CN110305049A - A method of producing low coloration poly-thiol compound - Google Patents
A method of producing low coloration poly-thiol compound Download PDFInfo
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- CN110305049A CN110305049A CN201910613620.5A CN201910613620A CN110305049A CN 110305049 A CN110305049 A CN 110305049A CN 201910613620 A CN201910613620 A CN 201910613620A CN 110305049 A CN110305049 A CN 110305049A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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Abstract
The invention belongs to optical resin technical fields, more particularly to a kind of method for producing low coloration poly-thiol compound, specific preparation process is as follows: surfactant is added in isothiuronium salts in alkaline solution, reaction is hydrolyzed, obtain polymercaptan crude mixture, separation, washing, drying, can be obtained the low poly-thiol compound of coloration.The production method is easy to operate, and raw material is easy to get, and dosage is few, and low energy consumption, is not necessarily to used device, and products obtained therefrom not only can satisfy the needs of the industries such as fine chemistry industry, also improve the quality of downstream product, the excellent optical resin lens of easily prepared performance.
Description
Technical field
The invention belongs to optical resin technical fields, and in particular to a method of produce low coloration poly-thiol compound.
Background technique
Compared with unorganic glass, optical resin has apparent superiority in terms of being applied to glasses.Polyurethane-type light
Learn the important development direction that resin is Novel optical resin in recent years.With high refractive index, high Abbe number, low-gravity, high-impact
The features such as hitting property are especially suitable for the spectacle lens of high folding in production.Such resin raw material is mainly with multi-thioalcohol compound and isocyanide
Acid esters is prepared for raw material.Yellow colour index is an important indicator of optical resin material, and determines optical resin yellow and refer to
Several keys is then the coloration of multi-thioalcohol compound.
Korean Patent 1993-0006918 discloses a kind of preparation method of sulphur urethane eyeglass, although this eyeglass exists
Excellent in terms of the indexs such as Abbe number and light transmittance, but lead to the optical resin lens hair of synthesis since product coloration is poor
Huang, product are unqualified.Impurity in Korean Patent 10-2008-0090529 analysis raw material will lead to mercaptan compound colour difference.
Patent CN104066716A research discovery, which has to simultaneously control two kinds of impurity in raw material, can just obtain the low polysulfide alcoholization of coloration
Object is closed, control condition is stringent, not easy to operate.Patent CN107311898A is mainly the iron content passed through in strict control reaction raw materials
The multi-thioalcohol compound with lower coloration is measured, to meet the ingredient requirement for preparing excellent optical resin lens, is needed
Strict control iron content is wanted, complicated for operation, technique is cumbersome, at high cost.Patent CN107311899A discloses a kind of using reduction
The method that method handles the higher multi-thioalcohol compound of coloration, complex steps are at high cost, and the period is long, and energy consumption is high.It has not yet to see
The method for obtaining low coloration poly-thiol compound by controlling synthetic reaction step.
Summary of the invention
For the above technical issues, the present invention provides a kind of methods for producing low coloration poly-thiol compound, improve
The quality of optical resin lens.The production method is easy to operate, and raw material is easy to get, and dosage is few, and low energy consumption, is not necessarily to used device, fits
Close industrialized production.
To achieve the goals above, the technical solution that the application takes is as follows:
Surfactant is added in isothiuronium salts in alkaline solution, and reaction is hydrolyzed, and obtains polymercaptan crude mixture,
Separation, washing, drying, can be obtained the low poly-thiol compound of coloration.
The surfactant be stearic acid, lauric acid, oleic acid, lauryl sodium sulfate, laurel alcohols sodium sulphate and
One of neopelex is several.
The dosage of surfactant is the 0.1%-1% of isothiuronium salts quality.If proportion is too low, do not have effective
Effect.If proportion is excessively high, can waste raw material.
Preferably, PH >=10 of alkaline solution, using isothiuronium salts under alkaline condition carry out alkaline hydrolysis, thus arrive polysulfide
Alcohol.
