of the carcinogenic problem of nitrosamine, therefore it is the master of domestic and international sulfenamide type accelerators at present
One of kind, the market demand is wanted to increase very fast.
The method of existing production CBS is with captax（Chemical name is 2- thiol benzothiazoles, and molecular formula is
C7H5NS2）With excessive cyclohexylamine into salt, CBS then is obtained under oxidant effect, through filtering, washing, drying, dries（Or
Granulation）Rubber vulcanizing accelerator CBS finished product is obtained, remaining mother liquor will be finally filtered again carries out rectifying, and recovery has neither part nor lot in reaction
Cyclohexylamine.Due to containing cyclohexylamine in mother liquor, and accelerator CBS can be dissolved in cyclohexylamine, so if by the direct rectifying of mother liquor
Discharge afterwards can cause the loss of CBS, have impact on product yield, increased production cost；Meanwhile, if by the direct rectifying of mother liquor,
Rectifying is operated at more than 100 DEG C, and accelerator CBS can be decomposed to form the resinous impurities of complicated component at this temperature, be changed into
Solid waste, causes to waste, and also add processing cost, have impact on environment, does not meet national environmental protection policy.
The content of the invention
It is an object of the invention to provide a kind of processing method of rubber vulcanizing accelerator CBS mother liquor, the method is to CBS mother liquors
Processed, separated CBS before mother liquor rectifying, fully reclaimed ring amine and CBS, reduced the product of solid waste
It is raw, reduce the discharge capacity of waste water.
It is a further object of the present invention to provide a kind of using method of rubber vulcanizing accelerator CBS mother liquor, will CBS mother liquors
Method of the recovery in CBS synthesis, the method applies mechanically disposing mother liquor, reduces a water（I.e. without the pure water for using,
Similarly hereinafter）Use, reduce the discharge capacity of waste water, improve product yield, reduce production cost.
To reach above-mentioned purpose, the present invention is achieved by following technical proposals：
A kind of processing method of rubber vulcanizing accelerator CBS mother liquor, comprises the following steps：
（1）CBS mother liquors are stood at 20~35 DEG C, 0~15 DEG C of standing is cooled to again after mother liquor is tentatively divided into three layers,
Until each interlayer boundary line of CBS mother liquors is clear；
（2）The CBS mother liquors positioned at middle part are extracted, intermediate layer mother liquor is designated as, it is stood at normal temperatures, stood
CBS is enriched to the lower floor of intermediate layer mother liquor in journey, and cyclohexylamine is then enriched to the upper strata of intermediate layer mother liquor；
（3）The upper strata of intermediate layer mother liquor is carried out into rectifying, cyclohexylamine is reclaimed, by lower floor's direct reuse of intermediate layer mother liquor in
In CBS productions.
In above-mentioned processing method, by the adjustment to mother liquor temperature, the various composition in mother liquor is set to be enriched with and be separated,
Available composition is carried out by different methods again be separately recovered utilization, it is to avoid the waste of resource.Wherein step（1）In,
Mother liquor is divided into three layers, and ground floor is the superiors of mother liquor, is the lighter Gugulipid of proportion, and the second layer is located at the centre of mother liquor,
For water phase, ring amine and CBS are concentrated mainly on this layer, and third layer is located at the bottom of mother liquor, is the viscosity such as the larger resin of proportion
Material, their agglomerating caking ground are present.
Further, after CBS mother liquors extract intermediate layer mother liquor, the resin of CBS mother liquors upper strata and bottom is merged together, and is led to
Distillation can reclaim the cyclohexylamine for wherein containing after crossing steam heating.Because the cyclohexylamine concentration for obtaining is low, need to again pass through rectifying
Concentrate to the content side for specifying can be back in production.Remaining resin is at high operating temperatures into flowing after reclaiming cyclohexylamine
Oily liquids, then be for further processing.
In the above method, the lower floor of the intermediate layer mother liquor obtained by treatment（It is designated as reclaiming mother liquor）Middle cyclohexylamine content is
4 ~ 10wt%, accelerator CBS content is 2 ~ 5wt%.By the recycled of the recovery mother liquor, the CBS in mother liquor can be reclaimed, carried
CBS yields high.
Present invention also offers a kind of method of mother liquid recycle synthetic rubber aniline fluid bed, the method be first according to
The processing method of above-mentioned rubber vulcanizing accelerator CBS mother liquor is pre-processed to CBS mother liquors, then takes the lower floor of intermediate layer mother liquor
As recovery mother liquid recycle in the synthetic method of rubber vulcanizing accelerator CBS.
In above-mentioned mother liquid recycle method, step includes：Water, surfactant, captax, a recovery mother liquor are mixed
Uniformly, being subsequently adding cyclohexylamine carries out salt-forming reaction, adds the sodium hypochlorite to carry out oxidation reaction in the way of being added dropwise again after reaction,
Reaction solution is processed after reaction, is obtained rubber vulcanizing accelerator CBS.
In above-mentioned mother liquid recycle method, there is the cyclohexylamine of 50 ~ 65% molal volumes in reaction cyclohexylamine used to reclaim ring
Hexylamine.
In above-mentioned mother liquid recycle method, captax：Surfactant：Water：The mass ratio for reclaiming mother liquor is 1：
0.002~0.005：0.6~1.2：1~2, preferably 1：0.002~0.004：0.8~1.2：1.2~1.5.
In above-mentioned mother liquid recycle method, captax：Cyclohexylamine：The mol ratio of sodium hypochlorite is 1：2.0~2.6：1.0~
1.3, preferably 1：2.0~2.6：1.2.
In above-mentioned mother liquid recycle method, the surfactant is aliphatic alcohol polyoxyethylene or alkylphenol-polyethenoxy
Ether.
In above-mentioned mother liquid recycle method, the incorporation time of water, surfactant, captax and a recovery mother liquor is 30
~60 minutes.
In above-mentioned mother liquid recycle method, captax will be controlled into cyclohexylamine in the case of the stirring that heats up fully into salt
The salt time was at 30~60 minutes.
In above-mentioned mother liquid recycle method, the temperature of oxidation reaction is 20 ~ 50 DEG C, preferably 30~40 DEG C.
In above-mentioned mother liquid recycle method, the time that dropwise addition sodium hypochlorite is reacted is 150 ~ 240 minutes, preferably 180-
240 minutes.
In above-mentioned mother liquid recycle method, following steps are specifically included：
（1）To a water, and surfactant is added in kettle with slurry, stirring is opened；
（2）Captax mashing is added, recovery mother liquor is then added, continues stirring to pulp；
（3）Slurry dnockout pumps after mashing is transferred to synthesis reactor, adds the recovery cyclohexylamine of reaction integral molar quantity 50 ~ 65%,
Then add fresh cyclohexylamine to supply, stirring heats up, make captax with cyclohexylamine fully into salt；
（4）Sodium hypochlorite is added dropwise at 20~50 DEG C, control time for adding was added dropwise sodium hypochlorite and reaches at 150~240 minutes
To after the 90% of ormal weight, frequent sampling and testing reaction end reaches terminal and stops that sodium hypochlorite is added dropwise, and continuing to stir 15
After minute, terminal keeps not changing；
（5）Filtered after completion of the reaction, filtering is mother liquid obtained to be processed according to above-mentioned mother liquor processing method, to follow
Ring set use, filters resulting material and obtains rubber vulcanizing accelerator CBS product after washing, drying up, dry or wash, dry up, granulate.
In the above method, captax is first moistened with a water containing surfactant, solved due to using back merely
Receive mother liquor it is with slurry when M is united the shortcoming of caking, mother liquid recycle amount is added more than the 50% of water up to reaction.
CBS mother liquors are processed and the mother liquor after treatment is circulated by the present invention to be applied mechanically, and process is simple, be easy to behaviour
Make, rectifying recovery ring amine is carried out to mother liquor again after CBS is first isolated during mother liquid disposal, alleviate rectifying and reclaim cyclohexylamine
Pressure, reduce energy consumption, reduce the waste residue amount produced in distillation process, meet national environmental protection policy.The present invention is by mother liquor
Reuse, by the cyclohexylamine recycling in mother liquor, not only reduces the discharge capacity of waste water, also correspondingly reduces a water and ring
The consumption of amine, reduces production cost, while the CBS for being dissolved in and reclaiming in mother liquor has been reclaimed in mother liquor reuse, product is averagely received
Rate improves 2.5%, and the accelerator CBS steady quality for synthesizing, and content reaches more than 98.0%, meets the requirements.
Specific embodiment
With reference to specific embodiment, the invention will be further described, following embodiments be only it is exemplary, it is not right
Its content is defined.
Embodiment 1
1st, remaining CBS mother liquors after filtering product CBS are taken, are added into standing tank, the stratification at 20~35 DEG C,
After mother liquor is tentatively divided into three layers, then be cooled to 0~15 DEG C of standing, be layered mother liquor obvious, the division is clearly demarcated for each interlayer, proportion compared with
The viscous materials such as big resin are separated out agglomerating caking from mother liquor, positioned at the bottom, and the lighter Gugulipid floating of proportion
In the superiors of mother liquor, water layer is located at intermediate layer.
2nd, the mother liquor in the middle of extracting, by this middle mother liquor stratification, the less clear liquid of upper strata CBS contents at normal temperatures again
Separate and collect, cyclohexylamine reuse is reclaimed in rectifying after concentration, and the liquid of lower floor CBS enrichments is back to CBS productions as mother liquor is reclaimed
In, cyclohexylamine content is 4 ~ 10wt% in reclaiming mother liquor, and accelerator CBS content is 2 ~ 5wt%.
3rd, will stand and extracted after middle mother liquor what Distillation recovery after remaining mother liquor steam heating wherein contained in tank
Cyclohexylamine, the content that the cyclohexylamine of the low concentration for obtaining reaches regulation through rectifying concentrate again is back to production, remains under distillation still
The resin in portion is then released into the oily liquids of flowing from distillation still bottom at high operating temperatures.
Embodiment 2
To 450 liters of the water of addition one time and surfactant in kettle with slurry（Aliphatic alcohol polyoxyethylene）1.2 kilograms, unlatching is stirred
Mix, add 500 kilograms of raw material captax mashing, then add 750 liters of mother liquor of recovery, continue stirring to pulp, when amounting to mashing
Between be 50~60 minutes；Slurry dnockout pumps is transferred to synthesis reactor, adds reaction integral molar quantity 50%（It is pure）Recovery cyclohexylamine,
Then to add and add industrial cyclohexylamine according to what reaction ratio gauge was calculated, stirring heats up, make M with cyclohexylamine fully into salt,
At 50~60 minutes, captax was 1 with the reaction mol ratio of cyclohexylamine to control salt time：2.3；In oxidation temperature after reaction
Sodium hypochlorite is added dropwise at 30 DEG C of degree, captax is 1 with the reaction mol ratio of sodium hypochlorite：1.20, control time for adding exists
200~240 minutes, after dropwise addition sodium hypochlorite reaches the 90% of ormal weight, frequent sampling and testing reaction end, less than reaction end,
Then continue to add sodium hypochlorite, after reaching reaction end stop be added dropwise sodium hypochlorite, and continue stirring 15 minutes after, terminal
Holding does not change.Filtered after completion of the reaction, collect mother liquor and the method according to embodiment 1 is processed, to reclaim again
With material is through washing, drying up, dry（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS for synthesizing contains
Amount reaches 98.2%, yield 95.8%.
Embodiment 3
To 500 liters of the water of addition one time and surfactant in kettle with slurry（APES）1.5 kilograms, unlatching is stirred
Mix, add 500 kilograms of raw material captax mashing, then add 700 liters of mother liquor of recovery, continue stirring to pulp, when amounting to mashing
Between be 50~60 minutes；Slurry dnockout pumps is transferred to synthesis reactor, adds reaction integral molar quantity 55%（It is pure）Recovery cyclohexylamine,
Then to add and add industrial cyclohexylamine according to what reaction ratio gauge was calculated, stirring heats up, make M with cyclohexylamine fully into salt,
At 40~60 minutes, captax was 1 with the reaction mol ratio of cyclohexylamine to control salt time：2.5；In oxidation temperature after reaction
Sodium hypochlorite is added dropwise at 35 DEG C of degree, captax is 1 with the reaction mol ratio of sodium hypochlorite：1.20, control time for adding exists
180~210 minutes, after dropwise addition sodium hypochlorite reaches the 90% of ormal weight, frequent sampling and testing reaction end, less than reaction end,
Then continue to add sodium hypochlorite, after reaching reaction end stop be added dropwise sodium hypochlorite, and continue stirring 15 minutes after, terminal
Holding does not change.Filtered after completion of the reaction, collect mother liquor and the method according to embodiment 1 and processed, material through washing,
Dry up, dry（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS content for synthesizing reaches 98.3%, receives
Rate 95.6%.
