CN108586206A - One kettle way prepares 4,4 '-butylidenebis（6- tertiary butyl metacresols）Method - Google Patents
One kettle way prepares 4,4 '-butylidenebis（6- tertiary butyl metacresols）Method Download PDFInfo
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- CN108586206A CN108586206A CN201810331298.2A CN201810331298A CN108586206A CN 108586206 A CN108586206 A CN 108586206A CN 201810331298 A CN201810331298 A CN 201810331298A CN 108586206 A CN108586206 A CN 108586206A
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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
- C07C37/20—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 using aldehydes or ketones
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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Abstract
The present invention relates to a kind of one kettle ways to prepare 4,4 ' butylidenebis（6 tertiary butyl metacresols）Method, using 6 tertiary butyl metacresols, n-butanal as raw material, methanol is solvent, hydrochloric acid is that aromatic hydrocarbon solvent is added after completion of the condensation reaction in the method for 4,4 ' butylidenebis of catalyst preparation (6 tertiary butyl metacresol), the mixed solvent of methanol solvate and aromatic hydrocarbon solvent composition makes reaction mixture all dissolve and be layered under the reflux temperature of methanol, sour water layer is separated, organic layer heating steams remaining methanol, and post-processing obtains crystalline product.The present invention solves the problems, such as that a large amount of sour waters need neutralisation treatment in production process, avoids using a large amount of lye, while avoiding the pollution problem of the neutralization product brought due to the use of lye.The process of sour water separation contributes to the raising of product fusing point and light transmittance index, the sour water separated that can partly or entirely reuse, and reduces pollution treatment cost.
Description
Technical field
The present invention relates to a kind of methods that one kettle way prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), belong to polyene
Hydrocarbon and rubber antioxidant manufacturing technology field.
Background technology
4,4 '-butylidenebis (6- tertiary butyls metacresol) are used as polyolefin and rubber antioxidant, and preparation method is to use
6- tertiary butyls metacresol and n-butanal react under conditions of acid catalyst to be produced.It is used acid be inorganic acid or organic acid, such as
Hydrochloric acid is also especially big using the quantity of acid.
In US 2970151, salt acid as catalyst generates 4,4 '-butylidenebis (6- tertiary butyls metacresol), after the completion of reaction
Steam fugitive constituent, it is therefore an objective to deacidify, benzene is then added, be washed with water extra acid.It is then to be added after completion of the reaction in example 2
Then heptane filters out product, rinse, dry, then is recrystallized with benzene solvent.
US 28318974 is that the preparation method of 4,4 '-alkylidene bis-phenols is improved, and it is reaction dissolvent that alcohol is used in improved method,
A large amount of water is used after the completion of reaction, and reaction mixture is repeatedly washed, after neutrality or subacidity, addition solvent (heptan
Alkane), product is obtained by filtration.This method for removing acid will not only use a large amount of water, but also when material is not completely dissolved, quilt
The acid for being wrapped in the inside does not wash clean.
In US 2822404 1,6- tertiary butyls metacresol and para-acetaldehyde hydrochloric acid make catalyst reaction, after the completion of reaction
Sodium carbonate is added to neutralize, then crude product recrystallizes in benzene -ol mixture.
In JP 2012-136548A, during producing 4,4 '-butylidenebis (6- tertiary butyls metacresol), material reaction is complete
Crude product, again with methanol recrystallization are obtained by filtration after being neutralized afterwards and with sodium hydrate aqueous solution.
6- tertiary butyls metacresol and n-butanal salt acid as catalyst, react in methanol solution, after the completion of reaction if
Methanol and acid directly are steamed, is the simplest and the most direct method, but found in actual mechanical process, with being evaporated, material takes off cruelly
The phenomenon that Splash, is serious.Since strong acid is very big to the corrosion of equipment, if carrying out instant neutralisation treatment, this meeting to acid after having reacted
A large amount of alkali is consumed, and a large amount of neutralized reaction products generated equally need to administer, the method that a large amount of acid neutralize is unfavorable for industrializing
Using.
4,4 '-butylidenebis (6- tertiary butyls metacresol) are dissolved in methanol, ethyl alcohol, ethyl acetate or acetone.From US3761525
In learn its do not dissolve in petroleum hydrocarbon solvent, mixed phenol and n-butanal of the document in 2- Butylated Hydroxytoluenes and 6- tert-butyl-m-cresols
In the product of three kinds of structures of reaction production antioxidant, major part can be got rid of by handling reactant with petroleum hydrocarbon solvent
4,4 '-butylidenebis (the 6- tertiary butyls metacresol) solid generated.
