CN103613523B - A kind of Thiocarbamic acid derivatives and preparation method thereof - Google Patents
A kind of Thiocarbamic acid derivatives and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of preparation method of simple to operate, environmental protection to prepare a kind of Thiocarbamic acid derivatives, with organic thiosulfate and thiocarbamate sodium for raw material, methylene dichloride can be added and formaldehyde adds fast response in reaction process, reaction terminates rear suction filtration and isolates solid product, filtrate can recycle and reuse, continuous production Thiocarbamic acid derivatives.The methylene dichloride boiling point added in reaction process is low, can reduce temperature of reaction, reduce energy consumption, and methylene dichloride is nonflammable, improves the safety performance in production process.
Description
Technical field
The invention belongs to rubber industry processing aid field, be specifically related to a kind of anti-recovery agent Thiocarbamic acid derivatives and preparation method thereof.
Background technology
Rubber is a kind of chain macromolecular material, add vulcanizing agent and with it crosslinking reaction can occur, form tridimensional network, make rubber become resilient material from plastic material, rubber is had in wide temperature range elasticity is high, plasticity is little, intensity is large use properties.When cross-linked rubber over cure or under being in use exposed to anaerobism thermal ageing condition in process of production, will reversion be there is in sulfur cross-linking sizing material, in addition, many sizing materials heat-dissipating is in use enough to cause cross-linked network to be degraded, so that cause product easily to damage, work-ing life shortens, and reversion can cause rubber item inside and surface property heterogeneity, affect the use properties of product, thus people constantly make great efforts to explore the reversion resistance how improving rubber item.
In tyre industry, simultaneously the traditional method being used for improving sizing material anti-reversion behaviour increases accelerator level to reduce sulfur consumption, and effectively utilize added sulphur, the generation reducing polysulfidic bond obtains higher stability.Some are also had to have the auxiliary agent improving effect, as soap can improve processing characteristics as multi-functional processing aid, cure efficiency can be improved again, also be widely used in rubber industry, most is representational is the zinc soap compound of fragrant acids, effectively can improve the anti-reversion behaviour of NR sulfuration.In addition, some company is proposed offset-type vulcanization system to make up the loss of cross-link bond, keeps the cross-linking density of sizing material, as DuralinkHTS (two hydration hexa-methylenes 1,6-bisthiosulfate disodium salt), Perkalink900 (1,3-lemon imide methyl) benzene etc.
About Monsanto Chemicals develops DuralinkHTS at first in the 1980s, is used for improving the stability of polysulfide crosslink bond, but finds that it can also increase processing safety afterwards.DuralinkHTS contains sulphur atom and carbon atom, during sulfuration, HTS inserts a hexa-methylene disulfide group group in polysulfide crosslink bond, embed longer softness in cross-link bond structure and there is the alkyl of thermostability, the generation of this composite crosslinking key can make the cross-linked rubber aging resistance of resistance to anaerobism improve, improve the thermostability of cross-link bond, thus improve the flexibility of sizing material under dynamic operation, improve the antireversion of sizing material.
KA-9188, chemical name is 1, two (the N of 6-, the curing of N-dibenzyl thiocarbamyl) hexane, be the tentative product of German BayerAG, be applicable to produce the cross-linked rubber of the natural rubber (NR) of high anti-recovery, synthetic polyisoprene (IR), styrene-butadiene rubber(SBR) (SBR), divinyl rubber (BR) and these elastomeric Blend rubber.
KA-9188 chemical structural formula is as follows:
KA-9188 is a kind of new and effective multiple crosslinking agent with complete promotor residue, the structure both with dithiocarbamatetype accelerator in its molecule, also with the dithio hexane group of postcure stablizer.KA-9188 anti-revert the mechanism of action and HTS similar, the sulphur sulfur bonds in rubber vulcanization process Middle molecule structure, middle C6 aliphatic chain is connected in rubber molecule together with two sulphur at its two ends, plays the effect of sulfuration.In over cure process due to cross-link bond in introduce C6 aliphatic chain, in C6 aliphatic chain, the bond energy of carbon-carbon bond is greater than sulphur sulfide linkage, so carbon-carbon bond can not rupture, the cross-linked network of sizing material is more stable, and reversion phenomenon can not occur.Secondly, in KA9188 structure, the structure at two ends is vulcanization accelerator, can play the effect of accelerated stock sulfuration.
