CN105503677A - Preparation method of environment-friendly and efficient sulfurization crosslinking agent 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane - Google Patents
Preparation method of environment-friendly and efficient sulfurization crosslinking agent 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane Download PDFInfo
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- CN105503677A CN105503677A CN201510891653.8A CN201510891653A CN105503677A CN 105503677 A CN105503677 A CN 105503677A CN 201510891653 A CN201510891653 A CN 201510891653A CN 105503677 A CN105503677 A CN 105503677A
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- hexane
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- sulphur
- dibenzyl
- amino formyl
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- -1 N,N-dibenzyl carbamyl disulfide Chemical compound 0.000 title abstract description 5
- 239000003431 cross linking reagent Substances 0.000 title abstract description 3
- 238000005987 sulfurization reaction Methods 0.000 title abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000005864 Sulphur Substances 0.000 claims description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000004073 vulcanization Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000007613 environmental effect Effects 0.000 claims description 23
- YKVABMCSVUSETE-UHFFFAOYSA-N dibenzylcarbamodithioic acid;sodium Chemical compound [Na].C=1C=CC=CC=1CN(C(=S)S)CC1=CC=CC=C1 YKVABMCSVUSETE-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 150000003385 sodium Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 4
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 abstract 1
- NGCCQISMNZBKJJ-UHFFFAOYSA-N 2,6-dichloro-3-methylquinoline Chemical compound ClC1=CC=C2N=C(Cl)C(C)=CC2=C1 NGCCQISMNZBKJJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 11
- 239000012467 final product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07C333/16—Salts of dithiocarbamic acids
-
- 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
-
- 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
- C07C333/24—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to carbon atoms of six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of an environment-friendly and efficient sulfurization crosslinking agent 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane. The preparation method comprises steps as follows: sodium dibenzyldithiocarbamate is synthesized firstly and then reacts with 1,6-dichlorohexane, 1,6-bis(N,N-dibenzyl carbamyl sulfide) hexane is generated, the composition reacts with sulfur, and a product, namely, 1,6-bis(N,N-dibenzyl carbamyl disulfide) hexane is generated. The prepared product contains little inorganic salt and has high purity; the preparation method is simple, practicable and environment-friendly, little waste water is produced in the preparation process, and environmental pollution is reduced.
Description
Technical field
The present invention relates to the preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, belong to rubber ingredients synthesis technique field.
Background technology
Natural rubber has reversion phenomenon in high temperature or long-time sulfidation, and reversion can reduce the cross-linking density of cross-linked rubber, and then reduces mechanical property and the dynamic property of cross-linked rubber.1; 6-bis-(N; N-dibenzyl thiocarbamoyl two sulphur) hexane is a kind of new and effective multiple crosslinking agent; both there is the effect of vulcanization accelerator; have again the effect of anti-recovery, its cross-link bond formed has the stability of monosulfidic bond and cystine linkage, has again the kindliness of similar polysulfide crosslink bond simultaneously; stable cross-linked network can be formed in sulfidation, improve the anti-reversion behaviour of sizing material.
Be mainly Material synthesis with the two sodothiol dihydrate of hexa-methylene-1,6-and dibenzyl aminodithioformic acid sodium in the synthetic method of current this product.Wherein Germany is being reaction conditions containing formaldehyde, toluene and weakly alkaline environment, take water as solvent, sintetics, but this preparation method has following shortcoming: 1. can produce a large amount of containing formaldehyde, waste water containing a small amount of toluene, and have unpleasant toxic odor, more difficult; 2. this speed of response is comparatively slow, and the reaction times of needs is longer.In addition, in China, with dioxy six alkane, methylene dichloride and toluene etc. for solvent, sintetics, but there is following shortcoming in this preparation method: two kinds of raw materials are all the salts being insoluble in organic solvent, in nonhomogeneous system, carry out so this replacement(metathesis)reaction is more difficult, the reaction times of needs is long.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, product purity prepared by this synthetic method is high, and required time is short, the toxic wastewater generated is few, and industrialization cost is low.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, comprises step as follows:
(1) with dibenzylamine, sodium hydroxide and dithiocarbonic anhydride for raw material, join in solvent, after having reacted, obtain the solution containing dibenzyl aminodithioformic acid sodium;
(2) 1 is added to obtained the containing in the solution of dibenzyl aminodithioformic acid sodium of step (1), 6-dichloro hexane and catalyzer, react at reflux, after completion of the reaction, suction filtration, filter cake is washed, remove side product chlorinated sodium, suction filtration again after washing, filter cake obtains 1 after drying, 6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane;
(3) by obtained 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and sulphur joins in organic solvent, react at temperature 70-100 DEG C, after completion of the reaction, removing organic solvent, obtains 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product.