There is the example that product is much rinsed with heptane in the literature, however product is often produced without recrystallization and washing
The fusing point and light transmittance of product can be low.
Invention content
The object of the present invention is to provide a kind of one kettle way prepare 4,4 '-butylidenebis (6- tertiary butyls metacresol) method,
For solving the problems, such as that a large amount of sour waters need neutralisation treatment in production process, this method avoid to use a large amount of lye, together
When avoid due to the use of lye bring neutralization product pollution problem.The process of sour water separation in method is equivalent to recrystallization
Primary washing in the process, this contributes to the raising of product fusing point and light transmittance index, and the sour water separated can be weighed partly or entirely
It is multiple to use, pollution treatment cost is reduced, there are a prodigious economic interests, and sour water is for absorbing industrial chlorinations hydrogen exhaust gas up to after a certain concentration
It can reuse, be conducive to environmentally protective industrial applications.
A kind of method that one kettle way prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), with 6- tertiary butyls metacresol, just
Butyraldehyde is raw material, and methanol is solvent, and hydrochloric acid is in the method for 4,4 '-butylidenebis of catalyst preparation (6- tertiary butyls metacresol),
Aromatic hydrocarbon solvent is added after completion of the condensation reaction, the mixed solvent that methanol solvate and aromatic hydrocarbon solvent form makes reaction mixture
It all dissolves and is layered under the reflux temperature of methanol, separate sour water layer, organic layer heating steams remaining methanol, and post-processing obtains
Crystalline product.
Post-processing washes, cools down, filter, filter cake is dried in vacuo to obtain crystalline product to neutralize.
Aromatic hydrocarbon solvent is used for product purification.
The reflux temperature of methanol is 72-78 DEG C.
The envelope-bulk to weight ratio of the methanol solvate dosage and reactant 6- tertiary butyl metacresol dosages is 0.5-1.5.Its
In, by volume, reactant 6- tertiary butyl metacresols dosage is by weight for methanol solvate dosage.The unit of envelope-bulk to weight ratio is
ml/g。
The aromatic hydrocarbon solvent is toluene, dimethylbenzene, trimethylbenzene or petroleum-type aromatic hydrocarbon solvent oil it is one or more.
Aromatic hydrocarbon solvent amount used is more than reaction mixture in the case of in the mixed solvent methanol eddy, reaction mass
The amount all dissolved.
Aromatic hydrocarbon solvent amount used be aromatic hydrocarbon solvent and water generate under the temperature of azeotropic point or do not generate azeotropic point but
The reaction mixture of identical quantity is set all to dissolve the amount of required aromatic hydrocarbon solvent at 100 DEG C.Aromatic hydrocarbon used is molten at this time
The amount of agent is optimum amount.
The dosage of aromatic hydrocarbon solvent is 2.5-10 with the envelope-bulk to weight ratio of reactant 6- tertiary butyl metacresol dosages.Wherein,
By volume, reactant 6- tertiary butyl metacresols dosage is by weight for methanol solvate dosage.The unit of envelope-bulk to weight ratio is ml/g.
Be added 6- tertiary butyl metacresols, methanol and concentrated hydrochloric acid stirring, heated material temperature to 30-40 DEG C, be added dropwise methanol and
N-butanal mixture, time 30-60 minutes used, then for material under 72-78 DEG C of methanol eddy state, insulated and stirred was 4 small
When, after the completion of condensation reaction, aromatic hydrocarbon solvent is added, continuing insulated and stirred makes material be completely dissolved, and stops stirring, stratification
After separate sour water, be neutralized to neutrality with ammonium hydroxide reagent under the stirring of material organic phase, the lower heating of organic phase stirring steams methanol etc. and waves
Object is sent out, is washed, is cooled down, is filtered, filter cake is dried in vacuo to obtain crystalline product.
Product is in aromatic hydrocarbon solvent for 4,4 '-butylidenebis (6- tertiary butyls metacresol), at relatively high temperatures, has larger
Solubility, such as have in the aromatic hydrocarbon solvent oil that boiling range is 140-200 DEG C in 84 DEG C of toluene solvant or at 100 DEG C
Larger solubility, when as recrystallization solvent, rate of charge is relatively high.Such as 4,4 '-butylidenebis (6- tertiary butyls metacresol)
Product is in toluene solvant, when rate of charge is up to 7 or 7.5, material could be made all to dissolve at 84 DEG C, this is because water washing operations
It can only be carried out under 84 DEG C of the azeotropic point of toluene and water；And the aromatic hydrocarbon solvent oil that boiling range is 140-200 DEG C is in 100 DEG C of temperature
When, rate of charge has reached 8 or 8.5, when being recrystallized using mother liquor, then rate of charge is up to 9.5 or higher.
The mixed solvent of methanol and aromatic hydrocarbon solvent composition, has 4,4 '-butylidenebis (6- tertiary butyls metacresol) product
There is cosolvent so that product increases in the mixed solvent, at a lower temperature solubility, such as is recrystallized with toluene
When solvent, in reaction mass, after a certain amount of toluene solution is added, at 46 DEG C, material can all dissolve simultaneously temperature
Split-phase, sour water are easy for being separated out, and have a large amount of methanol solvate in the sour water branched away, can reuse, dense for acid
The reduction problem of degree is used for hydrogen chloride absorption after sour water centralized collection, is reused after reaching a certain concentration.This avoids due to acid
So that the problem of product yield is declined after concentration reduces.Sour water, which can also be partially or wholly used for lower secondary response dispensing, to be made
A certain amount of concentrated hydrochloric acid is added when with, use.
It separates in the material after sour water, containing remaining methanol and minimal amount of sour water, can be neutralized with a small amount of lye, alkali
The preferred ammonium hydroxide of liquid, then heat up and steam methanol, exist without apparent water phase, water phase is first separated in the presence of having water phase, under stirring
When heating steams, material not will produce bumping phenomenon.The methanol steamed contains by-product, raw material and solvent etc., without processing
It is directly used as next use, the yield of product can be substantially reduced.
After the methanol stratification steamed, solvent can be merged into use next time in mother liquor, under methanol mutually also can be used in
Secondary production dispensing uses, and when material is warming up to 100-110 DEG C, stops steaming, then cool under solvent azeotrope with water point, or
When there is no the solvent of azeotropic point just under 100 DEG C of the boiling point of water, water washing is added, mainly washes away the salt for neutralizing and generating, washing
After material afterwards is warming up to fully dissolved again, then decrease temperature crystalline, temperature drop to 30 DEG C hereinafter, filtering, and filter cake fat hydrocarbon is molten
Agent is rinsed, flushing liquor and mother liquor separate collection, and filter cake vacuum drying obtains product.
The preferred petroleum ether of fat hydrocarbon solvent, No. 120 solvent naphthas or heptane, more preferable heptane.
When sour water detaches, some dirts are had at boundary, need to be separated with water phase, the process of sour water, phase are separated
Interface has some dirts and can be separated with sour water, a water washing operations being equivalent in recrystallization process, contributes to product molten
The raising of point and light transmittance index.
Compared with prior art, the invention has the advantages that：
The present invention solves the problems, such as that a large amount of sour waters need neutralisation treatment in production process, avoids and uses a large amount of alkali
Liquid, while avoiding the pollution problem of the neutralization product brought due to the use of lye.The process of sour water separation contributes to product fusing point
With the raising of light transmittance index, the sour water separated can be reused partly or entirely, reduce pollution treatment cost, there is prodigious economic profit
Benefit, and sour water can be reused for absorbing after industrial chlorinations hydrogen exhaust gas reaches a certain concentration, be conducive to environmentally protective industrialization
Using.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but is not intended to limit the embodiment of the present invention.
Embodiment 1
In 1000 milliliters of four-hole boiling flasks with reflux, blender, 111 grams of 6- tertiary butyl metacresols of addition, 100
Ml methanol and 30 grams of concentrated hydrochloric acids (mass fraction 36%), under stirring, heated material temperature is to 40 DEG C, slowly with normal pressure buret
10 ml methanols and 24 grams of n-butanal mixtures are added, the 60 minutes time used, then material is in 75 ± 3 DEG C of methanol eddy states
Under, 500 milliliters of 200# petroleum-types aromatic hydrocarbon solvent oil is added in 4 hours of insulated and stirred, and insulated and stirred makes material at 73 ± 2 DEG C
Between be completely dissolved after, stop stirring, separate 73 milliliters of sour water, the stirring of material organic phase using the method for changing bottle after stratification
It is lower to be neutralized to neutrality with 1.5 milliliters of ammonium hydroxide reagent, do not find there is water phase after standing.The lower heating of organic phase stirring steams methanol etc. and waves
Object is sent out, temperature of charge stops when being raised to 100 DEG C, steams 41 milliliters of methanol etc., and 20 milliliters of washings of distilled water are added in material once,
After point water in the case of organic phase fully dissolved, stirring cooling when dropping to 20 DEG C, filters, 100 milliliters of aromatic hydrocarbon solvent oils of filter cake
It rinses, then uses 100 milliliters of heptane, rinse in three times, 70 DEG C of vacuum drying 4 hours, product weighs 99 grams, yield 76.7%, molten journey：
210.2-211.5 DEG C, light transmittance (425,500)：94.8 97.1.