Chinese Patent Application No. is disclose a kind of method that dithiocarbamic acid prepares dithiol derivatives in 200510078884.3: under water, carbonyl compound and organic solvent exist, pH is 7 ~ 14, temperature of reaction is under 0 ~ 90 DEG C of condition, diphenyl-methyl nabam and hexa-methylene 1, the two thiosulfuric acid disodium dihydrate of 6-reacts, and synthesizes dithiol derivatives.In technical scheme disclosed in this patent (see specification sheets 11-16 page), organic solvent can be aromatic solvent, aliphatic hydrocarbon or clicyclic hydrocarbon, as toluene, chlorobenzene, normal hexane, hexanaphthene, this several solvent is inflammable liquid, reduces the security in production process; And toluene, normal hexane, hexanaphthene equal solvent density ratio water are little, are in layer waterborne, easily contact with air and cause fire.In addition, when this patent adopts solvent method to prepare dithiol derivatives, a large amount of waste liquid containing organic solvent can be produced, contaminate environment.
For improving the security in production process, in the present invention, provide a kind of technical scheme of environmental protection to prepare Thiocarbamic acid derivatives.With organic thiosulfate and thiocarbamate sodium for raw material, can add methylene dichloride and formaldehyde to improve reaction efficiency in preparation process, methylene dichloride density ratio water is large, is positioned at subsurface layer, operational safety; And after the completion of reaction, after suction filtration, can product be isolated, the filtrate after suction filtration can be recycled, continuous production Thiocarbamic acid derivatives.
Summary of the invention
The invention provides a kind of preparation method of simple to operate, environmental protection, with organic thiosulfate and thiocarbamate sodium for raw material, methylene dichloride can be added and formaldehyde adds fast response in reaction soln, reaction terminates rear suction filtration and isolates solid product, filtrate can recycle and reuse, continuous production Thiocarbamic acid derivatives.The methylene dichloride boiling point added in reaction process is low, can reduce temperature of reaction, reduce energy consumption, and methylene dichloride is nonflammable, improves the safety performance in production process.In addition, in the present invention, filtrate can recycle, continues to use as reaction solvent, can the Thiocarbamic acid derivatives of continuous production height yield, reduces environmental pollution.
The Thiocarbamic acid derivatives structural formula prepared by aforesaid method is as follows:
Wherein, R
1, R
2, R
3, R
4can be identical or different, be selected from the one in hydrogen, methyl, ethyl, butyl, phenyl, benzyl independently of one another, R
1r
2n-, R
3r
4n-also can be formed as pyrrolidyl.
The preparation method of Thiocarbamic acid derivatives is as follows:
Step (1) adopts the reaction vessel that whipping appts, temperature regulating device and reflux condensate device are housed, and adds the organic thiosulfate aqueous solution;
Step (2) adds sodium bicarbonate and optional formaldehyde in the above-mentioned organic thiosulfate aqueous solution, and 15 ~ 30 DEG C are stirred 30 ~ 120min;
Step (3) optionally adds methylene dichloride;
Step (4) dropwise adds thiocarbamate sodium solution, 15 ~ 30 DEG C of stirring reaction 3 ~ 6h;
Step (5) stops stirring, and suction filtration, after washing solid product, 60 ~ 80 DEG C are dried to constant weight, obtain Thiocarbamic acid derivatives.
Wherein, the organic thiosulfate in step (1) can be the two sodothiol dihydrate (HTS) of 1,6-, and the mass percentage concentration of the organic thiosulfate aqueous solution is 10 ~ 20%.