The present invention is preferred, and described in step (1), solvent is methyl alcohol, ethanol or Virahol.
The present invention is preferred, and in step (1), the mol ratio of dibenzylamine, sodium hydroxide and dithiocarbonic anhydride is 1:(1.0 ~ 1.3): (1.1 ~ 1.3), the mass ratio of dibenzylamine and solvent is 1:(5 ~ 8).
The present invention is preferred, and in step (1), dithiocarbonic anhydride joins in reaction system in dropping mode, dropwises in 30min, in step (1), temperature of reaction is 0-50 DEG C, and the reaction times is 3-5 hour, preferably, temperature of reaction is 10-35 DEG C, and the reaction times is 4-5 hour.
The present invention is preferred, in step (2) 1, the add-on of 6-dichloro hexane be 1.0:(2.1 ~ 2.3 containing the mol ratio of dibenzyl aminodithioformic acid sodium in dibenzyl aminodithioformic acid sodium solution), wherein, the yield of dibenzyl aminodithioformic acid sodium calculates with 95%.
The present invention is preferred, and the catalyzer in step (2) is KI or KBr, and the add-on of catalyzer is 0.1 ~ 0.5% of dibenzyl aminodithioformic acid sodium quality.
The present invention is preferred, and the temperature of reaction in step (2) is 70-85 DEG C, and the reaction times is 3-5 hour.The temperature of reaction of this step depends on the boiling point of solvent for use.
The present invention is preferred, and in step (2) after completion of the reaction, suction filtration, washes filter cake, remove side product chlorinated sodium, suction filtration again after washing, filter cake obtains 1 after drying, 6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, solvent can reuse.
The present invention is preferred, and organic solvent described in step (3) is toluene, dimethylbenzene or 120# solvent oil.
The present invention is preferred, in step (3) 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) mol ratio of hexane and sulphur is 1:(2.0 ~ 2.2), 1, the mass ratio of 6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and organic solvent is 1:(5 ~ 8).
The present invention is preferred, and step (3) temperature of reaction is 80-95 DEG C, and the reaction times is 5-7 hour.
The present invention is preferred, and step (3) organic solvent adopts underpressure distillation mode to remove.
Synthetic route of the present invention is as follows:
Beneficial effect of the present invention is as follows:
Preparation method of the present invention, dibenzyl aminodithioformic acid sodium is in a solvent without the need to extracting, direct employing is containing the solution and 1 of dibenzyl aminodithioformic acid sodium, the reaction of 6-dichloro hexane, effectively can guarantee production safety, the potentially contaminated that personnel cause intermediate production process can be avoided again.Meanwhile, simplify production operation, reduce the discharge of waste liquid, reduce the energy consumption in intermediate leaching process; And dibenzyl aminodithioformic acid sodium is dissolved in solvent of the present invention, 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and byproduct sodium chloride are insoluble to solvent, can remove the unreacted dibenzyl aminodithioformic acid sodium of minute quantity and 1 after suction filtration, 6-dichloro hexane, after further filter cake being washed, remove side product chlorinated sodium, make obtain 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane purity improves; 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and sulphur can be dissolved in organic solvent of the present invention, homogeneous system in building-up process, and reaction is easily carried out, and substantially reduces the reaction times.In this building-up reactions, side reaction is few, and the product purity obtained is high, productive rate is high, and only can produce the waste water of a small amount of sodium chloride-containing, produces without other refuses, really reaches the production process of green non-pollution.
Accompanying drawing explanation
Fig. 1 is 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product infrared spectrogram that the embodiment of the present invention 1 obtains.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but institute of the present invention protection domain is not limited thereto.