Preferably, the alkali in alkaline solution be one of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate or
Several mixing of person.
Preferably, alkali is sodium carbonate, potassium carbonate in alkaline solution.
Preferably, hydrolysising reacting temperature is 30-70 DEG C.
Preferably, hydrolysising reacting temperature is 45-60 DEG C.If reaction temperature is low, reaction speed is slow, and the reaction time is long.If
Reaction temperature is high, then energy consumption is high, while side reaction occurs and generates impurity.
Preferably, hydrolysis time 2-5h.
Preferably, hydrolysis time 2.5-3.5h.If the reaction time is short, reaction is incomplete；If the reaction time is long,
It then wastes time, it is also possible to will lead to the generation of other reactions.
The synthesis of isothiuronium salts is synthesized according to technical solution in patent CN105906773B, and isothiuronium salts is by polynary
Alcohol, thiocarbamide and acid-mixed carry out salt-forming reaction after closing and are formed.Wherein, for 1 mole of polyol compound, preferably 2.8-
3.5 moles of thiocarbamide makes its reaction, and preferably 3-5 moles of acid reacts 2-10h at 90-120 DEG C.Acid is hydrochloric acid, sulfuric acid, hydrogen bromine
One or more of acid, phosphoric acid.The synthesis of isothiuronium salts is not limited to patent CN105906773B, for other methods synthesis
Isothiuronium salts may be equally applicable for the present invention.
Polyalcohol is mainly reacted by mercaptoethanol, epichlorohydrin and aqueous slkali under certain condition, wherein comprising simultaneously
Entirely do not include following several:
Preferably, dry to be adsorbed by drying, desiccant is one of silica gel, calcium oxide, magnesium sulfate and phosphorus pentoxide
Or several mixing.
Present invention firstly provides poly-thiol compound process is prepared, during isothiuronium salts alkaline hydrolysis, surface-active is added
Agent, surfactant has good humidification solubilizing effect, although it cannot directly be participated in hydrolysis reaction, is added
Surfactant can promote isothiuronium salts that hydrolysis occurs, so that isothiuronium salts hydrolyzes to the greatest extent obtains polysulfide alcoholization
Close object.In the existing technique for generating polymercaptan, surfactant, the centre that isothiuronium salts generates during hydrolyzing is not added
When product reaches a certain amount of, the positive of reaction can be inhibited to carry out, so that hydrolysis is not thorough, obtained product coloration is high, pure
It spends that low, yield is low, surfactant is being added, hydrolysis is thoroughly carried out, the alkaline hydrolysis degree of reaction is increased, is reducing
The generation of foreign pigment reduces the coloration of product to improve the purity of product.
In conclusion the invention discloses a kind of methods for producing low coloration poly-thiol compound.Production method operation
Simply, raw material is easy to get, and dosage is few, and low energy consumption, safety and environmental protection, is not necessarily to used device, and products obtained therefrom not only can satisfy fining
The needs of the industries such as work, also improve the quality of downstream product, and the excellent optical resin lens of easily prepared performance meet visitor
The requirement at family and market has biggish society and economic value.
Specific embodiment
Invention is described further combined with specific embodiments below, those skilled in the art can be made to further understand
The present invention, but not as the limitation to summary of the invention, all technologies based on principle of the present invention all belong to the scope of the present invention.
Embodiment 1
(a) 190g polyalcohol A is poured into four-hole boiling flask, puts into 115g (3mol) thiocarbamide and 152g mass fraction is 36%
Hydrochloric acid (3mol), 100 DEG C of back flow reaction 3.5h form isothiuronium salts；
(b) it is cooled to room temperature, it is 12 that sodium carbonate liquor regulation system pH, which is added, while 0.52g lauric acid is added, and is heated to
30 DEG C, reaction 2h is hydrolyzed, obtains polymercaptan crude mixture；
(c) the mixed separation of the crude product for obtaining step (b) is filtered using washing twice using 5% silica dehydrator
Obtain the low poly-thiol compound of coloration.
