CN109534960A - Based on H2SO4-SiO2The method suitable for industrially prepared Symwhite-337 of solid acid catalyst - Google Patents
Based on H2SO4-SiO2The method suitable for industrially prepared Symwhite-337 of solid acid catalyst Download PDFInfo
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- CN109534960A CN109534960A CN201811415027.1A CN201811415027A CN109534960A CN 109534960 A CN109534960 A CN 109534960A CN 201811415027 A CN201811415027 A CN 201811415027A CN 109534960 A CN109534960 A CN 109534960A
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- solid acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
Abstract
The present invention discloses a kind of based on H2SO4‑SiO2The method suitable for industrially prepared Symwhite-337 of solid acid catalyst.In high-performance solid acid H2SO4‑SiO2Under catalytic action, Symwhite-337 is made in one-step synthesis.Method of the invention can be applied to industrial production, and high efficiency manufacture Symwhite-337, in the case where meeting superiority condition possessed by effective catalyst, recovery resorcinol raw material and organic solvent are realized and simplify process route, reduce environmental protection pressure.
Description
Technical field
The invention belongs to the field of chemical synthesis, it is specifically related to solid acid H2SO4-SiO2For catalyst, one-step synthesis benzene
The method of ethyl resorcinol.
Background technique
Symwhite-337 as novel whitening agent, be widely used in various whitenings, nti-freckle, anti-aging product, it is existing
The potent whitening composition of high-end international cosmetic is had become, mechanism of action is tyrosinase inhibitor, can effectively inhibit B16 black
Color oncocyte synthesis of melanin, external activity are 210 times of kojic acid, 32 times of arbutin, while Symwhite-337
It is a outstanding antioxidant.
Currently, the common effective catalyst for preparing phenethyl (cumenyl) phenol compound is sulfuric acid, other catalysis
Agent such as minerals, atlapulgite, ion exchange resin, zeolite replace inorganic acid, ion exchange resin and zeolite catalyst, because
The reason of preparation cost and catalytic capability etc., research rests on the laboratory development stage.Wherein with sulphur acid as catalyst
The advantages of be that reaction temperature is low, reaction speed is fast.The disadvantage is that sulfuric acid has oxidation stain to product, stainless steel equipment is corroded tight
Weight, and environment-protection wastewater emission request limits its application.
Summary of the invention
The object of the present invention is to provide one kind with solid acid H2SO4-SiO2For catalyst, it is applied to industrial production, efficiently makes
The method for making Symwhite-337 compound.
It is another object of the present invention in the case where meeting superiority condition possessed by effective catalyst, recovery resorcinol
Raw material and organic solvent, which are realized, simplifies process route, reduces environmental protection pressure.
The present invention is achieved through the following technical solutions: being based on H2SO4-SiO2Solid acid catalyst is suitable for industry system
The method of standby Symwhite-337, the method is as follows:
1. organic solvent is added into reaction kettle, under stirring, resorcinol and catalyst solid acid H is added2SO4-SiO2,
It is vacuumized after closed, under nitrogen protection, reaction kettle is warming up to 65-110 DEG C, after temperature plateau, be slowly dropped into styrene, protected
Temperature reaction 3-4 hours detects fully reacting through liquid phase, stops reaction, obtain reaction product.
2. post-processing: organic solvent is added in the reaction product obtained to step 1), recycles solid acid by heat filtering
H2SO4-SiO2, spare, filtrate under agitation, slowly cools to 0 DEG C, there is the precipitation of solid resorcinol；It filters again, Gu
Recycled after body organic solvent washing it is spare, filtrate be concentrated into solid be precipitated after mixed solvent is added, be heated to 70-80 DEG C it is molten
Xie Hou is cooled to -5 DEG C under stiring, there is crystal precipitation, filters pressing after being precipitated completely to crystal for heat preservation 2-3 hours, solid mixing
After solvent washing, filtering is dried in vacuo in 50 DEG C, obtains target product Symwhite-337.It is all in last handling process to have
Solvent and mixed solvent are all carrying out recycling and reusing after washing and filtering.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, in molar ratio, resorcinol: styrene=2.5~1:1.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, in molar ratio, resorcinol: styrene=2.5:1.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, solid acid H2SO4-SiO2Quality be styrene quality 0.5-5%.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, solid acid H2SO4-SiO2Quality be styrene quality 3%.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, solid acid H2SO4-SiO2In, in mass ratio, H2SO4:SiO2=0.5-1:1.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, the organic solvent be toluene, benzene or n-hexane.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, the mixed solvent be by volume, n-hexane: toluene=1:1~5.
Further, above-mentioned based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared Symwhite-337
Method, in step 1), reaction kettle is warming up to 65-110 DEG C, 95 DEG C of optimal reaction temperature.
The present invention uses styrene and resorcinol for raw material, applying solid acid H2SO4-SiO2For catalyst, by Fu
Symwhite-337 compound is made in gram alkylated reaction, and reaction equation is as follows:
The beneficial effects of the present invention are:
1) present invention is the synthetic method that catalyst is made with solid acid, and this method has sulfuric acid as the excellent of catalyst
Point, the reaction time is short, temperature is low, yield is high, overcomes sulfuric acid severe corrosion to equipment again, especially caused by its oxidisability
Byproduct of reaction is more, color is deep and difficult disadvantage is separated with product, and present invention process is efficient, stablizes, and is suitble to high-end market high-purity
Product demand is spent, catalyst preparation is at low cost, can be recycled.
2) present invention is cleaning technology process: by filtering in post-processing, recycling solid acid and recycled are realized
Raw material resorcinol, organic solvent toluene, n-hexane energy recovery, this technique are discharged without phenol wastewater, clean for green
Technique has the characteristics that economic, environmental protection, is suitble to big industrially prepared.
In short, the present invention uses solid acid H2SO4-SiO2For catalysis, realizes and both kept sulfuric acid as effective catalyst
Advantage avoids byproduct of reaction caused by the strong corrosive of liquid acid, especially its oxidisability more again and separates hardly possible with product
Disadvantage, solid acid catalyst is recyclable to be applied, and without environmentally friendly discharge of wastewater.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is the efficient liquid phase detection level figure of Symwhite-337 prepared by the present invention.
Specific embodiment
Embodiment 1 is based on H2SO4-SiO2The method suitable for industrially prepared Symwhite-337 of solid acid catalyst
Process flow is as shown in Figure 1, the method is as follows:
(1) toluene of 50L is added into reaction kettle, starts stirring, the resorcinol of addition 31.7kg (288mol) (mw:
110.11), the catalyst solid acid H of 0.15kg2SO4-SiO2(H in mass ratio2SO4:SiO2=1:1), after closed, vacuumize,
Nitrogen is replaced 3 times, under nitrogen protection, reaction kettle is warming up to 95 DEG C, after temperature plateau, is slowly dropped into 15kg (144mol)
Styrene, control feed time 1.5-2 hour, insulation reaction 3 hours, detect fully reacting through liquid phase, stop reacting, yield
84%.
(2) 10 liters of toluene are added into step (1) products therefrom, solid acid H is recycled by heat filtering2SO4-SiO2It urges
Agent, spare, filtrate under agitation, slowly cools to 0 DEG C, there is the precipitation of solid resorcinol, filtering, solid resorcinol
It is spare that recycling is washed with 10 liters (5 liters X2 times) of toluene.8 liters of mixed solvents of addition after solid is precipitated have been concentrated the filtrate to (to press
Volume ratio, n-hexane: toluene=1:1) it is heated to 75 DEG C after completely dissolution, it is cooled to -5 DEG C under stiring, there is crystal precipitation, protects
Filters pressing after being precipitated completely to crystal for temperature 2 hours, obtained solid is with 20 liters of mixed solvents (by volume, n-hexane: toluene=1:1)
Washing 2 times, mixed solvent recovery, obtained solid are dried in vacuo in 50 DEG C, white crystal 22.6kg are obtained, as between phenethyl
Benzenediol (mw:214.26), liquid phase detection level 98.2%, product yield 87%, product fusing point: 76-78 DEG C.
IR/cm-
1(KBr):3377,3019,2965,2928,1603,1509,1490,1383,1272,1212,1159,1113,
971,838,804,749,699,546.
1HNMR(600MHz,CDCl3,TMS)δ:7.069-7.211(m,5H),6.849(d,1H),6.217(s,1H),
6.165(d,1H),4.272(m,1H)1.413(d,3H).
Embodiment 2
(1) design " three factor two is horizontal " reaction condition parameter such as table 1, method is with embodiment 1, as a result such as table 2.
Table 1
| Horizontal factor | Resorcinol: styrene molar ratio | Solid acid H2SO4-SiO2Additive amount quality % | Reaction temperature |
| 1 | 1:1 | 0.5 | 65 |
| 2 | 2.5:1 | 5 | 110 |
Table 2
By Tables 1 and 2 as it can be seen that through " three factor two is horizontal " orthogonal, key reaction condition priority are as follows:
Benzenediol: styrene molar ratio > solid acid H2SO4-SiO2Additive amount > reaction temperature.
Embodiment 3
(1) toluene of 50L is added into reaction kettle, starts stirring, the resorcinol of addition 39.6kg (360mol) (mw:
110.11), the catalyst solid acid H of 0.45kg2SO4-SiO2(H in mass ratio2SO4:SiO2=1:1), after closed, vacuumize,
Nitrogen is replaced 3 times, under nitrogen protection, reaction kettle is warming up to 95 DEG C, after temperature plateau, is slowly dropped into 15kg (144mol)
Styrene (mw:104.15), control feed time 1.5-2 hour, insulation reaction 3 hours, detect fully reacting through liquid phase, production
Rate 89% stops reaction.
