CN106588611A - Process for producing benzophenone ultraviolet ray absorbent - Google Patents
Process for producing benzophenone ultraviolet ray absorbent Download PDFInfo
- Publication number
- CN106588611A CN106588611A CN201611031017.9A CN201611031017A CN106588611A CN 106588611 A CN106588611 A CN 106588611A CN 201611031017 A CN201611031017 A CN 201611031017A CN 106588611 A CN106588611 A CN 106588611A
- Authority
- CN
- China
- Prior art keywords
- reaction
- production technology
- thing
- halogenated alkyl
- benzophenone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Abstract
The invention discloses a process for producing a benzophenone ultraviolet ray absorbent, and the process includes mixing of a benzophenone compound A and an alkyl halide for alkylation to obtain a benzophenone compound B. The alkyl halide can be prepared by the reaction of a primary alcohol and thionyl chloride under catalysis of a tertiary amine. Further, hydration and distillation of the system after the completion of the alkylation are carried out in order to eliminate crystallization and purification steps. The process is simplified, a high purity product is obtained, solvent consumption is reduced, and the cost is reduced.
Description
Technical field
The present invention relates to field of fine chemical, more particularly to a kind of production technology of benzophenone ultraviolet absorbent.
Background technology
UV absorbent is a kind of light stabilizer, can absorb sunlight and the ultraviolet part in fluorescence light source, and itself
Do not change again.Benzophenone ultraviolet absorbent can strong absorbing wavelength be 270～330nm ultraviolet, can
For various plastics, such as polyethylene, polypropylene, polystyrene, ABS resin, Merlon, polrvinyl chloride, polyester and asphalt mixtures modified by epoxy resin
Fat etc., has the preferable compatibility, volatility little with resin, and which also acts as the light stabilizer of various coating.
At present, the more employing phase transfer catalyst of the process route of benzophenone ultraviolet absorbent is in alkaline aqueous solution
In prepared by the reaction of benzophenone cpd and halogenated alkyl thing, thrown in such as Chinese patent CN100591650C in a kettle.
Add water, with quaternary ammonium salt or tertiary amine as catalyst, make the alkyl bromide and 2,4-DihydroxyBenzophenone back flow reaction in alkali liquor
Octabenzone is prepared, the purification of Jing ethyl alcohol recrystallizations and various post processings after reaction, is needed, reaction time consumption is long
And post processing is loaded down with trivial details.And reacted using 2,4-DihydroxyBenzophenone and dicaprylyl carbonate in Chinese patent CN102503795A,
Ethyl alcohol recrystallization purified product Octabenzone is adopted after the completion of reaction, reaction condition is used in the invention
In commercial production, time-consuming, and also has potential safety hazard when such as ethanol carries out centrifugation after recrystallization using organic solvent.
Therefore, production technology reasonable in design, while high-purity benzophenone ultraviolet g. absorbent products are obtained,
Simplify production technology, improve the problem that production security is current urgent need to resolve.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Using suitable in course of reaction
Catalyst and feeding mode, save crystallisation step after reaction, add antioxidant and suppress side reaction, i.e., during distilation
Production technology, reduces cost and waste discharge can be simplified while high purity product is ensured, so as to complete the present invention.
It is an object of the invention to provide following aspect：
(1) a kind of production technology of benzophenone ultraviolet absorbent, including by benzophenone cpd A, alkyl halide
Mix for thing, be alkylated reaction, benzophenone cpd B is obtained, wherein,
The structure of the benzophenone cpd A is：
The structure of the benzophenone cpd B is
Wherein, R1Selected from hydrogen, alkyl and alkoxyl one or more, R2Selected from C5～C12Alkyl, preferably C6～C8Alkane
Base.
(2) production technology according to above-mentioned (1), wherein, the halogenated alkyl thing can pass through what is comprised the steps
It is prepared by method：C is added in reaction vessel5～C12Primary alconol, evacuation make pressure in reaction vessel be -0.03MPa～-
0.05Mpa, after being warming up to 50～60 DEG C, is slowly added dropwise thionyl chloride under liquid level, after thionyl chloride completion of dropwise addition insulation 1～
4h, it is post-treated to obtain halogenated alkyl thing；
The post processing includes carrying out system after reaction 2～4 washings, be subsequently adding alkali adjust temperature of reaction system to
PH is in alkalescence；The alkali is inorganic base, is appointed in alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate
One or more of meaning, preferably alkali carbonate, more preferably sodium carbonate；Add alkali adjust after reaction system pH be 7～
12, preferably 8～10.