It is examined using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that the embodiment of the present invention 1 obtains
It surveys, the results showed that, the coloration for the poly-thiol compound that the embodiment of the present invention 1 obtains is 10Hazen.
Embodiment 2
(a) 200g polyalcohol B is poured into four-hole boiling flask, puts into 123g thiocarbamide (3.2mol) and 177g mass fraction is
36% hydrochloric acid (3.5mol), 110 DEG C of back flow reaction 2h form isothiuronium salts；
(b) it is cooled to room temperature, investment ammonia spirit tune system pH is 13, while 4g lauryl sodium sulfate is added, and is heated
To 45 DEG C, reaction 2.5h is hydrolyzed, obtains polymercaptan crude mixture；
(c) the mixed separation of the crude product for obtaining step (b), it is dried using 6% phosphorus pentoxide using washing twice
The low poly-thiol compound of coloration can be obtained in filter.
It is examined using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that the embodiment of the present invention 2 obtains
It surveys, the results showed that, the coloration for the poly-thiol compound that the embodiment of the present invention 2 obtains is 9Hazen.
Embodiment 3
(a) 180g polyalcohol A is poured into four-hole boiling flask, puts into 126g thiocarbamide (3.3mol) and 203g mass fraction is
36% hydrochloric acid (4mol), 112 DEG C of back flow reaction 2.5h form isothiuronium salts；
(b) it is cooled to room temperature, it is 10 that sodium hydroxide solution tune system pH, which is added, while 2g dodecyl benzene sulfonic acid is added
Sodium, is heated to 70 DEG C, and hydrolysis 3.5h obtains polymercaptan crude mixture；
(c) the mixed separation of the crude product for obtaining step (b), using washing twice, using 10% calcium oxide dry filter
The low poly-thiol compound of coloration can be obtained.
It is examined using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that the embodiment of the present invention 3 obtains
It surveys, the results showed that, the coloration for the poly-thiol compound that the embodiment of the present invention 3 obtains is 8Hazen.
Embodiment 4
(a) 185g polyalcohol B is poured into four-hole boiling flask, puts into 134g thiocarbamide (3.5mol) and 253g mass fraction is
36% hydrochloric acid (5mol), 115 DEG C of back flow reaction 2h form isothiuronium salts；
(b) it is cooled to room temperature, it is 11 that solution of potassium carbonate tune system pH, which is added, while 5g laurel alcohols sodium sulphate is added, and is added
For heat to 60 DEG C, hydrolysis 5h obtains polymercaptan crude mixture；
(c) the mixed separation of the crude product for obtaining step (b), using washing twice, using 10% calcium oxide dry filter
The low poly-thiol compound of coloration can be obtained.
It is examined using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that the embodiment of the present invention 4 obtains
It surveys, the results showed that, the coloration for the poly-thiol compound that the embodiment of the present invention 4 obtains is 9Hazen.
Comparative example 1
(a) 185g polyalcohol B is poured into four-hole boiling flask, puts into the salt that 110g thiocarbamide and 200g mass fraction are 36%
Acid, 112 DEG C of back flow reaction 2h form isothiuronium salts；
(b) it is cooled to room temperature, potassium hydroxide solution regulation system pH is added as 12,50 DEG C, reaction 3h is hydrolyzed, obtain
Polymercaptan crude mixture；
(c) crude product for obtaining step (b) is mixed separates, and using washing twice, is using 4% magnesium sulfate dry filter
The low poly-thiol compound of coloration can be obtained.
It is detected, is tied using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that comparative example 1 obtains
Fruit shows that the coloration for the poly-thiol compound that comparative example 1 obtains is 15Hazen.