In step (2), the mol ratio of sodium bicarbonate and organic thiosulfate is 0.5: 1 ~ 1.5: 1, and the mol ratio of formaldehyde and organic thiosulfate is 0: 1 ~ 1.8: 1, is preferably 0.5: 1 ~ 1.5: 1; The formaldehyde added can be formalin, and the mass percentage concentration of formalin is 20 ~ 35%.When synthesizing that in Thiocarbamic acid derivatives process, formaldehyde consumption is 0, the reaction times can longer (>=8h), and reaction solution be emulsion after the completion of reaction, and after needing sedimentation 24h, Thiocarbamic acid derivatives is just understood and be separated out from solution.
In step (3), the mol ratio of methylene dichloride and organic thiosulfate is 0: 1 ~ 5: 1, is preferably 0.5: 1 ~ 3: 1.In synthesis Thiocarbamic acid derivatives process, the consumption of methylene dichloride can be 0, this the reaction time can extend (>=8h), and can emulsion be obtained after the completion of reaction, after needing sedimentation 24h, Thiocarbamic acid derivatives just can be separated out from solution; When methylene chloride is higher than amount ranges of the present invention, the target product obtained becomes particulate state, is wherein enclosed with Na
2sO
3by product, reduces product purity.
In step (4), thiocarbamate sodium solution mass percentage concentration is 20 ~ 25%, and the mol ratio of thiocarbamate sodium and organic thiosulfate is 1.8: 1 ~ 2.1: 1.Thiocarbamate sodium can be selected from monomethyl nabam, Sodium dimethyldithiocarbamate 40min, Thiocarb, NB sodium dibutyl dithiocarbamate, phenyl nabam, dibenzyl aminodithioformic acid sodium, Sodium tetramethylenedithiocarbamate one or more.
Filtrate after step (5) suction filtration can recycle and reuse, the Thiocarbamic acid derivatives of continuous production height yield.Because the filtrate pH value obtained is 11 ~ 12, in this solution environmental, can decomposition reaction be there is in the organic thiosulfate in raw material, be unfavorable for the carrying out reacted, and the product purity obtained also can reduce, therefore need again to add in the filtrate of reclaiming after sodium bicarbonate carrys out the pH value to 9 of regulator solution, use as the solvent preparing Thiocarbamic acid derivatives next time.
Compared with prior art, its usefulness is in the present invention:
(1) methylene dichloride added in reaction solution, its advantage is that methylene dichloride boiling point is low, reduces temperature of reaction, reduce energy consumption, and methylene dichloride belongs to non-combustible liquid, and density ratio water is large, is positioned at subsurface layer, operational safety;
(2) reaction terminates rear filtrate and can reclaim, and continues to use as reaction solvent, can the Thiocarbamic acid derivatives of continuous production height yield, reduces environmental pollution.
Technique of the present invention is simple, energy consumption is low, reproducible, meet the developing direction of safety, green, environmental protection, therefore there is great development prospect.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.It should be noted that; what below enumerate is only some specific embodiments of the present invention; in obvious the present invention, these embodiments only illustrate technical scheme in the present invention for explaining in detail and are not used in and limit the scope of the invention; other all distortion of directly deriving from content of the present invention or associating, all should think protection scope of the present invention.
Embodiment 1
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, take 14.2g bis-hydration hexa-methylene 1,6-bisthiosulfate disodium salt (DuralinkHTS, purchased from Flexsys) join in flask, add 36.4g water, stir after HTS is dissolved, add 3.2g sodium bicarbonate, 3.4g mass percentage concentration is the formalin of 35%, after 20 DEG C of stirring 30min, add 9.2g methylene dichloride.Then drip 94.5g mass percentage concentration be 25% dibenzyl aminodithioformic acid sodium solution (dibenzyl aminodithioformic acid sodium, purchased from lark prestige Science and Technology Ltd., purity: 98%), 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 26.4g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 95.3%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-dibenzyl thiocarbamyl) hexane of continuous production 1,6-.
The filtrate taken after 40g suction filtration is poured in above-mentioned reaction vessel, after adding the pH value to 9 of 4.0g manganese hydrogen sodium regulating solution, add 14.2gHTS, after stirring makes HTS dissolve, add the formalin that 3.0g mass percentage concentration is 35%, 20 DEG C are stirred 30min, add 8.0g methylene dichloride, then the dibenzyl aminodithioformic acid sodium solution that 94.5g mass percentage concentration is 25% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 24.7g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 89.1%.
Embodiment 2
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 8.2gHTS joins in flask, add 80g water, after stirring makes HTS dissolve, add 1.0g sodium bicarbonate, 3.5g mass percentage concentration is the formalin of 20%, 20 DEG C are stirred 30min, add 5.9g methylene dichloride.Then the dibenzyl aminodithioformic acid sodium solution that 60.0g mass percentage concentration is 20% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 6.6g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 92.7%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-dibenzyl thiocarbamyl) hexane of continuous production 1,6-.
The filtrate taken after 80g suction filtration is poured in above-mentioned reaction vessel, add after the pH value of solution is adjusted to 9 by 3.0g sodium bicarbonate, add 6.8gHTS, after stirring makes HTS dissolve, add the formalin that 2.5g mass percentage concentration is 20%, 20 DEG C are stirred 30min, add 4.0g methylene dichloride, then the dibenzyl aminodithioformic acid sodium solution that 60.0g mass percentage concentration is 20% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 6.4g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 89.9%.
Embodiment 3
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 14.5gHTS joins in flask, add 24g water, after stirring makes HTS dissolve, add 5.2g sodium bicarbonate, 9.2g mass percentage concentration is the formalin of 20%, 25 DEG C are stirred 30min, add 1.7g methylene dichloride.Then the dibenzyl aminodithioformic acid sodium solution that 102.0g mass percentage concentration is 25% is dripped, 25 DEG C of stirring reaction 4h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 13.6g1 in 70 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 95.4%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-dibenzyl thiocarbamyl) hexane of continuous production 1,6-.
Filtrate the pouring into taken after 80g suction filtration is equipped with in the 500mL four-hole boiling flask of whipping appts, thermometer and reflux exchanger, add after the pH value of solution is adjusted to 9 by 3.0g sodium bicarbonate, add 15.0gHTS, after stirring makes HTS dissolve, add the formalin that 6.5g mass percentage concentration is 20%, 25 DEG C are stirred 30min, add 9.0g methylene dichloride, then the dibenzyl aminodithioformic acid sodium solution that 105.0g mass percentage concentration is 20% is dripped, 25 DEG C of stirring reaction 4h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 13.1g1 in 70 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 89.1%.
Embodiment 4
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 9.0gHTS joins in flask, add 40g water, after stirring makes HTS dissolve, add 2.2g sodium bicarbonate, 1.2g mass percentage concentration is the formalin of 25%, 25 DEG C are stirred 30min, add 4.4g methylene dichloride.Then the dibenzyl aminodithioformic acid sodium solution that 69.8g mass percentage concentration is 22% is dripped, 25 DEG C of stirring reaction 3h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 8.3g1 in 75 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 91.9%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-dibenzyl thiocarbamyl) hexane of continuous production 1,6-.
The filtrate taken after 40g suction filtration is poured in above-mentioned reaction vessel, after adding the pH value to 9 of 3.0g manganese hydrogen sodium regulating solution, add 9.0gHTS, after stirring makes HTS dissolve, add the formalin that 5.0g mass percentage concentration is 20%, 20 DEG C are stirred 30min, add 3.5g methylene dichloride, then the dibenzyl aminodithioformic acid sodium solution that 69.8g mass percentage concentration is 22% is dripped, 20 DEG C of stirring reaction 4.5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 7.9g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 87.4%.
Embodiment 5
First reaction process: make solvent with water.