(3) production technology according to above-mentioned (1) or (2), wherein, the production technology is also included to alkylated reaction
After the completion of reaction after system washed and distilled, and/or
Water-washing process includes：Add water in system to after reaction, stir, upper organic phase is shifted after stratification to distillation
Kettle；
Still-process includes：Step 1, in 1x10-2～1x10-3Distill out in 120～180 DEG C under pa vacuum conditions organic
Halogenated alkyl thing in phase；Step 2, is continuously heating to 220～240 DEG C, distills out benzophenone cpd B；
Before distillation, antioxidant is added in system to after reaction, 1～2h of stirring mixing at 60～65 DEG C；The antioxygen
Agent in hindered phenol anti-oxidants, phosphite antioxidant or the thio esters antioxidant any one or it is many
Kind, the hindered phenol anti-oxidants include single phenolic Hinered phenols antioxidant and many phenolic Hinered phenols antioxidants, preferably
Ground, the antioxidant are hindered phenol anti-oxidants and phosphite antioxidant compound use.
The production technology of a kind of benzophenone ultraviolet absorbent provided according to the present invention, with following beneficial effect
Really：
(1) process conditions of present invention synthesis benzophenone ultraviolet absorbent are simple, time-consuming short, improve production effect
Rate；
(2) modifying agent is added in alkylated reaction, each phase reaction thing is fully contacted in making reaction system, accelerate reaction speed
Degree；
(3) consersion unit is transformed, when making synthesis of alkyl halides, thionyl chloride can slowly add under primary alconol liquid level
Enter, promote reaction mass contact fully and production environment safety can be ensured；
(4) solvent crystallization link is saved when the present invention is purified to benzophenone ultraviolet absorbent crude product, distill
After directly obtain high purity product, reduce organic solvent consumption, there is no security hidden trouble during centrifugation, and saved from
Energy consumption and cost of labor during heart post-drying.
Description of the drawings
The gas chromatogram of Octabenzone of the Fig. 1 to prepare in embodiment 1；
The gas chromatogram of Octabenzone of the Fig. 2 to prepare in embodiment 2；
The gas chromatogram of Octabenzone of the Fig. 3 to prepare in comparative example 1.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
Special word " exemplary " means " being used as example, embodiment or illustrative " here.Here as " exemplary "
Illustrated any embodiment is should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the drawings
In terms of kind, but unless otherwise indicated, it is not necessary to accompanying drawing drawn to scale.
The invention discloses a kind of production technology of benzophenone ultraviolet absorbent, the production technology is included hexichol
Methanone compounds A, the mixing of halogenated alkyl thing, are alkylated reaction, benzophenone cpd B are obtained, wherein,
The structure of the benzophenone cpd A is：
The structure of the benzophenone cpd B is
Wherein, R1Selected from hydrogen, alkyl and alkoxyl one or more, the alkyl such as-CH3、-CH2CH3、-CH2(CH2)2CH3、-CH(CH3)2、-C(CH3)3, the alkoxyl such as-OCH3、-OCH2CH3Or-OCH (CH3)2。
R2Selected from C5～C12Alkyl, preferably C6～C8Alkyl, such as-(CH2)5CH3、-(CH2)6CH3Or-(CH2)7CH3。
In the present invention, the R in halogenated alkyl thing and benzophenone cpd B2Accordingly, it is C5～C12Chloro thing or C5~
C12Bromo-derivative, such as 1- n-octyl chlorides, 1- chloro n-decanes, 1- chlorinated dodecanes, 1- n-butyl bromide, 1- bromo pentane silanes or 1- bromos ten
Dioxane, preferably C6～C8Chloro thing.
In further preferred embodiment, the benzophenone cpd A is 1 with the mol ratio of halogenated alkyl thing:
(1.02～1.20).In theory, benzophenone cpd A and the reaction equivalent of halogenated alkyl thing are 1:1, to make reaction more thorough
Bottom, selects halogenated alkyl thing somewhat excessive.Preferably, benzophenone cpd A and the mol ratio of halogenated alkyl thing are 1:(1.05
～1.10).