Comparative example 2
(a) 185g polyalcohol A is poured into four-hole boiling flask, puts into the salt that 110g thiocarbamide and 200g mass fraction are 36%
Acid, 112 DEG C of back flow reaction 2h form isothiuronium salts；
(b) 40 DEG C are down to, toluene 250g is added into isothiuronium salts, then is passed through the ammonium hydroxide that mass fraction is 20% and is passed through
255g, 50 DEG C are hydrolyzed reaction 6h, obtain polymercaptan crude mixture；
(c) the mixed separation of the crude product for obtaining step (b), using carrying out washing-acid elution-washing-neutralizing treatment-water
It washes, adopts and remove toluene and micro moisture under heating decompression, be then filtered under diminished pressure with 1.2 μm of PTFE type molecular filter,
Obtain poly-thiol compound.
It is detected, is tied using coloration of the high-accuracy multifunctional spectrophotometric color measurement instrument to the polymercaptan product that comparative example 2 obtains
Fruit shows that the coloration for the poly-thiol compound that comparative example 2 obtains is 10Hazen.
The present invention provides a kind of method for producing low coloration poly-thiol compound, is put forward for the first time and prepares poly-thiol compound mistake
Journey during isothiuronium salts alkaline hydrolysis, is added surfactant, makes to obtain the polymercaptan of low coloration.Using normal in comparative example 1
The method of the isothiuronium salts alkaline hydrolysis of rule, the coloration of obtained poly-thiol compound are 15Hazen, hence it is evident that are higher than polysulfide in embodiment
The coloration of alcoholic compound.Using the method for alkaline hydrolysis in patent CN105906773B in comparative example 2, obtained poly-thiol compound
Coloration be 10Hazen, it is suitable with the coloration of the poly-thiol compound arrived that embodiment in the present invention obtains, but comparison text
It joined organic solvent in part 2, cumbersome in the process of subsequent removing, the process of the production of increase increases production cost, raw
Period growth is produced, efficiency is lower, while the step in documents 2 is cumbersome, complicated, is not easy to operate.But literary with comparison
2 effect of part quite even effect than documents 2 also than get well, the reaction time shortens, simple process, and safety and environmental protection is high-efficient.
Therefore, the present invention provides a kind of method for producing low coloration poly-thiol compound, can be adapted for industrialized production.
Claims (10)
1. a kind of method for producing low coloration poly-thiol compound, which is characterized in that specific preparation process is as follows:
Surfactant is added in isothiuronium salts in alkaline solution, and reaction is hydrolyzed, and obtains polymercaptan crude mixture, point
From the low poly-thiol compound of coloration can be obtained in washing, drying.
2. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the surface
Activating agent dosage is the 0.1%-1% of isothiuronium salts quality.
3. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the surface
Activating agent is stearic acid, lauric acid, oleic acid, lauryl sodium sulfate, laurel alcohols sodium sulphate and neopelex
One of or it is several.
4. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the alkali
PH >=10 of property solution.
5. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the alkalinity
Alkali in solution is one of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate or several mixing.
6. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the hydrolysis
Reaction temperature is 30-70 DEG C.
7. a kind of method for producing low coloration poly-thiol compound according to claim 6, which is characterized in that the hydrolysis
Reaction temperature is 45-60 DEG C.
8. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that the hydrolysis
Reaction time is 2-5h.
9. a kind of method for producing low coloration poly-thiol compound according to claim 8, which is characterized in that the hydrolysis
Reaction time is 2.5-3.5h.
10. a kind of method for producing low coloration poly-thiol compound according to claim 1, which is characterized in that described
Dry is to be adsorbed by drying, and desiccant is the mixing of one or more of silica gel, calcium oxide, magnesium sulfate and phosphorus pentoxide.
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| CN110835409A (en) * | 2019-12-03 | 2020-02-25 | 山东益丰生化环保股份有限公司 | Method for producing polythiol by using microchannel reactor through continuous reaction |
| CN112358613A (en) * | 2020-10-27 | 2021-02-12 | 山东益丰生化环保股份有限公司 | Polythiol for optical resin and preparation method and application thereof |
| CN112430326A (en) * | 2020-11-27 | 2021-03-02 | 山东益丰生化环保股份有限公司 | Polythiol compound, preparation method and application thereof |
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