Embodiment 1
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, step is as follows:
(1) in 1000mL there-necked flask, 39.4g dibenzylamine, 8.4g sodium hydroxide and 190g ethanol is dropped into, 20min is stirred at 20 DEG C, take 16g dithiocarbonic anhydride in constant pressure funnel, in 30min, dithiocarbonic anhydride is added drop-wise in this there-necked flask, continue stirring at 20 DEG C 3 hours, after having reacted, obtain the ethanolic soln containing dibenzyl aminodithioformic acid sodium.
(2) take 14.7g1,6-dichloro hexane and 0.2gKI join in this flask, connect prolong, be warming up to system backflow with electric mantle, stir 4 hours under reflux state, after reaction terminates, be cooled to room temperature, suction filtration obtains white filter cake, by filter cake as in 500mL beaker, add about 150g water, stir 10min, suction filtration, filter cake is dried, and obtains 61g white solid 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, overall yield is 91.8%.
(3) 26.6g1 is taken, 6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g toluene is in 500mL there-necked flask, connect prolong, open water of condensation, 80 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam toluene, obtain that content is 98% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.6g, productive rate is 94.6%, the fusing point of final product is 91 DEG C, and ash content (750 DEG C/2h) is 0.2%.
Embodiment 2
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, with embodiment 1, difference is:
Step (1) temperature of reaction is 30 DEG C, obtains the ethanolic soln containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtain 60.5g white solid 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, overall yield is 91%.
Step (3) obtains 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.4g that content is 97%, and productive rate is 94%, and the fusing point of final product is 90 DEG C, and ash content (750 DEG C/2h) is 0.1%.
Embodiment 3
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, with embodiment 1, difference is:
Step (1) temperature of reaction is 10 DEG C, obtains the ethanolic soln containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtain 60g white solid 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, overall yield is 90.2%.
Step (3) obtains 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.5g that content is 97%, and productive rate is 94.3%, and the fusing point of final product is 90 DEG C, and ash content (750 DEG C/2h) is 0.1%.
Embodiment 4
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, with embodiment 1, difference is:
Step (1) solvent for use is Virahol, obtains the aqueous isopropanol containing dibenzyl aminodithioformic acid sodium.
Step (2) filter cake is dried, and obtain 59.7g white solid 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, overall yield is 89.9%.
Step (3) obtains 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.2g that content is 96%, and productive rate is 93.3%, and the fusing point of final product is 90 DEG C, and ash content (750 DEG C/2h) is 0.1%.
Embodiment 5
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, with embodiment 1, difference is:
Step (2) takes 14.7g1, and 6-dichloro hexane and 0.2gKBr join in this flask, connects prolong, be warming up to system backflow with electric mantle, stir 4 hours under reflux state, after reaction terminates, be cooled to room temperature, suction filtration obtains white filter cake, by filter cake as in 500mL beaker, add about 150g water, stir 10min, suction filtration, filter cake is dried, and obtains 59.8g white solid 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, overall yield is 90.1%.
Step (3) takes 26.6g1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g toluene is in 500mL there-necked flask, connect prolong, open water of condensation, 80 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam toluene, obtain that content is 96% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27g, productive rate is 92.6%, the fusing point of final product is 90 DEG C, and ash content (750 DEG C/2h) is 0.3%.
Embodiment 6
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, step (1) and (2) are with embodiment 1, and difference is:
Step (3) takes 26.6g1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g toluene is in 500mL there-necked flask, connect prolong, open water of condensation, 80 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam toluene, obtain that content is 95% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.8g, productive rate is 95.3%, the fusing point of final product is 91 DEG C, and ash content (750 DEG C/2h) is 0.2%.
Embodiment 7
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, step (1) and (2) are with embodiment 1, and difference is:
Step (3) takes 6.6g1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g dimethylbenzene is in 500mL there-necked flask, connect prolong, open water of condensation, 80 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam dimethylbenzene, obtain that content is 95% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.2g, productive rate is 94%, the fusing point of final product is 91 DEG C, and ash content (750 DEG C/2h) is 0.2%.
Embodiment 8
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, step (1) and (2) are with embodiment 1, and difference is:
Step (3) takes 26.6g1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g120# solvent oil be in 500mL there-necked flask, connect prolong, open water of condensation, 80 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam solvent oil, obtain that content is 96% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.2g, productive rate is 93.3%, the fusing point of final product is 91 DEG C, and ash content (750 DEG C/2h) is 0.2%.