In a preferred embodiment, also added with acid binding agent in alkylated reaction, the acid binding agent is selected from inorganic base
Or organic base, the organic base in pyridine, triethylamine, Feldalat NM, potassium ethoxide or the potassium tert-butoxide any one or more, institute
Inorganic base is stated selected from alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate, such as sodium hydroxide, hydroxide
In potassium, calcium hydroxide, sodium carbonate or potassium carbonate any one or more, preferably alkali carbonate.
In further preferred embodiment, the acid binding agent is (0.6～1.2) with the mol ratio of halogenated alkyl thing:
1.By-product hydrogen halide is generated in alkylation process, system is made in acidity, and benzophenone cpd A and alkane in the present invention
The alkylated reaction of base halides is reacted for SN2, and hydrionic increase is unfavorable for halogenated alkyl thing to benzophenone cpd A's
Attack, adds alkaline matter regulation system acid-base value, makes system pH be 7～12, the carrying out that SN2 can be promoted to react.Preferably, tie up
Sour agent is (0.8～1.0) with the mol ratio of halogenated alkyl thing:1.
In a preferred embodiment, also added with catalyst in alkylated reaction, the catalyst selected from sodium bromide,
In potassium bromide, sodium iodide or potassium iodide any one or more, preferred potassium bromide, potassium bromide is cheap to be easy to get, anti-in efficient catalytic
Should while reduce production cost.
In further preferred embodiment, the catalyst is (0.001 with the weight ratio of benzophenone cpd A
～0.005):1, preferably (0.002～0.004):1.
In a preferred embodiment, also added with modifying agent in alkylated reaction, the modifying agent is lived selected from surface
In property agent or emulsifying agent any one or more.The surfactant is selected from methylsulfuric acid octadecyltrimethylammonium, chlorination
In alkyl trimethyl ammonium, Dioctadecyldimethylammonium chloride or Polyethylene Glycol any one or more.The emulsifying agent such as fat
Fat acid Polyethylene oxide (9) ester (LAE-9), Emulsifier LM-102 (LM-102), octyl phenol Polyethylene oxide (3) ether (OPE-3)
Or in castor oil polyoxyethylene (10) ether (EL-10) any one or more, the modifying agent is preferably PEG-4000.
In further preferred embodiment, the modifying agent is (0.002 with the weight ratio of benzophenone cpd A
～0.008):1, preferably (0.004～0.006):1.
From the foregoing, benzophenone cpd A, halogenated alkyl thing, acid binding agent and catalyst in the present invention, are potentially included,
React for heterogeneous system, thus be necessary to add modifying agent, be fully contacted each phase reaction thing, accelerate response speed.
In a preferred embodiment, the alkylated reaction in enamel reaction still in 150 DEG C～200 DEG C next time
1～4h of stream, flow back preferably at 170 DEG C～180 DEG C 2～3h, with stirring in course of reaction.
In the present invention, it is prepared by the method that the halogenated alkyl thing can pass through to comprise the steps：Add in reaction vessel
Enter C5～C12Primary alconol, after being warming up to 50～60 DEG C, adds thionyl chloride, thionyl chloride to add after terminating and be incubated 1～4h, reacted
Cheng Hou, it is post-treated to obtain halogenated alkyl thing.
In a preferred embodiment, as thionyl chloride is fuming liquidss, there is intense stimulus abnormal smells from the patient, make protochloride
Sulfone is slowly added under primary alconol liquid level, reaction mass contact can be promoted abundant, and avoid smoke phenomenon from producing.The thionyl chloride
Mol ratio with primary alconol is (1.02～1.20):1, preferably (1.05～1.10):1；
In a preferred embodiment, the preparation of halogenated alkyl thing is carried out in enamel reaction still.The enamel is anti-
Answer kettle to be improved on the basis of existing reactor, the through-hole type charge door of existing reactor is transform as and can pass to reactor
The duct type charge door of bottom, or two charge doors are set at reaction kettle cover, one of them is through-hole type charge door, another
It is set to pass to the duct type charge door of reactor bottom, the addition of through-hole type charge door easy solid reactant, and pipeline
Formula charge door facilitates being slowly added for liquid reactants.In the present invention, the transformation of reactor is primarily to be easy to thionyl chloride to exist
It is subsurface to be slowly added to.
In a preferred embodiment, in course of reaction the pressure of reaction vessel be maintained at -0.03MPa～-
0.05Mpa.Thionyl chloride can release hydrogen sulfide and hydrogen chloride toxic gas with alcohol reaction, and evacuation makes to bear into micro- in reaction vessel
Pressure condition, promotes reaction to carry out to forward direction, and can ensure production environment safety.