Embodiment 2
The present embodiment is same as Example 1, the difference lies in that with reflux, 1000 milliliters four mouthfuls of blender
In flask, 73 milliliters of the sour water separated in 111 grams of 6- tertiary butyls metacresols and embodiment 1 is added, then add 5 grams of concentrated hydrochloric acid (matter
Measure score 36%) and 40 ml methanols.In addition after separating sour water, the aromatic hydrocarbon solvent oil mother liquor 700 generated in embodiment 1 is added
Milliliter.As a result：Product weighs 95 grams, yield 73.6%, molten journey：209.8-210.8 DEG C, light transmittance (425,500)：95.8 97.0.
Embodiment 3
With reflux, in 1000 milliliters of four-hole boiling flasks of blender, it is added 111 grams of 6- tertiary butyl metacresols, in example 2
70 milliliters of the sour water separated, then add 30 millis after the methanol solution split-phase steamed in 5 grams of concentrated hydrochloric acids (mass fraction 36%) and example 2
It rises.Other operations are with embodiment 2, as a result：Product weighs 87.5 grams, yield 67.8%, molten journey：208.1-209.1 DEG C, light transmittance
(425,500)：94.7 97.1.
Embodiment 4
With 1 device of embodiment and operating method, the difference is that：200# petroleum-type aromatic hydrocarbon solvent oils are changed to 500 milli of toluene
It rises, after toluene is added, material has all dissolved at 46 DEG C, separates 71 milliliters of sour water phase；Organic phase 2.5 milliliters of neutralizations of ammonium hydroxide
Afterwards, heating steams methanol, obtains 95 milliliters of distillate.After material cools to 85 DEG C, 20 milliliters of washings of distilled water are added once, then add
Washing is primary again after the fully dissolved that heats up after 100 milliliters of 20 milliliters of water and toluene.The other the same as in Example 1 operates.Product weighs 81.5
Gram, yield 63.2%, molten journey：210.7-211.7 DEG C, light transmittance (425,500)：96.9 98.5.
Embodiment 5
With 1 device of embodiment and operating method, the difference is that：200# petroleum-type aromatic hydrocarbon solvent oils are changed to dimethylbenzene 500
Milliliter, the other the same as in Example 1 operation, wherein separating 84 milliliters of sour water, steams 61 milliliters of methanol solution.As a result：Product weighs 91.5 grams,
Yield 71%, molten journey：209.1-211.1 DEG C, light transmittance (425,500)：96.3 98.1.
Comparative example 1
With the device and dispensing of embodiment 1 and operation, the difference is that：After the completion of reaction, it is changed to that 700 milliliters of water are added,
After washing several times, 100 milliliters of heptane are added, filter after dnockout, then with 100 milliliters of heptane, rinse filter cake in three times, filter cake is true
Empty 90 DEG C of dryings 4 hours, product weigh 106 grams, yield 82%, molten journey；208.3-209.4 DEG C, light transmittance (425,500)：92.2,
94.7。
Claims (10)
1. a kind of method that one kettle way prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), it is characterised in that：With 6- tertiary butyls
Metacresol, n-butanal are raw material, and methanol is solvent, and hydrochloric acid is 4,4 '-butylidenebis of catalyst preparation (6- tertiary butyls metacresol)
Method in, be added aromatic hydrocarbon solvent after completion of the condensation reaction, the mixed solvent of methanol solvate and aromatic hydrocarbon solvent composition makes
Reaction mixture is all dissolved and is layered under the reflux temperature of methanol, separates sour water layer, and organic layer heating steams remaining methanol,
Post-processing obtains crystalline product.
2. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
It is, post-processes to neutralize, wash, cool down, filter, filter cake is dried in vacuo to obtain crystalline product.
3. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
It is, aromatic hydrocarbon solvent is used for product purification.
4. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
It is, the reflux temperature of methanol is 72-78 DEG C.
5. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
It is, the envelope-bulk to weight ratio of the methanol solvate dosage and reactant 6- tertiary butyl metacresol dosages is 0.5-1.5.
6. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
Be, the aromatic hydrocarbon solvent is toluene, dimethylbenzene, trimethylbenzene or petroleum-type aromatic hydrocarbon solvent oil it is one or more.
7. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
It is, aromatic hydrocarbon solvent amount used is more than reaction mixture in the case of in the mixed solvent methanol eddy, and reaction mass is whole
The amount of dissolving.
8. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), feature
Be, aromatic hydrocarbon solvent amount used be aromatic hydrocarbon solvent and water generate under the temperature of azeotropic point or do not generate azeotropic point but
The reaction mixture of identical quantity is set all to dissolve the amount of required aromatic hydrocarbon solvent at 100 DEG C.
9. the method that one kettle way according to claim 1 or 6 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol),
It is characterized in that, the dosage of aromatic hydrocarbon solvent is 2.5-10 with the envelope-bulk to weight ratio of reactant 6- tertiary butyl metacresol dosages.
10. the method that one kettle way according to claim 1 prepares 4,4 '-butylidenebis (6- tertiary butyls metacresol), special
Sign is, 6- tertiary butyl metacresols, methanol and concentrated hydrochloric acid stirring is added, and methanol and just is added dropwise to 30-40 DEG C in heated material temperature
Butyraldehyde mixture, time 30-60 minutes used, then material was under 72-78 DEG C of methanol eddy state, 4 hours of insulated and stirred,
After the completion of condensation reaction, aromatic hydrocarbon solvent is added, continuing insulated and stirred makes material be completely dissolved, and stops stirring, after stratification
Sour water is separated, neutrality is neutralized to ammonium hydroxide reagent under the stirring of material organic phase, the lower heating of organic phase stirring steams the volatilizations such as methanol
Object is washed, and is cooled down, and is filtered, and filter cake is dried in vacuo to obtain crystalline product.
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| CN201810331298.2A CN108586206B (en) | 2018-04-13 | 2018-04-13 | Method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by one-pot method |
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| CN201810331298.2A CN108586206B (en) | 2018-04-13 | 2018-04-13 | Method for preparing 4, 4' -butylidene bis (6-tert-butyl-m-cresol) by one-pot method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651213A (en) * | 2019-01-31 | 2019-04-19 | 淄博万科化工有限公司 | The production method of antioxidant 300 |
| CN110302845A (en) * | 2019-07-25 | 2019-10-08 | 安徽时联特种溶剂股份有限公司 | A kind of antioxidant BBMC catalyst for synthesizing recovery method |
| CN115304638A (en) * | 2022-08-25 | 2022-11-08 | 江苏福基新材料研究院有限公司 | 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite synthesis method |
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| CN106146258A (en) * | 2016-08-04 | 2016-11-23 | 富士胶片精细化学（无锡）有限公司 | A kind of preparation method of 2,2 ' butylidenes double (4 methyl 6 tert-butyl phenol) |
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| US2831897A (en) * | 1954-04-09 | 1958-04-22 | Monsanto Chemicals | Process of making 4, 4'-alkylidene bisphenols |
| JP2007269711A (en) * | 2006-03-31 | 2007-10-18 | Api Corporation | Method for producing 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) improved in hue |
| CN104591972A (en) * | 2014-12-05 | 2015-05-06 | 沈阳师范大学 | Preparation method for 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651213A (en) * | 2019-01-31 | 2019-04-19 | 淄博万科化工有限公司 | The production method of antioxidant 300 |
| CN110302845A (en) * | 2019-07-25 | 2019-10-08 | 安徽时联特种溶剂股份有限公司 | A kind of antioxidant BBMC catalyst for synthesizing recovery method |
| CN115304638A (en) * | 2022-08-25 | 2022-11-08 | 江苏福基新材料研究院有限公司 | 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite synthesis method |
| CN115304638B (en) * | 2022-08-25 | 2023-10-24 | 江苏福基新材料研究院有限公司 | Synthesis method of 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite |
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| CN108586206B (en) | 2020-12-18 |
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Denomination of invention: Preparation of 4,4 '- butylene bis (6-tert butyl m-cresol) by one pot method Effective date of registration: 20211130 Granted publication date: 20201218 Pledgee: Industrial Commercial Bank of China Ltd. Zibo Zhangdian branch Pledgor: Zibo Wanke Chemical Co.,Ltd. Registration number: Y2021980013667 |
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