CN104402783B - A kind of preparation method of sulfhydryl compound - Google Patents
A kind of preparation method of sulfhydryl compound Download PDFInfo
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- CN104402783B CN104402783B CN201410777256.3A CN201410777256A CN104402783B CN 104402783 B CN104402783 B CN 104402783B CN 201410777256 A CN201410777256 A CN 201410777256A CN 104402783 B CN104402783 B CN 104402783B
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- -1 sulfhydryl compound Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000004480 active ingredient Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 229920006295 polythiol Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920002578 polythiourethane polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- KPRYYQKFHVHLFR-UHFFFAOYSA-N CNCCNC(CN)CNCCN Chemical compound CNCCNC(CN)CNCCN KPRYYQKFHVHLFR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical group C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000012485 toluene extract Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application provides a kind of preparation method of sulfhydryl compound, comprise the following steps: under the effect of catalyzer, the compound shown in formula II and hydrogen sulfide are reacted at the temperature of 30 DEG C ~ 90 DEG C, obtains the sulfhydryl compound shown in formula I; Described catalyzer is the loaded catalyst of cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of molybdenum system.The method reaction conditions of the hydrogen sulfide sulfhydrylation that the application provides is gentleer than traditional method, have that energy consumption is low, wastewater flow rate greatly reduces the advantage greatly reduced with raw materials cost, and described hydrogen sulfide sulfhydrylation method can shorten the production cycle of a few hours than traditional technology, thus brings more economic benefits and social benefit.Further, the sulfhydryl compound prepared by the application is applied as oil phase product, and without the need to the extraction of organic solvent as toluene, direct separatory washs, and namely the application's post-treating method is simple and easy to do, effective.
Description
Technical field
The invention belongs to optical resin technical field, particularly relate to a kind of preparation method of sulfhydryl compound.
Background technology
The specific refractory power of main flow glasses lens is about 1.5 in the market, and therefore as made high power lens, must be realized by the thickness increasing glasses lens, this also just adds the weight of glasses simultaneously.Compared with opticglass, optical resin has that quality is light, shock resistance and the easy advantage such as machine-shaping, can be applied to the products such as glasses lens better.See table 1, table 1 is eyeglass optical resin main Types.
Table 1 eyeglass optical resin main Types
At present, on market with polythiol and isocyanic ester for optical resin prepared by raw material is mainly polythiourethane resinoid, wherein, polythiol is the oligopolymer that a class contains multi-active base group sulfydryl, also can be described as polythiol.From table 1, the resinoid specific refractory power of polythiourethane can up to 1.77, other resins on market.Because the specific refractory power of resin material is higher, prepared eyeglass can curvature larger, can make eyeglass thinner, lighter, be more suitable for wearing, polythiourethane resinoid is one of prior development direction of Novel optical resin in recent years.
When adopting low-molecular-weight mercaptan to be optical resin synthesis material, its stink directly affects the health of direct labor.And the polythiol preparing macromolecule greatly can reduce stink, in addition, due to the active reactive group that sulfydryl is mercaptan, the number increasing mercapto groups on molecule not only can promote the carrying out of crosslinking reaction, shorten the preparation process of resin, and the specific refractory power of resin can be improved, thus synthesize high-end resin material.Therefore, research and develop the polythiol with many sulfydryls to have great importance.At present, domestic a lot of producer all adopts the sulfhydryl compound shown in the formula I of external import to prepare optical resin.