Embodiment 4
To 550 liters of the water of addition one time and surfactant in kettle with slurry（Aliphatic alcohol polyoxyethylene）1.8 kilograms, unlatching is stirred
Mix, add 500 kilograms of raw material captax mashing, then add 650 liters of mother liquor of recovery, continue stirring to pulp, when amounting to mashing
Between be 40 ~ 50 minutes；Slurry dnockout pumps is transferred to synthesis reactor, adds reaction integral molar quantity 60%（It is pure）Recovery cyclohexylamine, so
Add afterwards and add industrial cyclohexylamine according to what reaction ratio gauge was calculated, stirring heats up, make M with cyclohexylamine fully into salt, control
At 50 ~ 60 minutes, captax was 1 with the reaction mol ratio of cyclohexylamine to salt time processed：2.2；In oxidizing temperature 40 after reaction
Sodium hypochlorite is added dropwise at DEG C, captax is 1 with the reaction mol ratio of sodium hypochlorite：1.20, control time for adding 160 ~
200 minutes, be added dropwise after sodium hypochlorite reaches the 90% of ormal weight, frequent sampling and testing reaction end, less than reaction end, then after
It is continuous to add sodium hypochlorite, stop being added dropwise sodium hypochlorite after reaching reaction end, and after continuing stirring 15 minutes, terminal keeps
Do not change.Filtered after completion of the reaction, collect mother liquor and the method according to embodiment 1 is processed, material is through being washed, being blown
It is dry, dry（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS content for synthesizing reaches 98.5%, yield
95.5%。
Embodiment 5
To 600 liters of the water of addition one time and surfactant in kettle with slurry（APES）2.0 kilograms, unlatching is stirred
Mix, add 500 kilograms of raw material captax mashing, then add 600 liters of mother liquor of recovery, continue stirring to pulp, when amounting to mashing
Between be 30 ~ 40 minutes；Slurry dnockout pumps is transferred to synthesis reactor, adds reaction integral molar quantity 55%（It is pure）Recovery cyclohexylamine, so
Add afterwards and add industrial cyclohexylamine according to what reaction ratio gauge was calculated, stirring heats up, make M with cyclohexylamine fully into salt, control
At 30 ~ 40 minutes, captax was 1 with the reaction mol ratio of cyclohexylamine to salt time processed：2.1；In oxidizing temperature 28 after reaction
Sodium hypochlorite is added dropwise at DEG C, captax is 1 with the reaction mol ratio of sodium hypochlorite：1.20, control time for adding 150 ~
180 minutes, be added dropwise after sodium hypochlorite reaches the 90% of ormal weight, frequent sampling and testing reaction end, less than reaction end, then after
It is continuous to add sodium hypochlorite, stop being added dropwise sodium hypochlorite after reaching reaction end, and after continuing stirring 15 minutes, terminal keeps
Do not change.Filtered after completion of the reaction, collect mother liquor and the method according to embodiment 1 is processed, material is through being washed, being blown
It is dry, dry（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS content for synthesizing reaches 98.6%, yield
95.2%。
Comparative example 1
To 1200 liters of the water of addition one time and surfactant in kettle with slurry（APES）2.0 kilograms, open
Stirring, adds 500 kilograms of raw material captax mashing, and beating time is 30 ~ 40 minutes；Slurry dnockout pumps is transferred to synthesis reactor, plus
Enter to react total amount 55%（It is pure）Recovery cyclohexylamine, then to add and add industrial hexamethylene according to what reaction ratio gauge was calculated
Amine, stirs and heats up, and makes M with cyclohexylamine fully into salt, and control salt time was 30 ~ 40 minutes, the reaction of captax and cyclohexylamine