(2) 10 liters of toluene are added into reaction solution, solid acid H is recycled by heat filtering2SO4-SiO2Catalyst, filtrate exist
Under stirring condition, 0 DEG C is slowly cooled to, there is a precipitation of solid resorcinol, filtering, solid resorcinol is with 12 liters (6 liters X2 times)
Toluene washing recycling it is spare.Concentrated the filtrate to after solid is precipitated be added 10 liters of mixed solvents (by volume, n-hexane:
Toluene=1:1) it is heated to 75 DEG C after completely dissolution, it is cooled to -5 DEG C under stiring, there is crystal precipitation, keeps the temperature 2 hours to crystal
Filters pressing after being precipitated completely, obtained solid are washed 2 times with 20 liters of mixed solvents (by volume, n-hexane: toluene=1:1), gained
Solid is dried in vacuo in 50 DEG C, obtains white crystal 24.2kg, liquid phase detection level 98.4%, product yield 88%, and product is molten
Point: 76-78 DEG C.
Claims (9)
1. being based on H2SO4-SiO2The method suitable for industrially prepared Symwhite-337 of solid acid catalyst, which is characterized in that
Method is as follows:
1) organic solvent is added into reaction kettle, under stirring, resorcinol and catalyst solid acid H is added2SO4-SiO2, closed
After vacuumize, under nitrogen protection, reaction kettle is warming up to 65-110 DEG C, after temperature plateau, is slowly dropped into styrene, heat preservation is anti-
It answers 3-4 hours, detects fully reacting through liquid phase, stop reaction, obtain reaction product；
2) it post-processes: organic solvent is added in the reaction product obtained to step 1), solid acid H is recycled by heat filtering2SO4-
SiO2, spare, filtrate under agitation, slowly cools to 0 DEG C, there is the precipitation of solid resorcinol；It filters again, solid isophthalic
Recycled after diphenol organic solvent washing it is spare, filtrate be concentrated into solid be precipitated after mixed solvent is added, be heated to 70-80 DEG C
After dissolution, it is cooled to -5 DEG C under stiring, has crystal precipitation, filters pressing after being precipitated completely to crystal for heat preservation 2-3 hours, solid is used mixed
After bonding solvent washing, filtering is dried in vacuo in 50 DEG C, obtains target product Symwhite-337.
2. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that in molar ratio, resorcinol: styrene=2.5~1:1.
3. according to claim 2 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that in molar ratio, resorcinol: styrene=2.5:1.
4. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that solid acid H2SO4-SiO2Quality be styrene quality 0.5-5%.
5. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that solid acid H2SO4-SiO2Quality be styrene quality 3%.
6. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that solid acid H2SO4-SiO2In, in mass ratio, H2SO4:SiO2=0.5-1:1.
7. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that the organic solvent is toluene, benzene or n-hexane.
8. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that the mixed solvent is n-hexane: toluene=1:1~5 by volume.
9. according to claim 1 be based on H2SO4-SiO2Solid acid catalyst is suitable for industrially prepared phenethyl isophthalic two
The method of phenol, which is characterized in that in step 1), reaction kettle is warming up to 95 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610023A (en) * | 2015-01-19 | 2015-05-13 | 烟台腾辉化工有限公司 | Preparation technology of 4-(1-phenylethyl)-1,3-resorcinol |
| CN105237359A (en) * | 2015-11-10 | 2016-01-13 | 辽宁大学 | Preparation method of phenethyl/cumenyl phenol chemicals |
| CN105693475A (en) * | 2016-03-15 | 2016-06-22 | 辽宁大学 | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol |
| CN107266292A (en) * | 2017-07-24 | 2017-10-20 | 湖北阿泰克生物科技股份有限公司 | A kind of method for synthesizing Symwhite-337 |
-
2018
- 2018-11-26 CN CN201811415027.1A patent/CN109534960A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610023A (en) * | 2015-01-19 | 2015-05-13 | 烟台腾辉化工有限公司 | Preparation technology of 4-(1-phenylethyl)-1,3-resorcinol |
| CN105237359A (en) * | 2015-11-10 | 2016-01-13 | 辽宁大学 | Preparation method of phenethyl/cumenyl phenol chemicals |
| CN105693475A (en) * | 2016-03-15 | 2016-06-22 | 辽宁大学 | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol |
| CN107266292A (en) * | 2017-07-24 | 2017-10-20 | 湖北阿泰克生物科技股份有限公司 | A kind of method for synthesizing Symwhite-337 |
Non-Patent Citations (1)
| Title |
|---|
| 余磊等: "苯乙基间苯二酚的合成工艺研究 ", 《化学与生物工程》 * |
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