Three sulfydryls in sulfhydryl compound (polythiol) shown in formula I not only make it have very high specific refractory power, and more can react with isocyano and prepare optical resin, be a kind of important source material preparing optical resin.The Chinese patent literature that publication number is CN1164540A discloses the preparation method of the sulfhydryl compound shown in a kind of formula I, its synthesis detailed process is: 2 mercapto ethanol and sodium hydroxide are reacted, then Epicholorohydrin is added drop-wise in the above-mentioned mixed solution be obtained by reacting and reacts, add hydrochloric acid HCl to be again precipitated, to obtain the liquid triol shown in formula II after precipitate and separate, principal reaction formula is such as formula shown in (1).Aforesaid method then in described liquid triol, adds HCl and thiocarbamide refluxes, and form the isothiuronium salts hydrochlorate shown in formula III, reaction formula is such as formula shown in (2); Finally add sodium hydroxide solution, described isothiuronium salts hydrochlorate is hydrolyzed, the sulfhydryl compound shown in production I, reaction formula is such as formula shown in (3).For the aftertreatment of described sulfhydryl compound, aforesaid method adopts toluene to extract, and carries out acidity and washing successively afterwards, originally alkaline product is washed till neutrality, is washed off by residual salt simultaneously; Finally toluene anhydrous sodium sulphate is carried out drying, through concentrated obtained sulfhydryl compound shown in formula I.
Aforesaid method first prepares polyol, then adopts thiocarbamide-hydrochloric acid method to make conversion of hydroxyl become isothiuronium salts, finally adopts alkaline solution scission of link to generate polythiol.Although this method has obtained the sulfhydryl compound shown in formula I, there is following problem in its synthetic route: adopt thiocarbamide to prepare isothiuronium salts, cost is higher; With content about 36% concentrated hydrochloric acid for catalyst preparing isothiuronium salts, produce a lot of waste water because concentrated hydrochloric acid consumption is large; Take sodium hydroxide as hydrolyst, because its alkalescence is comparatively strong, and the sulfhydryl compound shown in formula I shows slightly acidic, and sodium hydroxide is easy to react with the sulfydryl (-SH) of described sulfhydryl compound generate water-soluble sulfydryl sodium salt (-SNa
+), be unfavorable for that follow-up toluene extracts described sulfhydryl compound, and also bring a large amount of waste water; Technique from triol to polythiol is consuming time long, adds production cost.
Summary of the invention
In view of this, the application provides a kind of preparation method of sulfhydryl compound, and the method reaction conditions of the sulfhydryl compound shown in preparation formula I of the present invention is gentle, can reduce energy consumption, reduces waste water, greatly reduces raw materials cost, shortens the production cycle.
The application provides a kind of preparation method of sulfhydryl compound, comprises the following steps:
Under the effect of catalyzer, the compound shown in formula II and hydrogen sulfide are reacted at the temperature of 30 DEG C ~ 90 DEG C, obtains the sulfhydryl compound shown in formula I; Described catalyzer is the loaded catalyst of cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of molybdenum system;
Preferably, described catalyzer comprises:
Carrier, described carrier is aluminum oxide, cerium oxide or molecular sieve; With
Load active ingredient on the carrier, described active ingredient is at least one in the oxide compound of cobalt and the oxide compound of molybdenum.
Preferably, the preparation method of the compound shown in described formula II comprises the following steps:
Be under the condition of 10 DEG C ~ 30 DEG C in temperature, 2 mercapto ethanol and alkaline compound solution reacted, reacts and obtain sulfydryl metal-salt after at least 10 minutes; Add Epicholorohydrin afterwards, react at the temperature of 30 DEG C ~ 60 DEG C, obtain the compound shown in formula II.
Preferably, described alkaline compound solution is sodium hydroxide solution or potassium hydroxide solution;
Described 2 mercapto ethanol is (2 ~ 3) with the molar equivalent ratio of Epicholorohydrin: 1;
Described alkaline compound solution neutral and alkali compound is (1 ~ 2) with the molar equivalent ratio of Epicholorohydrin: 1.
Preferably, the charge capacity of described active ingredient is 10% ~ 50%; The consumption of described catalyzer is 0.01% ~ 10% of Epicholorohydrin quality.
Preferably, the reaction between described 2 mercapto ethanol and alkaline compound solution is at N
2carry out under existent condition.
Preferably, the molar equivalent of the compound shown in described formula II and hydrogen sulfide is than being 1:(3 ~ 6).
Preferably, the time of the compound shown in described formula II and the reaction between hydrogen sulfide is at least 3 hours.
Preferably, after the compound shown in described formula II and the reaction between hydrogen sulfide terminate, the lower floor's oil phase be obtained by reacting is cut out, is washed to neutrality, after filtration, obtain the sulfhydryl compound shown in formula I.
Preferably, when the compound shown in described formula II and hydrogen sulfide react, also comprise: remaining hydrogen sulfide will be reacted through cushioning laggard row tail gas absorption.
Compared with prior art, the application with cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and molybdenum system mixing loaded catalyst for catalyzer, be under the condition of 30 DEG C ~ 90 DEG C in temperature, compound shown in formula II and hydrogen sulfide are reacted, obtains the sulfhydryl compound shown in formula I.The application is in the preparation process of polythiol, controlling certain temperature adopts hydrogen sulfide carry out sulfhydrylation and instead of traditional thiocarbamide-hydrochloric acid method, and this process is realized by the loaded catalyst adding cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of molybdenum system.The method reaction conditions of the hydrogen sulfide sulfhydrylation that the application provides is gentleer than traditional method, have that energy consumption is low, wastewater flow rate greatly reduces the advantage greatly reduced with raw materials cost, and described hydrogen sulfide sulfhydrylation method can shorten the production cycle of a few hours than traditional technology, thus brings more economic benefits and social benefit.
Further, the sulfhydryl compound prepared by the application is applied as oil phase product, and without the need to the extraction of organic solvent as toluene, direct separatory washs, and namely the application's post-treating method is simple and easy to do, effective.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only the embodiment of the application, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is that the content with the sulfhydryl compound of formula I structure of the embodiment of the present application 1 preparation is to the liquid phase spectrogram of time;
Fig. 2 is that the reaction monomers with the sulfhydryl compound of formula I structure of the embodiment of the present application 1 preparation is to the liquid phase spectrogram of time;
Fig. 3 is that the content with the sulfhydryl compound of formula I structure of the embodiment of the present application 1 preparation is to the liquid mass spectrum of charge mass.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present application, be clearly and completely described the technical scheme in the embodiment of the present application, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not making the every other embodiment obtained under creative work prerequisite, all belong to the scope of the application's protection.
This application provides a kind of preparation method of sulfhydryl compound, comprise the following steps:
Under the effect of catalyzer, the compound shown in formula II and hydrogen sulfide are reacted at the temperature of 30 DEG C ~ 90 DEG C, obtains the sulfhydryl compound shown in formula I; Described catalyzer is the loaded catalyst of cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of molybdenum system;
The method that the application provides is by adding specific catalyzer etc., with hydrogen sulfide, hydroxyl can be converted into sulfydryl, thus the obtained sulfhydryl compound with formula I structure, breach traditional thiocarbamide-hydrochloric acid technique like this, greatly reduce reaction cost and greatly reduce waste water, being beneficial to application.
The embodiment of the present application adds specific catalyzer in the compound shown in formula II, between the temperature of 30 DEG C ~ 90 DEG C, pass into hydrogen sulfide, preferably reacts under the condition stirred, obtains the sulfhydryl compound shown in formula I.
The application is to have the compound of formula II structure for raw material, and it is polyol, namely the liquid triol with formula II structure mentioned above.The source of the application to the compound described in formula II is not particularly limited, and preferably prepares in accordance with the following methods:
Be under the condition of 10 DEG C ~ 30 DEG C in temperature, 2 mercapto ethanol and alkaline compound solution reacted, reacts and obtain sulfydryl metal-salt after at least 10 minutes; Add Epicholorohydrin afterwards, react at the temperature of 30 DEG C ~ 60 DEG C, obtain the compound shown in formula II.
The embodiment of the present application is reacted after 2 mercapto ethanol and alkaline compound solution mixing in the reactor, and the temperature of reaction controls, at 10 DEG C ~ 30 DEG C, to react after at least 10 minutes, obtain sulfydryl metal-salt.The present invention preferably first adds 2 mercapto ethanol in reactor, then slowly drips alkaline compound solution wherein and prepares sulfydryl metal-salt; Described reactor is preferably equipped with the four-hole boiling flask of thermometer, agitator and breather, under agitation reacts after mixing.