In a preferred embodiment, also added with catalyst in halogenated alkyl thing preparation process, the catalyst choosing
From tertiary amine, preferably in DMF, N,N-dimethylacetamide or N, N- dimethylpropionamide any one or
It is various.
In further preferred embodiment, the catalyst is (0.001～0.005) with the weight ratio of primary alconol:1,
Preferably (0.002～0.004):1.
In a preferred embodiment, post processing, the rear place are carried out to thionyl chloride and the reacted system of alcohol
Reason includes carrying out system after reaction 2～4 washings, is subsequently adding alkali and water or aqueous alkali adjusts temperature of reaction system to pH in alkali
Property；Reaction system pH after adding alkali to adjust is 7～12, preferably 8～10.
In further preferred embodiment, the alkali is inorganic base, selected from alkali metal hydroxide, alkaline-earth metal hydrogen
In oxide, alkali carbonate or alkali metal hydrogencarbonate any one or more, preferably alkali carbonate, more preferably
For sodium carbonate.Alkali carbonate is weak base, can promote product alkyl halide for thing compared to strong alkali compound such as sodium hydroxide etc.
Generation is hydrolyzed, and alkali carbonate is not reacted for thing with product alkyl halide, and more stable to the regulation of reaction system acid-base value, no
Easily there is alkali phenomenon.
In a preferred embodiment, the sour gas for generating in halogenated alkyl thing preparation process and in water-washing process
Body (HCl and SO2) bis- grades of film-falling absorption tower series connection of elder generation Jing absorb HCl and obtain by-product hydrochloric acid, then Jing alkali cleanings are processed and absorb SO2It is laggard
End of line gas is emptied.
In the present invention, the production technology of benzophenone ultraviolet absorbent is also included to after the completion of alkylated reaction
System is washed and is distilled, i.e., mixed with halogenated alkyl thing by benzophenone cpd A, and benzophenone cpd B is obtained
Afterwards, excessive reactant halogenated alkyl thing is reclaimed, and product benzophenone cpd B is purified.
Water-washing process includes：Add water in system to after reaction, stir 30～60min, stand 30～60min, separate lower floor
Waste water, upper strata product are transferred to be distilled in high temperature distillation kettle.
Still-process includes：Step 1, in 1x10-2～1x10-3Distill out in 120～180 DEG C under pa vacuum conditions organic
Halogenated alkyl thing in phase；Step 2, is continuously heating to 220～240 DEG C, distills out benzophenone cpd B.
In step 1, the condensed device of halogenated alkyl thing for distilling out carries out B-grade condensation recovery, wherein, B-grade condensation includes
+ 5 DEG C of one-level water-cooled and one-level freeze -15 DEG C so as to which the response rate is not less than 98%.
In step 2, system after distillation is lowered the temperature (less than 200 DEG C), after being passed through noble gases, is removed bottoms,
The preferred nitrogen of the noble gases.The purpose for being passed through noble gases is：Residue after distillation is finished contains Organic substance, if directly leading to
Enter air, burning easily occurs at a higher temperature and even explodes, the incombustibility of noble gases can avoid such situation from occurring.
In a preferred embodiment, before distillation, antioxidant is added in system to after reaction, at 60～65 DEG C
Stirring 1～2h of mixing.
In further preferred embodiment, the antioxidant is selected from hindered phenol anti-oxidants, phosphorous acid esters
In antioxidant or thio esters antioxidant any one or more, the hindered phenol anti-oxidants include that single phenolic is obstructed
Phenolic antioxidant such as diethyl 3,5-di-t-butyl-4-hydroxybenzyl phosphonate (antioxidant 1222), 3- (3,5- di-t-butyls-
4- hydroxy phenyls) propanoic acid n-octadecane alcohol ester (antioxidant 1076), Butylated hydroxyanisole (BHA), 2,6- di-t-butyl -4-
Methylphenol (BHT) or 2,6- di-t-butyl -4 (dimethyl aminomethyl) phenol, many phenolic Hinered phenols antioxidant such as tertiary butyls pair
Benzodiazepiness (TBHQ)；
The phosphite antioxidant include three (2,4- di-tert-butyl-phenyl) phosphite ester (antioxidant 168),
Two hard ester group pentaerythritol phosphites (antioxidant 618), four phosphite ester of octaethyl tetramethylolmethane, 2,2 '-ethylenebis
(4,6- di-tert-butyl-phenyl) fluorophosphite (Ethanox398) or four (- 4 hydroxyphenyl of 2,5- di-t-butyl) bis- uncles of -2,5-
Butylhydroquinone's bis-phosphite (2P5B)；
The thio esters antioxidant includes thio-2 acid two (lauryl alcohol) ester (DLTP), thio-2 acid two (ten
Triol) ester (DTDTP), thio-2 acid two (tetradecyl alchohol) ester (DMTP), thio-2 acid two (octadecanol) ester (DSTP)；
Preferably, the antioxidant selects hindered phenol anti-oxidants and phosphite antioxidant compound use.