Adopt the 500mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 18.2gHTS joins in flask, add 80g water, after stirring makes HTS dissolve, add 4.4g sodium bicarbonate, 5.2g mass percentage concentration is the formalin of 30%, 30 DEG C are stirred 30min, add 6.6g methylene dichloride.Then dripping 147.7g mass percentage concentration is 20% dibenzyl aminodithioformic acid sodium solution, 30 DEG C of stirring reaction 4h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 17.2g1 in 80 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 95.2%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-dibenzyl thiocarbamyl) hexane of continuous production 1,6-.
The filtrate taken after 80g suction filtration is poured in above-mentioned reaction vessel, add after the pH value of solution is adjusted to 9 by 6.0g sodium bicarbonate, add 14.2gHTS, after stirring makes HTS dissolve, add the formalin that 6.0g mass percentage concentration is 20%, 20 DEG C are stirred 30min, add 5.5g methylene dichloride, then the dibenzyl aminodithioformic acid sodium solution that 94.5g mass percentage concentration is 25% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 12.5g1 in 60 DEG C of baking ovens, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 89.9%.
Embodiment 6
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 14.2gHTS joins in flask, add 36.4g water, after stirring makes HTS dissolve, add 3.2g sodium bicarbonate, 3.4g mass percentage concentration is the formalin of 35%, 20 DEG C are stirred 30min, add 9.2g methylene dichloride.Then drip 68.4g mass percentage concentration be 20% Thiocarb solution (Thiocarb, purchased from Chemical Reagent Co., Ltd., Sinopharm Group, purity: 98%), 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 14.5g1 in 60 DEG C of baking ovens, two (curing of N, N-diethyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 81.7%.
Second reaction process: make solvent with the filtrate after suction filtration, two (curing of N, the N-diethyl thiocarbamyl) hexane of continuous production 1,6-.
The filtrate taken after 40g suction filtration is poured in above-mentioned reaction vessel, add after the pH value of solution is adjusted to 9 by 4.0g sodium bicarbonate, add 14.2gHTS, after stirring makes HTS dissolve, add the formalin that 3.0g mass percentage concentration is 35%, 20 DEG C are stirred 30min, add 8.0g methylene dichloride, then the Thiocarb solution that 68.4g mass percentage concentration is 20% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 13.4g1 in 60 DEG C of baking ovens, two (curing of N, N-diethyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 75.5%.
Embodiment 7
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 14.2gHTS joins in flask, add 36.4g water, after stirring makes HTS dissolve, add 3.2g sodium bicarbonate, 3.4g mass percentage concentration is the formalin of 35%, 20 DEG C are stirred 30min, add 9.2g methylene dichloride.Then drip 52.1g mass percentage concentration be 22% Sodium dimethyldithiocarbamate 40min solution (Sodium dimethyldithiocarbamate 40min, purchased from lark prestige Science and Technology Ltd., purity: 98%), 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 14.7g1 in 60 DEG C of baking ovens, two (curing of N, N-dimethyl thio carbamyl) the hexane pressed powder of 6-, counting yield yield is about 77.8%.
Second reaction process: make solvent with the filtrate after suction filtration, continuous production Thiocarbamic acid derivatives.
The filtrate taken after 40g suction filtration is poured in above-mentioned reaction vessel, add after the pH value of solution is adjusted to 9 by 4.0g sodium bicarbonate, add 14.2gHTS, after stirring makes HTS dissolve, add the formalin that 3.0g mass percentage concentration is 35%, 20 DEG C are stirred 30min, add 8.0g methylene dichloride, then the Sodium dimethyldithiocarbamate 40min solution that 52.1g mass concentration is 22% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 13.9g1 in 60 DEG C of baking ovens, two (curing of N, N-dimethyl thio carbamyl) the hexane pressed powder of 6-, counting yield yield is about 73.6%.
Embodiment 8
First reaction process: make solvent with water.