The embodiment of the present invention for raw material, slowly drips alkaline compound solution with 2 mercapto ethanol (can referred to as mercaptoethanol) subsequently.Described alkaline compound solution can be sodium hydroxide solution or potassium hydroxide solution, also can be other organic and inorganic middle strong base solutions, be obtained by reacting sulfydryl metal-salt with 2 mercapto ethanol.In one embodiment of the invention, described alkaline compound solution is sodium hydroxide (NaOH) solution, is obtained by reacting sulfydryl sodium salt with 2 mercapto ethanol.
In the present invention, the reaction between described 2 mercapto ethanol and alkaline compound solution is preferably at N
2carry out under existent condition.The temperature of the reaction between described 2 mercapto ethanol and alkaline compound solution is 10 DEG C ~ 30 DEG C, is preferably 15 DEG C ~ 25 DEG C; The time of described reaction is at least 10 minutes, is preferably 10 minutes.
After obtaining sulfydryl metal-salt, the embodiment of the present application adds a certain proportion of Epicholorohydrin to above-mentioned reaction system, after adding, temperature is increased to 30 DEG C ~ 60 DEG C and reacts, the compound shown in production II.
The embodiment of the present invention is raw material with Epicholorohydrin, is added dropwise in above-mentioned reaction system, and reaction generates triol.Described 2 mercapto ethanol is (2 ~ 3) with the molar equivalent ratio of Epicholorohydrin: 1, is preferably (2.1 ~ 2.5): 1.Described alkaline compound solution neutral and alkali compound is preferably (1 ~ 2) with the molar equivalent ratio of Epicholorohydrin: 1, is more preferably (1.1 ~ 1.5): 1.In the present invention, described in add Epicholorohydrin temperature be 10 DEG C ~ 30 DEG C, be preferably 15 DEG C ~ 25 DEG C.Adding the temperature that Epicholorohydrin carries out reacting is 30 DEG C ~ 60 DEG C, is preferably 35 DEG C ~ 55 DEG C; The time of reaction is preferably 30 minutes.
Embodiment of the present invention preparation has the reaction formula of the oxy-compound of formula II structure such as formula shown in (1):
After obtaining the compound shown in formula II, the embodiment of the present invention stops passing into N
2, be warming up to 30 DEG C ~ 90 DEG C and add specific catalyzer in above-mentioned system, pass into hydrogen sulfide, and be communicated with snubber assembly and device for absorbing tail gas, open stirring and react, after reaction certain hour, obtain the sulfhydryl compound shown in formula I.
The present invention adopts hydrogen sulfide to carry out the mercaptolation of hydroxyl, and because hydrogen sulfide is the main exhaust gas component of petrochemical industry, and in present invention process, it, as important source material, greatly reduces the cost of raw material.In the present invention, the molar equivalent of the compound shown in described formula II and hydrogen sulfide is than being preferably 1:(3 ~ 6), be more preferably 1:4.The embodiment of the present invention passes into hydrogen sulfide when reacting, and being preferably communicated with the conventional snubber assembly in this area and device for absorbing tail gas, react remaining hydrogen sulfide through cushioning laggard row tail gas absorption, is beneficial to react and aftertreatment is carried out.
The application, in the preparation process of polythiol, controls certain temperature and adopts hydrogen sulfide carry out sulfhydrylation and instead of traditional thiocarbamide-hydrochloric acid method, and this process realizes by adding catalyzer.Catalyzer used by the present invention is a series of catalyzer, comprises the loaded catalyst of cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of two kinds, molybdenum system.
In the present invention, described catalyzer preferably comprises:
Carrier, described carrier is aluminum oxide, cerium oxide or molecular sieve; With
Load active ingredient on the carrier, described active ingredient is at least one in the oxide compound of cobalt and the oxide compound of molybdenum.
In the loaded catalyst that the embodiment of the present invention is used, carrier can select the material that specific surface area is larger, such as aluminum oxide (Al
2o
3), cerium oxide (CeO
2) and molecular sieve etc.; The active ingredient of described supported on carriers can be the oxide compound (CoO of cobalt
x, x can change according to charge capacity) or the oxide compound (MoO of molybdenum
y, y also can change according to charge capacity), namely cobalt and molybdenum are distinguished load in the form of the oxide and, on carrier, can be distinguished load, also can load simultaneously.In one embodiment of the invention, the charge capacity of described active ingredient is 10% ~ 50%; The consumption of described catalyzer is 0.01% ~ 10% of Epicholorohydrin quality, is preferably 0.1% ~ 8%, is more preferably 1% ~ 6%.
The source of the present invention to described catalyzer is not particularly limited, and can commercially obtain, and the methods such as pickling process well known to those skilled in the art also can be adopted to prepare voluntarily.In one embodiment of the invention, described catalyzer is the loaded catalyst of cobalt system and the mixing of molybdenum system, is specially: 10%CoO
x-MoO
y/ Al
2o
3(10%CoO
x: 90%MoO
yload is at 100%Al
2o
3on); Its preparation method comprises the following steps:
By cobalt saline solution and the mixing of molybdenum salt brine solution, obtain mixing solutions;
By carrier impregnation in described mixing solutions, successively through placing and drying, finally carrying out roasting, obtaining catalyzer.
Wherein, described cobalt salt can be Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and molybdenum salt can be nitric acid molybdenum, and both mass ratios can be allocated as requested.Described carrier can be aluminum oxide, dipping nitrate mixed solution after, can 24h be placed, and at 120 DEG C dry 12h.Finally in retort furnace, carry out roasting, temperature can be 500 DEG C, can obtain 10%Co
2o
3-MoO
2/ Al
2o
3.In the embodiment that the present invention is other, described catalyzer is specially 10%Co
2o
3-MoO
2/ CeO
2.In the present invention, described catalyzer finally can filter residue form reclaim, and applies mechanically after dried.
After adding described catalyzer, the hydrogen sulfide sulfhydrylation method that the present invention adopts is carried out at the 30 DEG C ~ temperature of 90 DEG C, preferably 40 DEG C ~ 80 DEG C, obtains the sulfhydryl compound shown in formula I.As preferably, the time of the compound shown in described formula II and the reaction between hydrogen sulfide is at least 3 hours, is more preferably 3 hours.Hydrogen sulfide sulfhydrylation method described in the application can shorten the production cycle of a few hours than traditional technology, efficiency is higher.The reaction formula of the sulfhydryl compound shown in the embodiment of the present application preparation formula I is see formula (5):
After compound shown in described formula II and the reaction between hydrogen sulfide terminate, the lower floor's oil phase be obtained by reacting cuts out by the embodiment of the present application, is washed to neutrality (generally washing 2 ~ 3 times), after filtration, obtain water white product, be the sulfhydryl compound with formula I structure.Sulfhydryl compound prepared by the application is applied as oil phase product, and without the need to the extraction of organic solvent as toluene, direct separatory washs, and namely the application's post-treating method is simple and easy to do, effective.
The application carries out the test of liquid matter to the product obtained, and result shows, and described product is the sulfhydryl compound with formula I structure; The mass yield of reaction is more than 95%.Adopt Abbe refractometer, the application carries out refraction index test to the product obtained, and result shows, the sulfhydryl compound shown in the formula I that the present invention obtains has very high specific refractory power, can be used for preparing optical resin.
In order to understand the application further, below in conjunction with embodiment, the preparation method to the sulfhydryl compound that the application provides describes particularly.
Embodiment 1
Take cobalt nitrate hexahydrate and the 27.69g five water nitric acid molybdenum of 1.75g, be mixed with the aqueous solution that massfraction is 30% respectively, and be mixed to get nitrate mixed solution; Then 100g aluminum oxide be impregnated in above nitrate mixed solution, under normal temperature, place 24h, then in 120 DEG C of dry 12h, finally in retort furnace, carry out roasting in 500 DEG C, after 4h, obtain catalyzer (10%Co
2o
3-MoO
2/ Al
2o
3).
Embodiment 2,3
According to the method for embodiment 1, adopt different carrier ZSM-5 (purchased from Pingxiang City Zhong Xing filler company limited) and CeO
2, obtained 10%Co successively
2o
3-MoO
2/ ZSM-5 catalyzer and 10%Co
2o
3-MoO
2/ CeO
2catalyzer.
Embodiment 4
In the 500mL four-hole boiling flask that thermometer, agitator and breather be housed, add 15.6g mercaptoethanol (0.2mol), open and stir and continue to pass into N
2at the temperature of 30 DEG C, slowly drip 20.0gNaOH solution (0.15mol) react, 7.6g (0.1mol) Epicholorohydrin is dropwise slowly dripped after stablizing 10 minutes, after being added dropwise to complete, temperature is risen to 55 DEG C and stablize 30 minutes, obtain the oxy-compound with formula II structure.
Close N afterwards
2be warming up to 80 DEG C of catalyzer adding 0.2g embodiment 1 and prepare in above-mentioned reaction system, pass into 4 molar equivalent hydrogen sulfide, and be communicated with snubber assembly and device for absorbing tail gas, under agitation react, after stablizing 3 hours, the lower floor's oil phase obtained is cut out, by the warm water washing extremely neutrality that 23.1g temperature is 70 DEG C, filter and after drying, obtain colourless transparent liquid product; Catalyzer is then applied mechanically with the dried rear preparation of filter residue form.
The application carries out the test of liquid matter to the product obtained, result is see Fig. 1 to Fig. 3, Fig. 1 is that the content with the sulfhydryl compound of formula I structure of the embodiment of the present application 1 preparation is to the liquid phase spectrogram of time, Fig. 2 be the embodiment of the present application 1 prepare the reaction monomers with the sulfhydryl compound of formula I structure to the liquid phase spectrogram of time, Fig. 3 be the embodiment of the present application 1 prepare the content with the sulfhydryl compound of formula I structure to the liquid mass spectrum of charge mass.From Fig. 1 to Fig. 3, described product has formula I structure.Further, the mass yield of the application's reaction is all more than 95%, and final product purity is 92.7%.
The application carries out refraction index test according to method mentioned above to the product obtained, and result shows, and its specific refractory power is 1.6289.
Embodiment 5 ~ 7
According to the method for embodiment 4, prepare the sulfhydryl compound with formula I structure, difference is, the molar equivalent ratio of mercaptoethanol and sodium hydroxide is followed successively by 2:1,2.3:1.5 and 2.3:1.
Specific refractory power is followed successively by 1.6248,1.6265 and 1.6254.
Embodiment 8,9
According to the method for embodiment 4, prepare the sulfhydryl compound with formula I structure, difference is, adopts 10%Co prepared by embodiment 2 successively
2o
3-MoO
210%Co prepared by/ZSM-5 catalyzer and embodiment 3
2o
3-MoO
2/ CeO
2catalyzer.
Specific refractory power is followed successively by 1.6275 and 1.6270.
Comparative example
In the 500mL four-hole boiling flask that thermometer, agitator and breather be housed, add 15.6g mercaptoethanol (0.2 mole), open and stir and continue to pass into N
2at the temperature of 30 DEG C, slowly drip 20.0gNaOH solution (0.15 mole) react, 7.6g (0.1 mole) Epicholorohydrin is dropwise slowly dripped after stablizing 10 minutes, after being added dropwise to complete, temperature is risen to 55 DEG C and stablize 30 minutes, obtain the oxy-compound with formula II structure.
Close N afterwards
2, in above-mentioned system, add 50.7g hydrochloric acid soln (36%, 0.5 mole) and 30.4g thiocarbamide (0.4 mole) reacts, react 4 hours at the temperature of 112 DEG C.After described system temperature is down to 30 DEG C, passes into ammonia wherein and to be hydrolyzed reaction, react after 3 hours, the lower floor's oil phase obtained is cut out.With the warm water washing that temperature is 30 DEG C, and add hydrochloric acid and be adjusted to neutrality, filter after wash twice, drying, obtain colourless transparent liquid product.