Mol ratio is 1：2.1；Sodium hypochlorite is added dropwise at 28 DEG C of oxidizing temperature after reaction, captax rubs with the reaction of sodium hypochlorite
Your proportioning is 1：1.20, control time for adding after dropwise addition sodium hypochlorite reaches the 90% of ormal weight, often took at 150 ~ 180 minutes
Sample test reaction terminal, less than reaction end, then continues to add sodium hypochlorite, stops that time chlorine is added dropwise after reaching reaction end
Sour sodium, and continue stirring 15 minutes after, terminal keep do not change.Filtered after completion of the reaction, collected mother liquor, material is through water
Wash, dry up, drying（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS content 99.3% for synthesizing, yield
93.5%。
Other, from result in terms of the realities identical with comparative example in addition to replacing the water of part one time using the mother liquor for reclaiming of embodiment 5
The products obtained therefrom purity of example 5 slightly less than comparative example is applied, but is increased on yield, and the consumption of a water is substantially reduced.
Comparative example 2
To 600 liters of a water is added in kettle with slurry, stirring is opened, add 500 kilograms of raw material captax mashing, Ran Houzai
Add and reclaim 600 liters of mother liquor, continue stirring to pulp, it is 30 ~ 40 minutes to amount to beating time；Slurry dnockout pumps is transferred to synthesis
Kettle, adds reaction total amount 55%（It is pure）Recovery cyclohexylamine, then to add and add industry according to what reaction ratio gauge was calculated
Cyclohexylamine, stirring heats up, and makes M and cyclohexylamine fully into salt, control salt time at 30 ~ 40 minutes, captax and cyclohexylamine
Reaction mol ratio is 1：2.1；Sodium hypochlorite is added dropwise at 28 DEG C of oxidizing temperature after reaction, captax is anti-with sodium hypochlorite
It is 1 to answer mol ratio：1.20, control time for adding after dropwise addition sodium hypochlorite reaches the 90% of ormal weight, was passed through at 150 ~ 180 minutes
Normal sampling and testing reaction end, less than reaction end, then continues to add sodium hypochlorite, stops being added dropwise after reaching reaction end
Sodium hypochlorite, and continue stirring 15 minutes after, terminal keep do not change.Filtered after completion of the reaction, collected mother liquor, material warp
Wash, dry up, dry（Or granulation）Rubber vulcanizing accelerator CBS product is obtained afterwards.The accelerator CBS content for synthesizing 97.2%,
Yield 90.5%.Product appearance color and luster is partially yellow, wherein carrying the complete M particulates of very small amount unreacted secretly, poor quality, yield is low.
Claims (10)
1. a kind of processing method of rubber vulcanizing accelerator CBS mother liquor, it is characterized in that comprising the following steps：
（1）CBS mother liquors are stood at 20~35 DEG C, 0~15 DEG C of standing is cooled to again after mother liquor is tentatively divided into three layers, until
Each interlayer boundary line of CBS mother liquors is clear；
（2）The CBS mother liquors positioned at middle part are extracted, intermediate layer mother liquor is designated as, it is stood at normal temperatures, during standing
CBS is enriched to the lower floor of intermediate layer mother liquor, and cyclohexylamine is enriched to the upper strata of intermediate layer mother liquor；
（3）The upper strata of intermediate layer mother liquor is carried out into rectifying, cyclohexylamine is reclaimed, by lower floor's direct reuse of intermediate layer mother liquor in CBS
In production；The chemical name of the CBS is N- cyclohexyl-2-benzothiazole sulfonamides.
2. processing method according to claim 1, it is characterized in that：Extract remaining CBS mother liquors distillation after the mother liquor of intermediate layer
Reclaim cyclohexylamine.
3. a kind of method of mother liquid recycle synthetic rubber aniline fluid bed, it is characterized in that：According to the rubber described in claim 1
The processing method of glue aniline fluid bed mother liquor is pre-processed to CBS mother liquors, and the lower floor of intermediate layer mother liquor is female as reclaiming
Liquid is covered in the synthetic method for rubber vulcanizing accelerator CBS.
4. method according to claim 3, it is characterized in that：Water, surfactant, captax, a recovery mother liquor are mixed
Close uniform, being subsequently adding cyclohexylamine carries out salt-forming reaction, added in the way of being added dropwise again after reaction sodium hypochlorite aoxidize it is anti-
Should, reaction solution is processed after reaction, obtain rubber vulcanizing accelerator CBS；The chemical name of the captax is 2- mercaptos
Benzothiazole.
5. method according to claim 4, it is characterized in that：There are 50~65% molal volumes in reaction cyclohexylamine used
Cyclohexylamine is recovery cyclohexylamine.
6. method according to claim 4, it is characterized in that：Captax：Surfactant：Water：Reclaim the matter of mother liquor
Amount is than being 1：0.002~0.005：0.6~1.2：1~2；Captax：Cyclohexylamine：The mol ratio of sodium hypochlorite is 1：2.0~
2.6：1.0~1.3.
7. method according to claim 4, it is characterized in that：The surfactant is aliphatic alcohol polyoxyethylene or alkyl
Phenol polyethenoxy ether.
8. method according to claim 4, it is characterized in that：Water, surfactant, captax and reclaim mother liquor
Incorporation time is 30~60 minutes；Captax will control salt time with cyclohexylamine in the case of the stirring that heats up fully into salt
At 30~60 minutes.
9. method according to claim 4, it is characterized in that：The temperature of oxidation reaction is 20 ~ 50 DEG C.
10. method according to claim 4, it is characterized in that：The time that dropwise addition sodium hypochlorite is reacted is 150 ~ 240 points
Clock.
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| CN105399702A (en) * | 2015-12-17 | 2016-03-16 | 科迈化工股份有限公司 | Recycling and reusing method of solid matters in rubber vulcanization accelerator CBS production mother liquor |
| CN110577502B (en) * | 2019-09-16 | 2021-03-23 | 山东尚舜化工有限公司 | Method for improving yield of rubber accelerator TBBS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6245912B1 (en) * | 1999-07-30 | 2001-06-12 | Uniroyal Chemical Company, Inc. | Process for making N-alkyl bis(2-pyridyl) sulfenimides |
| WO2010084506A2 (en) * | 2009-01-23 | 2010-07-29 | Nocil Limited | Novel sulfenamide accelerators for replacement of conventional sulfenamide accelerator dcbs (dicyclohexyl benzothiazole sulfenamide) in steel cord skim (wire coating) compound |
| CN104311506A (en) * | 2014-09-30 | 2015-01-28 | 天津一化化工有限公司 | Synthetic process of rubber vulcanization accelerator CBS |
| CN104402841A (en) * | 2014-09-28 | 2015-03-11 | 天津一化化工有限公司 | Recovery and reutilization method of cyclohexylamine in CBS production technology |
-
2015
- 2015-04-16 CN CN201510180441.9A patent/CN104860829B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6245912B1 (en) * | 1999-07-30 | 2001-06-12 | Uniroyal Chemical Company, Inc. | Process for making N-alkyl bis(2-pyridyl) sulfenimides |
| WO2010084506A2 (en) * | 2009-01-23 | 2010-07-29 | Nocil Limited | Novel sulfenamide accelerators for replacement of conventional sulfenamide accelerator dcbs (dicyclohexyl benzothiazole sulfenamide) in steel cord skim (wire coating) compound |
| CN104402841A (en) * | 2014-09-28 | 2015-03-11 | 天津一化化工有限公司 | Recovery and reutilization method of cyclohexylamine in CBS production technology |
| CN104311506A (en) * | 2014-09-30 | 2015-01-28 | 天津一化化工有限公司 | Synthetic process of rubber vulcanization accelerator CBS |
Non-Patent Citations (1)
| Title |
|---|
| 促进剂CBS装置技术改造;陈绍华等;《石化技术与应用》;20060131;第24卷(第1期);第35-37页 * |
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