From the foregoing, substep distillation is carried out in this production technology to the system after alkylated reaction to realize reaction raw materials
(predominantly halogenated alkyl thing) is reclaimed and product is collected, and due to there is excessive halogenated alkyl thing in system, which at high temperature may be used
React with product benzophenone cpd B, the hydroxyl being further substituted with 2, produce by-product, and then affect product pure
Degree and yield.Antioxidant is added in the reaction system before distillation, especially, hindered phenol anti-oxidants and phosphorous acid esters
Antioxidant compound use, can effectively suppress the generation of side reaction.
In embodiment still more preferably, antioxidant mass concentration after the reaction in system is 1%～
5%, especially, hindered phenol anti-oxidants mass concentration after the reaction in system is 0.5%～3%, and phosphorous acid esters resist
Oxidant mass concentration after the reaction in system is 0.5%～3%.
In the present invention, content >=99.5% of benzophenone cpd B obtained Jing after distillation, its at 450 nm saturating
Light rate >=94.0%, light transmittance >=96.0% under 460nm, light transmittance >=97.0% under 500nm.
It is general using first distillation, the side of rear crystallization to the purification of benzophenone ultraviolet absorbent crude product in prior art
Method, i.e., be dissolved in organic solvent (such as ethanol) by the product for distilling out in crystallization kettle, is passed through chilled brine and cools to less than 5 DEG C,
The solid for obtaining is dried under the conditions of vacuum and low temperature after centrifugation.On the one hand this method of purification limits product
Purity and yield (side reaction occurs in still-process), on the other hand increase the consumption of organic solvent, and organic molten being centrifuged
There is potential safety hazard during agent (such as ethanol).
The present invention is entering to benzophenone ultraviolet absorbent crude product to solve above-mentioned problems of the prior art
Row purification when save solvent crystallization link, high purity product is directly obtained after distillation, organic solvent consumption is reduced, do not exist from
The security hidden trouble during heart, and saved energy consumption and cost of labor when drying.
Embodiment
Below by taking the production technology of Octabenzone (UV531) as an example, enter one by instantiation
The step description present invention.But these examples are only exemplary, do not constitute any restriction to protection scope of the present invention.
Embodiment 1
By 10kg 2,4 dihydroxyl benzophenones (UV-0), 10.5kg chloro octanes, 6kg soda (99%), the poly- second of 50g
In glycol -400 (99%), 30g potassium bromide (99%) input reactor, stirring is opened, 180 DEG C of back flow reaction are warmed up to, is incubated
After reaction 2h, after adding water stirring washing 30min, 30min is stood, lower floor's waste water is separated, upper strata product is transferred to high temperature distillation
It is to be distilled in kettle；
UV-531 crude products obtained in abovementioned alkylization reaction are added 2,6-, bis- uncles that 1% is added in rustless steel distillating still
Butyl -4- methylphenols (BHT) and 2% 3 (2,4- di-tert-butyl-phenyl) phosphite ester (antioxidant 168), heat up 65 DEG C,
Stirring insulation 1h, then in 1x10-2Under pa vacuum conditions heat up distillation, 130 DEG C of front-end volatiles be n-octyl chloride, Jing B-grade condensations
Reclaim (stainless steel condenser, condensation area 20m2,+5 DEG C of one-level water-cooled and one-level freeze -15 DEG C, and 98%) response rate is not less than
It is back in synthetic reaction；It is continuously heating to 225～235 DEG C and UV-531 finished products is distilled out by rectifying column.Distillation is finished, cooling
To less than 200 DEG C, being passed through nitrogen declines vacuum until pressure-fired, releases bottoms.UV531 finished products are in 55 DEG C of moltens
Under state, finished product is cut out by drum-type slicing machine.