Described product is the sulfhydryl compound with formula I structure, and its specific refractory power is 1.6286.
From above embodiment and comparative example, the hydrogen sulfide sulfhydrylation method that the application adopts is without the isothiuronium salts stage, conversion of hydroxyl is sulfydryl by one step, instead of traditional technology thiocarbamide-hydrochloric acid method, not only greatly reduce reaction cost, greatly reduce the large amount of sewage that hydrochloric acid and sodium hydroxide bring especially, save the reaction times, be a kind of operational path of efficient, energy-saving and environmental protection, be suitable for promoting.
Claims (10)
1. a preparation method for sulfhydryl compound, comprises the following steps:
Under the effect of catalyzer, the compound shown in formula II and hydrogen sulfide are reacted at the temperature of 30 DEG C ~ 90 DEG C, obtains the sulfhydryl compound shown in formula I; Described catalyzer is the loaded catalyst of cobalt system supported catalyst, molybdenum system supported catalyst or cobalt system and the mixing of molybdenum system;
2. preparation method according to claim 1, is characterized in that, described catalyzer comprises:
Carrier, described carrier is aluminum oxide, cerium oxide or molecular sieve; With
Load active ingredient on the carrier, described active ingredient is at least one in the oxide compound of cobalt and the oxide compound of molybdenum.
3. preparation method according to claim 1, is characterized in that, the preparation method of the compound shown in described formula II comprises the following steps:
Be under the condition of 10 DEG C ~ 30 DEG C in temperature, 2 mercapto ethanol and alkaline compound solution reacted, reacts and obtain sulfydryl metal-salt after at least 10 minutes; Add Epicholorohydrin afterwards, react at the temperature of 30 DEG C ~ 60 DEG C, obtain the compound shown in formula II.
4. preparation method according to claim 3, is characterized in that, described alkaline compound solution is sodium hydroxide solution or potassium hydroxide solution;
Described 2 mercapto ethanol is (2 ~ 3) with the molar equivalent ratio of Epicholorohydrin: 1;
Described alkaline compound solution neutral and alkali compound is (1 ~ 2) with the molar equivalent ratio of Epicholorohydrin: 1.
5. preparation method according to claim 4, is characterized in that, the charge capacity of described active ingredient is 10wt.% ~ 50wt.%; The consumption of described catalyzer is 0.01% ~ 10% of Epicholorohydrin quality.
6. preparation method according to claim 3, is characterized in that, the reaction between described 2 mercapto ethanol and alkaline compound solution is at N
2carry out under existent condition.
7. preparation method according to claim 1, is characterized in that, the molar equivalent of the compound shown in described formula II and hydrogen sulfide is than being 1:(3 ~ 6).
8. preparation method according to claim 1, is characterized in that, the time of the compound shown in described formula II and the reaction between hydrogen sulfide is at least 3 hours.
9. preparation method according to claim 1, is characterized in that, after the compound shown in described formula II and the reaction between hydrogen sulfide terminate, is cut out by the lower floor's oil phase be obtained by reacting, is washed to neutrality, after filtration, obtain the sulfhydryl compound shown in formula I.
10. preparation method according to claim 1, is characterized in that, when the compound shown in described formula II and hydrogen sulfide react, also comprises: will react remaining hydrogen sulfide through cushioning laggard row tail gas absorption.
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| CN1164540A (en) * | 1988-12-22 | 1997-11-12 | 三井东压化学株式会社 | Mercapto compound, high refractive index resin and lens and process for preparing them |
| WO2014027427A1 (en) * | 2012-08-14 | 2014-02-20 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
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| CN1164540A (en) * | 1988-12-22 | 1997-11-12 | 三井东压化学株式会社 | Mercapto compound, high refractive index resin and lens and process for preparing them |
| WO2014027427A1 (en) * | 2012-08-14 | 2014-02-20 | 三井化学株式会社 | Production method for polythiol compound, polymerizable composition for optical material and use therefor |
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