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 14.2gHTS joins in flask, add 36.4g water, after stirring makes HTS dissolve, add 3.2g sodium bicarbonate, 3.4g mass percentage concentration is the formalin of 35%, 20 DEG C are stirred 30min, add 9.2g methylene dichloride.Then drip 67.7g concentration be 20% Sodium tetramethylenedithiocarbamate solution (Sodium tetramethylenedithiocarbamate, grinds territory (Shanghai) chemical reagent company limited, purity: 99%), 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 15.4g1 in 60 DEG C of baking ovens, two (curing of tetramethyleneimine thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 79.5%.
Second reaction process: make solvent with the filtrate after suction filtration, continuous production Thiocarbamic acid derivatives.
The filtrate taken after 40g suction filtration is poured in above-mentioned reaction vessel, add after the pH value of solution is adjusted to 9 by 4.0g sodium bicarbonate, add 14.2gHTS, after stirring makes HTS dissolve, add the formalin that 3.0g mass percentage concentration is 35%, 20 DEG C are stirred 30min, add 8.0g methylene dichloride, then the Sodium tetramethylenedithiocarbamate solution that 67.7g mass percentage concentration is 20% is dripped, 20 DEG C of stirring reaction 5h.By above-mentioned solution suction filtration, after the solid phase prod obtained is washed, be dried to constant weight, obtain 14.4g1 in 60 DEG C of baking ovens, two (curing of tetramethyleneimine thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 78.0%.
Embodiment 9 (according to the embodiment in embodiment 1, but not adding formaldehyde solution in reaction process)
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, take 14.2gHTS and join in flask, add 36.4g water, stir after HTS is dissolved, add 3.2g sodium bicarbonate, 20 DEG C are stirred 30min, add 9.2g methylene dichloride.Then drip the dibenzyl aminodithioformic acid sodium solution that 94.5g mass percentage concentration is 25%, 20 DEG C of stirring reaction 8h, the reaction solution obtained is milk sap, separates out there are no solid.By suction filtration after above-mentioned solution left standstill 24h, after the solid phase prod obtained is washed, in 60 DEG C of baking ovens, be dried to constant weight, obtain 21.1g1, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 76.2%.
Embodiment 10 (according to the embodiment in embodiment 1, but not adding methylene dichloride in reaction process)
Adopt the 250mL four-hole boiling flask that whipping appts, thermometer and reflux exchanger are housed, taking 14.2gHTS joins in flask, adds 36.4g water, stirs after HTS is dissolved, add 3.2g sodium bicarbonate, 3.4g mass percentage concentration is the formalin of 35%, 20 DEG C are stirred 30min.Then drip the dibenzyl aminodithioformic acid sodium solution that 94.5g mass percentage concentration is 25%, 20 DEG C of stirring reaction 8h, the reaction solution obtained is milk sap, separates out there are no solid.By suction filtration after above-mentioned solution left standstill 24h, after the solid phase prod obtained is washed, after being dried to constant weight in 60 DEG C of baking ovens, obtain 20.5g1, two (curing of N, N-dibenzyl thiocarbamyl) the hexane pressed powder of 6-, counting yield yield is about 74.0%.
As can be seen from embodiment 9 and embodiment 10, in reaction process, do not add formaldehyde or methylene dichloride, extend the reaction times, and reaction to terminate rear solution be milk sap, product can not be separated out in time from solution, and can only separate out portioned product after leaving standstill 24h, the product yield obtained is lower.
The test result of S element percentage composition in the Thiocarbamic acid derivatives sample that embodiment 1 ~ 10 obtains is listed in table 1, wherein in embodiment 1-8, lastrow numerical value is the Thiocarbamic acid derivatives sample tests that the first reaction process (taking water as solvent) obtains, and next line numerical value is the Thiocarbamic acid derivatives sample tests that the second reaction process (making solvent with the filtrate of reclaiming) obtains.