The UV531 purity that said method is prepared is 99.6%, and yield is 92%, light transmittance at 450 nm >=
96.0%, light transmittance >=97.5% under 460nm, light transmittance >=98.2% under 500nm, gas chromatogram such as Fig. 1 institutes
Show.
Embodiment 2
By in 10kg n-octyl alcohols (99%) and 40g N,N-dimethylacetamide input enamel reaction still, pressure in kettle-
0.04MPa, is warmed up to 60 DEG C of insulations, is slowly dropped into 11kg thionyl chlorides, is incubated 3h after thionyl chloride completion of dropwise addition under liquid level,
Discharge after sample analysis are qualified, Jing after 3 washings, it is 8 to add solid soda ash and water to adjust to pH value, separates lower floor's waste water, on
It is standby that layer chloro octane enters storage tank；
By 10kg UV-0,11kg chloro octanes, 7kg soda (99%), 60g alkyl trimethylammonium chlorides (99%), 40g
In potassium bromide (99%) input reactor, stirring is opened, 170 DEG C of back flow reaction are warmed up to, after insulation reaction 2h, add water stirring
After washing 40min, 30min is stood, lower floor's waste water is separated, upper strata product is transferred to be distilled in high temperature distillation kettle；
UV-531 crude products obtained in abovementioned alkylization reaction are added the butylhydroxy that 2% is added in rustless steel distillating still
Methoxybenzene (BHA) and 3% 2 hard ester group pentaerythritol phosphite (antioxidant 618), heat up 65 DEG C, stirring insulation 1h, then
In 1x10-2Heat up under pa vacuum conditions distillation, is n-octyl chloride in 130 DEG C of front-end volatiles, and (rustless steel is cold for the recovery of Jing B-grade condensations
Condenser, condensation area 20m2,+5 DEG C of one-level water-cooled and one-level freeze -15 DEG C, and the response rate is not less than
In；It is continuously heating to 225～235 DEG C and UV-531 finished products is distilled out by rectifying column.Distillation is finished, and is cooled to less than 200 DEG C, is led to
Entering nitrogen declines vacuum until pressure-fired, releases bottoms.Finished product is cut into slices by drum-type under 55 DEG C of molten conditions
Machine cuts out finished product.
The UV531 purity that said method is prepared is 99.2%, and yield is 89%, light transmittance at 450 nm >=
94.5%, light transmittance >=96.0% under 460nm, light transmittance >=97.2% under 500nm, gas chromatogram such as Fig. 2 institutes
Show.
Comparative example
Comparative example 1
Operating procedure is same as Example 2, differs only in, and is added without tertiary amine catalytic in (1) chloro octane synthetic reaction
Agent；(2), after the completion of alkylated reaction, in system before it is distilled, it is added without antioxidant.
The UV531 purity that said method is prepared is 96.2%, and yield is 75%, and gas chromatogram is as shown in Figure 3.
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Various equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention
In the range of.Protection scope of the present invention is defined by claims.
Claims (10)
1. a kind of production technology of benzophenone ultraviolet absorbent, including benzophenone cpd A, halogenated alkyl thing are mixed
Close, be alkylated reaction, benzophenone cpd B is obtained.
2. production technology according to claim 1, it is characterised in that
The structure of the benzophenone cpd A is：
The structure of the benzophenone cpd B is
Wherein, R1In hydrogen, alkyl and alkoxyl one or more, R2Selected from C5～C12Alkyl, preferably C6～C8Alkyl.
3. production technology according to claim 1 and 2, it is characterised in that
The halogenated alkyl thing is C5～C12Chloro thing or C5～C12Bromo-derivative, such as 1- n-octyl chlorides, 1- chloro n-decanes, 1-
Chlorinated dodecane, 1- n-butyl bromide, 1- bromo pentane silanes or Dodecyl Bromide, preferably C6～C8Chloro thing；And/or
Also added with acid binding agent in reaction system, the acid binding agent is selected from inorganic base or organic base, preferred inorganic base；And/or
Also added with catalyst in reaction system, the catalyst is any one in sodium bromide, potassium bromide, sodium iodide or potassium iodide
Plant or various, preferred potassium bromide；And/or
Also added with modifying agent in reaction system, the modifying agent is selected from any one or more in surfactant or emulsifying agent.