Embodiment 9
The preparation method of a kind of environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, step (1) and (2) are with embodiment 1, and difference is:
Step (3) takes 26.6g1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane, 2.56g Sulfur and 160g toluene is in 500mL there-necked flask, connect prolong, open water of condensation, 90 DEG C are warming up to electric mantle, stir 5 hours at this temperature, after reaction terminates, revolve and steam solvent oil, obtain that content is 95% 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product 27.0g, productive rate is 92.6%, the fusing point of final product is 91 DEG C, and ash content (750 DEG C/2h) is 0.2%.
Claims (10)
1. the preparation method of an environmental protection, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, comprises step as follows:
(1) with dibenzylamine, sodium hydroxide and dithiocarbonic anhydride for raw material, join in solvent, after having reacted, obtain the solution containing dibenzyl aminodithioformic acid sodium;
(2) 1 is added to obtained the containing in the solution of dibenzyl aminodithioformic acid sodium of step (1), 6-dichloro hexane and catalyzer, react at reflux, after completion of the reaction, suction filtration, filter cake is washed, remove side product chlorinated sodium, suction filtration again after washing, filter cake obtains 1 after drying, 6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane;
(3) by obtained 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and sulphur adds in organic solvent, react at temperature 70-100 DEG C, after completion of the reaction, removing organic solvent, obtains 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane product.
2. the preparation method of environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, it is characterized in that, described in step (1), solvent is methyl alcohol, ethanol or Virahol.
3. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, in step (1), the mol ratio of dibenzylamine, sodium hydroxide and dithiocarbonic anhydride is 1:(1.0 ~ 1.3): (1.1 ~ 1.3), the mass ratio of dibenzylamine and solvent is 1:(5 ~ 8).
4. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, in step (1), dithiocarbonic anhydride joins in reaction system in dropping mode, dropwise in 30min, in step (1), temperature of reaction is 0-50 DEG C, and the reaction times is 3-5 hour, preferably, temperature of reaction is 10-35 DEG C, and the reaction times is 4-5 hour.
5. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, in step (2) 1, the add-on of 6-dichloro hexane be 1.0:(2.1 ~ 2.3 containing the mol ratio of dibenzyl aminodithioformic acid sodium in dibenzyl aminodithioformic acid sodium solution), wherein, the yield of dibenzyl aminodithioformic acid sodium calculates with 95%.
6. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, catalyzer in step (2) is KI or KBr, and the add-on of catalyzer is 0.1 ~ 0.5% of dibenzyl aminodithioformic acid sodium quality.
7. environmental protection according to claim 1, high performance vulcanization linking agent 1, the preparation method of 6-bis-(N, N-dibenzyl amino formyl two sulphur) hexane, is characterized in that, temperature of reaction in step (2) is 70-85 DEG C, and the reaction times is 3-5 hour.
8. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, organic solvent described in step (3) is toluene, dimethylbenzene or 120# solvent oil.
9. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, 1,6-bis-(N in step (3), N-dibenzyl amino formyl one sulphur) mol ratio of hexane and sulphur is 1:(2.0 ~ 2.2), the mass ratio of 1,6-bis-(N, N-dibenzyl amino formyl one sulphur) hexane and organic solvent is 1:(5 ~ 8).
10. environmental protection according to claim 1, high performance vulcanization linking agent 1,6-bis-(N, N-dibenzyl amino formyl two sulphur) preparation method of hexane, it is characterized in that, step (3) temperature of reaction is 80-95 DEG C, reaction times is 5-7 hour, and organic solvent adopts underpressure distillation mode to remove.
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Application publication date: 20160420 Assignee: SHANDONG DAIRUIKE NEW MATERIALS Co.,Ltd. Assignor: SHANDONG YANGGU HUATAI CHEMICAL Co.,Ltd. Contract record no.: X2024980005534 Denomination of invention: Preparation method of an environmentally friendly and efficient sulfurization crosslinking agent 1,6-di (N, N-dibenzylaminomethyl disulfide) hexane Granted publication date: 20170630 License type: Common License Record date: 20240510 |