The percentage composition of S element in table 1. embodiment 1 ~ 10 sample
As can be seen from the test result in table 1, in Thiocarbamic acid derivatives prepared in embodiment 1-10, the percentage composition of S element is close with theoretical value, illustrate that the purity of the Thiocarbamic acid derivatives of employing prepared by technical scheme of the present invention is higher, purity > 95%.
Claims (7)
1. a preparation method for Thiocarbamic acid derivatives, is characterized in that containing following steps:
Step (1) adopts the reaction vessel that whipping appts, temperature regulating device and reflux condensate device are housed, and adds the organic thiosulfate aqueous solution;
Step (2) adds sodium bicarbonate and formaldehyde in the above-mentioned organic thiosulfate aqueous solution, and 15 ~ 30 DEG C are stirred 30 ~ 120min;
Step (3) adds methylene dichloride;
Step (4) dropwise adds thiocarbamate sodium solution, and 15 ~ 30 DEG C are stirred 3 ~ 6h;
Step (5) stops stirring, and suction filtration, after washing solid product, 60 ~ 80 DEG C are dried to constant weight, obtain Thiocarbamic acid derivatives.
2. preparation method as claimed in claim 1, it is characterized in that the organic thiosulfate described in step (1) is the two sodothiol dihydrate of 1,6-, the mass percentage concentration of the organic thiosulfate aqueous solution is 10 ~ 20%.
3. preparation method as claimed in claim 1, is characterized in that the mol ratio of the sodium bicarbonate described in step (2) and organic thiosulfate is 0.5: 1 ~ 1.5: 1.
4. preparation method as claimed in claim 1, it is characterized in that the formaldehyde described in step (2) is formalin, formalin concentration is 20 ~ 35%, and the mol ratio of formaldehyde and organic thiosulfate is 0.5: 1 ~ 1.5: 1.
5. preparation method as claimed in claim 1, is characterized in that the mol ratio of the methylene dichloride described in step (3) and organic thiosulfate is preferably 0.5: 1 ~ 3: 1.
6. preparation method as claimed in claim 1, it is characterized in that the thiocarbamate sodium described in step (4) is selected from monomethyl nabam, Sodium dimethyldithiocarbamate 40min, Thiocarb, NB sodium dibutyl dithiocarbamate, phenyl nabam, dibenzyl aminodithioformic acid sodium, Sodium tetramethylenedithiocarbamate one or more.
7. preparation method as claimed in claim 1, it is characterized in that the thiocarbamate sodium solution mass percentage concentration described in step (4) is 20 ~ 25%, the mol ratio of thiocarbamate sodium and organic thiosulfate is 1.8: 1 ~ 2.1: 1.
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| CN105152997A (en) * | 2015-08-01 | 2015-12-16 | 江苏麒祥高新材料有限公司 | Preparation method for dithiocarbamic acid serial sulfuration cross-linking agent |
| CN105503677B (en) * | 2015-12-04 | 2017-06-30 | 山东阳谷华泰化工股份有限公司 | A kind of environmental protection, high performance vulcanization crosslinking agent 1,6 2（The sulphur of N, N dibenzyl amino formyl two）The preparation method of hexane |
| CN109233035B (en) * | 2018-08-22 | 2020-10-23 | 江苏麒祥高新材料有限公司 | Rubber anti-reversion agent with particle size of 40-100 mu m and novel synthesis method thereof |
| CN111763165B (en) * | 2019-04-02 | 2022-07-08 | 康一昕 | Preparation method of dithiocarbamic acid vulcanization crosslinking agent |
| CN112430204A (en) * | 2020-11-24 | 2021-03-02 | 江苏麒祥高新材料有限公司 | 1, 6-bis (N, N' -dibenzyl thiocarbamoyl disulfide) hexane as anti-reversion agent and preparation method thereof |
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| US20030088023A1 (en) * | 2000-02-04 | 2003-05-08 | Shinichi Motofusa | Rubber composition and pneumatic tire |
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| US20030088023A1 (en) * | 2000-02-04 | 2003-05-08 | Shinichi Motofusa | Rubber composition and pneumatic tire |
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