4. production technology according to claim 3, it is characterised in that
The benzophenone cpd A is 1 with the mol ratio of halogenated alkyl thing:(1.02～1.20), preferably 1:(1.05～
1.10)；And/or
The modifying agent is (0.002～0.008) with the weight ratio of benzophenone cpd A:1, preferably (0.004～
0.006):1；And/or
The benzophenone cpd A is preferably 2,4 dihydroxyl benzophenone；And/or
The alkylated reaction carries out 1～4h at 150 DEG C～200 DEG C of temperature, preferably carry out 2 at 170 DEG C～180 DEG C～
3h。
5. the production technology according to one of Claims 1-4, it is characterised in that
It is prepared by the method that the halogenated alkyl thing can pass through to comprise the steps：C is added in reaction vessel5～C12Primary alconol, rises
Temperature, after being preferably raised to 50～60 DEG C, is slowly added dropwise thionyl chloride under liquid level, is incubated after thionyl chloride completion of dropwise addition, preferred to protect
1～4h of temperature, it is after the completion of reaction, post-treated to obtain halogenated alkyl thing；
Preferably, reaction is carried out in enamel reaction still；And/or
In reaction vessel, pressure is maintained at -0.03MPa～-0.05Mpa.
6. production technology according to claim 5, it is characterised in that
The post processing includes carrying out system after reaction 2～4 washings, is subsequently adding alkali and adjusts reaction system pH in alkalescence；
And/or
Reaction system pH after adding alkali to adjust is 7～12, preferably 8～10.
7. the production technology according to claim 5 or 6, it is characterised in that also added with urging in halogenated alkyl thing preparation process
Agent, the catalyst are selected from tertiary amine, preferably DMF, N,N-dimethylacetamide or N, N- dimethyl propylene
In amide any one or more.
8. the production technology according to one of Claims 1-4, it is characterised in that
The production technology also includes system after alkylated reaction is washed and distilled；And/or
Water-washing process includes：Add water in system to after reaction, stir, upper organic phase is shifted after stratification to distillating still；
Still-process includes：
Step 1, in 1x10-2～1x10-3The halogenated alkyl thing distilled out in organic faciess in 120～180 DEG C under pa vacuum conditions；
Step 2, is continuously heating to 220～240 DEG C, distills out benzophenone cpd B.
9. production technology according to claim 8, it is characterised in that
Before distillation, antioxidant is added in system to after reaction, 1～2h of stirring mixing at 60～65 DEG C；
Preferably, the antioxidant is selected from hindered phenol anti-oxidants, phosphite antioxidant or thio esters antioxygen
In agent any one or more,
It is highly preferred that the antioxidant is hindered phenol anti-oxidants and phosphite antioxidant compound use；And/or
Antioxidant mass concentration after the reaction in system is 1%～5%.
10. production technology according to claim 8 or claim 9, it is characterised in that
In step 1, the condensed device of halogenated alkyl thing for distilling out carries out B-grade condensation recovery, wherein, B-grade condensation is preferably included
+ 5 DEG C of one-level water-cooled and one-level freeze -15 DEG C；And/or
In step 2, system after distillation is lowered the temperature, be passed through noble gases, remove bottoms, the preferred nitrogen of the noble gases
Gas；And/or
Content >=99.5% of the benzophenone cpd B obtained Jing after distillation, its light transmittance >=94.0% at 450 nm,
Light transmittance >=96.0% under 460nm, light transmittance >=97.0% under 500nm,
The benzophenone cpd B is preferably Octabenzone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611031017.9A CN106588611B (en) | 2016-11-17 | 2016-11-17 | A kind of production technology of benzophenone ultraviolet absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611031017.9A CN106588611B (en) | 2016-11-17 | 2016-11-17 | A kind of production technology of benzophenone ultraviolet absorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106588611A true CN106588611A (en) | 2017-04-26 |
| CN106588611B CN106588611B (en) | 2018-02-13 |
Family
ID=58592509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611031017.9A Active CN106588611B (en) | 2016-11-17 | 2016-11-17 | A kind of production technology of benzophenone ultraviolet absorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588611B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129432A (en) * | 2017-06-06 | 2017-09-05 | 如东金康泰化学有限公司 | A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone |
| CN109336754A (en) * | 2018-10-23 | 2019-02-15 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-9 |
| CN110655444A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Method for synthesizing 1-chloro-n-octane |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN112409149A (en) * | 2020-10-28 | 2021-02-26 | 利安隆(天津)新材料科技有限公司 | Preparation method of benzophenone ultraviolet absorbent |
| CN112125793B (en) * | 2020-09-16 | 2024-05-10 | 宜都市华阳化工有限责任公司 | 2, 4-Di-n-octoxybenzophenone and synthetic method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508870A (en) * | 2013-09-24 | 2014-01-15 | 江苏紫奇化工科技有限公司 | UV-531 clean synthetic method |
| CN104098454A (en) * | 2014-07-25 | 2014-10-15 | 襄阳市金达成精细化工有限责任公司 | Production method of ultraviolet light absorber |
-
2016
- 2016-11-17 CN CN201611031017.9A patent/CN106588611B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508870A (en) * | 2013-09-24 | 2014-01-15 | 江苏紫奇化工科技有限公司 | UV-531 clean synthetic method |
| CN104098454A (en) * | 2014-07-25 | 2014-10-15 | 襄阳市金达成精细化工有限责任公司 | Production method of ultraviolet light absorber |
Non-Patent Citations (1)
| Title |
|---|
| 陈彰评: "由醇催化转化为长链氯代烷", 《武汉大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129432A (en) * | 2017-06-06 | 2017-09-05 | 如东金康泰化学有限公司 | A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone |
| CN107129432B (en) * | 2017-06-06 | 2020-11-03 | 如东金康泰化学有限公司 | Synthesis method of ultraviolet absorbent 4,4' -dihexyl benzophenone |
| CN110655444A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Method for synthesizing 1-chloro-n-octane |
| CN109336754A (en) * | 2018-10-23 | 2019-02-15 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-9 |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN112125793B (en) * | 2020-09-16 | 2024-05-10 | 宜都市华阳化工有限责任公司 | 2, 4-Di-n-octoxybenzophenone and synthetic method and application thereof |
| CN112409149A (en) * | 2020-10-28 | 2021-02-26 | 利安隆(天津)新材料科技有限公司 | Preparation method of benzophenone ultraviolet absorbent |
| CN112409149B (en) * | 2020-10-28 | 2022-07-22 | 天津利安隆新材料股份有限公司 | Preparation method of benzophenone ultraviolet absorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106588611B (en) | 2018-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106588611B (en) | A kind of production technology of benzophenone ultraviolet absorbent | |
| US9371269B2 (en) | Method for preparing dialkyl carbonate | |
| CN107963958A (en) | The synthetic method of trans- 4- (trans- 4 '-alkyl-cyclohexyl) cyclohexyl. vinyl liquid crystal monomer | |
| CN101857576A (en) | Simple method for preparing cyproconazole by cyclopropyl methyl ketone | |
| CN101219935A (en) | Bromol production method | |
| CN106380450A (en) | Method for preparing low-energy consumption imidazoles ionic liquid | |
| CN107556155B (en) | A kind of method of the bis- bromine compounds of synthesis α, β- | |
| CN101337938A (en) | Method for synthesizing acetate ionic liquid | |
| CN105418388B (en) | Preparation method of flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane | |
| CN103788112B (en) | A kind of benzyl vitamin H takes off the method that benzyl prepares vitamin H | |
| CN112778100A (en) | Preparation method of high-purity flame retardant methyl tetrabromoether | |
| CN101723970B (en) | Method for preparing retardant resorcin phosphate | |
| CN107652172A (en) | A kind of ultra-violet absorber UV 531 synthetic method | |
| CN107501077A (en) | A kind of preparation method of 2 (4 bromomethyl) phenylpropionic acids | |
| CN101891693B (en) | New method for preparing fluconazole | |
| CN107641067B (en) | Alpha-bromination method of o-diketone | |
| CN103588729A (en) | Synthetic method of 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one | |
| CN104028310B (en) | A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst | |
| CN105330520B (en) | A kind of method for synthesizing double (2,3 dibromopropyl) ethers of tetrabromobisphenol A in water phase | |
| US6049014A (en) | Process for the manufacture of tetrabromobisphenol-A with co-production of n-propyl bromide | |
| CN105037419B (en) | A kind of preparation method of chlorination diphenyl phosphate | |
| CN105037087B (en) | Synthetic method of trisbromoneopentyl alcohol | |
| CN104945234B (en) | The preparation method of the methoxy benzophenone of 2,2 ' dihydroxy 4 | |
| CN102190569B (en) | Method for preparing Prasugrel intermediate alpha-cyclopropylcarbonyl-2-fluorobenzyl bromide | |
| CN102766054B (en) | Industrial synthesizing and purifying method of bis (4-nitrophenyl) carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |