CN102816053B - Method for improving crystalline state of synthetic 2,2'-ethylene-bis(4,6-di-tert-pentylphenol) product - Google Patents
Method for improving crystalline state of synthetic 2,2'-ethylene-bis(4,6-di-tert-pentylphenol) product Download PDFInfo
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Abstract
The invention discloses a method for improving a crystalline state of a synthetic 2,2'-ethylene-bis(4,6-di-tert-pentylphenol) product and belongs to the technical field of chemical crystallization. The method provided by the invention is characterized in that raw materials of 2,4-di-tert-pentylphenol and paraldehyde undergo a two-stage reaction in the presence of an aqueous reaction solvent containing an emulsifier, acidic catalysts and dispersing agents; an aging process is carried out in the two-stage reaction; in an first stage of the two-stage reaction, a reaction temperature is in a range of 90 to 97 DEG C and reaction time is in a range of 2 to 4h; in the aging process, an aging temperature is in a range of 15 to 30 DEG C and aging time is in a range of 12 to 24h; in a second stage of the two-stage reaction, a reaction temperature is in a range of 90 to 97 DEG C and reaction time is in a range of 3 to 5h; after the two-stage reaction is finished, reaction products are cooled and filtered; filter cake is washed by an ethanol solution and then is dried to form a crystal product.
Description
Technical field
The present invention is the technology method of two (4, the 6-di-tert-pentyl phenol) products of a kind of synthetic 2,2 '-ethylene.Be specifically related to paraldehyde, 2,4-di-tert-pentyl phenol is raw material, and mineral acid is catalyzer, carries out the technological method of phenol formaldehyde condensation reaction in water miscible liquid, improves targetedly product crystalline particle state, belongs to chemical crystallization technical field.
Background technology
Bisphenol cpd 2,2 '-ethylene two (4,6-di-tert-pentyl phenol) (being called for short oxidation inhibitor bis-phenol-H or bis-phenol-H) is a kind of antioxidant product, be mainly used in the macromolecular materials such as synthetic rubber, polyolefin plastics, engineering plastics, also be to prepare antioxidant of bisphenol monoacryate 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4, the main raw material of 6-bis-tertiary amyl phenyl acrylic compound.The chemical structural formula of product of the present invention suc as formula (
):
（
）
JP2000-239204A discloses with 40% acetaldehyde solution, 2,4-di-tert-pentyl phenol is raw material, containing anionic surfactant sodium dodecylbenzene sulfonate, 36% hydrochloric acid, is that catalyzer, water carry out condensation reaction in as reaction solvent and prepares bis-phenol-H product.Its weak point is: after reaction finishes to cool, the thick product obtaining is not regular crystalline particle, but xln is carried the partical that a small amount of impurity forms secretly, and both so-called agglomerated prod, need to refine and obtain qualified product through ethyl alcohol recrystallization; In addition, the processing method that acetaldehyde solution is raw material, remaining reaction mother liquor cannot recycle, and produces a large amount of sewage discharges, serious environment pollution in production.
In order to improve the deficiency of the technology of JP2000-239204A, in production, produce a large amount of sewage discharges, serious environment pollution problem, Chinese patent CN1994993A discloses take water as reaction solvent, mineral acid is catalyzer, Sodium dodecylbenzene sulfonate is anion surfactant, gas acetaldehyde or paraldehyde substitute 40% acetaldehyde solution, with 2,4-di-tert-pentyl phenol carries out condensation reaction preparation with the processing method of bis-phenol-H in emulsifying water system, and the technological method of employing reaction mother liquor circulation has solved the emission problem of waste water.Its weak point is the bis-phenol-H product generating after phenol formaldehyde condensation reaction, with crystallite figure, be mixed in reaction solution, the particle agglomeration state product that after cooling, microcrystal product formation comprises impurity, carries out solid-liquid separation difficulty on the one hand, as take actual production device as example, with 3M
3reactor, produces 730 kilograms of bis-phenol-H products, and adopting commercial size is 1 meter of whizzer, the solid-liquid separation that completes reaction mother liquor and product needs 26 ~ 28 hours, separation efficiency as can be seen here low, in addition, the washing with alcohol mother liquor containing in isolated solid filter cake is up to 12%; On the other hand, product purification purification difficult, after solid-liquid separation, filter cake need to be used dehydrated alcohol recrystallization, just can obtain bis-phenol-H xln product of regular particle.In ethyl alcohol recrystallization process, some bis-phenol-H product is dissolved in recrystallization mother liquor, to reclaim as far as possible completely, need to be by its thin up, separate out bis-phenol-H product, and then reclaim this part product, the recrystallization mother liquor producing in process, the washing mother liquor aqueous ethanolic solution that is different concns, Distillation recovery in batches, undoubtedly production process too complexity equipment increase, long flow path, ethanol consumption and energy consumption increase, production cost are increased.
In CN1994993A with anhydrous fat aldehyde, 2, 4-di-tert-pentyl phenol is raw material, mineral acid is catalyzer, in water miscible liquid, carrying out phenol formaldehyde condensation reaction prepares in bis-phenol-H process, alkanoic is gas acetaldehyde, although the thick product of the bis-phenol-H obtaining is reunion crystalline product, but with alkanoic be that paraldehyde is prepared the crystal habit that obtains agglomerated prod in the thick product process of bis-phenol-H and in degree, had larger difference, the former crystal habit is significantly better than the latter, the amount of carrying impurity secretly is less than the latter, the process operation of being convenient to solid-liquid separation and product purification is also better than the latter, illustrate anhydrous with alkanoic, 2, 4-di-tert-pentyl phenol is raw material, mineral acid is catalyzer, in water miscible liquid, carrying out phenol formaldehyde condensation reaction prepares in the processing method of bis-phenol-H, the alkanoic using is that the resulting reaction result of gas acetaldehyde is significantly better than using paraldehyde.
Paraldehyde is a kind of colourless oil liquid organic compound, molecular formula C
3h
12o
3be that with the difference of gas acetaldehyde it is water insoluble, the gas acetaldehyde acetaldehyde solution that at once forms soluble in water, with 2,4-di-tert-pentyl phenol carries out phenol formaldehyde condensation reaction to be prepared in bis-phenol-H process, paraldehyde need to be through a process that changes into acetaldehyde solution in sour water emulsion, so paraldehyde and gas phenol formaldehyde condensation reaction process that acetaldehyde carries out exist certain difference, from the experimentation of CN1994993A, can take a hint.Chinese patent CN101638356A discloses take water as reaction solvent, selecting a kind of anionic Anionic Gemini Surfactant is the composite mixed emulsifier of making of assistant for emulsifying agent, by improvement, react surfactivity, dispersiveness or the wettability of emulsion, phenol formaldehyde condensation reaction preparation 2 is carried out in improvement in water miscible liquid, 2 '-methylene-bis (4,6-DI-tert-butylphenol compounds) is the processing method of a series of bisphenol compound antioxidant products of master.Wherein the crystallized product in order to obtain as far as possible in preparing bis-phenol-H process, selects 40% acetaldehyde solution and 2,4-di-tert-pentyl phenol to react, and has avoided use paraldehyde.Chinese patent CN101704728A discloses take water as reaction solvent, to there is the liquid organic acid catalyst of phase transfer catalysis and emulsifying effect dual-use function, substitute inorganic acid catalyst and tensio-active agent, in emulsifying water system, carry out condensation reaction and prepare the processing method that 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol) is a series of bisphenol compound antioxidant products of master.Wherein the crystallized product in order to obtain as far as possible in preparing bis-phenol-H process, selects 40% acetaldehyde solution or gas acetaldehyde and 2,4-di-tert-pentyl phenol to react, and has also avoided use paraldehyde.
Prepare in the processing method of bis-phenol-H, although use free state acetaldehyde to be better than use paraldehyde as gas acetaldehyde or the resulting reaction result of 40% acetaldehyde solution, but, in 40% acetaldehyde solution natural storage process, the polycondensation of part acetaldehyde becomes paraldehyde or the methaldehyde, immiscible with former acetaldehyde solution, separate out rear formation oil, water layer two-phase, the charging capacity that can not measure in process of production acetaldehyde material; The storage of gas acetaldehyde raw material and transportation are inconvenient, and place for a long time acetaldehyde and can polycondensation become paraldehyde.Paraldehyde can be used as the stable form of acetaldehyde, is convenient to store, transportation and using, therefore prepare bis-phenol-H product select paraldehyde be raw material for convenience of, rationally.
JP2006-36685A discloses with paraldehyde, 2, and 4-di-tert-pentyl phenol is raw material, and 78% sulfuric acid is catalyzer, carries out condensation reaction in containing anion surfactant and heptane.Its weak point is: in reaction, need a large amount of organic solvent heptane, even if recycle, volatile solvent still has larger consumption, makes production process more complicated, and facility investment is large, and production cost is higher; In addition, reaction back end hydrogenation aqueous solution of sodium oxide neutralization reaction liquid, the aqueous sodium persulfate solution that contains anion surfactant easily dissolves in heptane, 2, the organism such as 4-di-tert-pentyl phenol, acetaldehyde, and the water of using with washing oil reservoir forms a large amount of waste water, will environment be caused to serious harm.Final this Technology cannot solve the crystalline state problem of bis-phenol-H product, therefore only prepares the n-heptane solution of bis-phenol-H, rather than the crystalline product of bis-phenol-H.
Summary of the invention
In order to improve JP2000-239204A, CN1994993A technology method, solve the crystal habit of production bis-phenol-H product to follow-up solid-liquid separation of carrying out reaction solution, the difficulty that product purification is purified and brought, the Technology that the present invention selects is: with 2, 4-di-tert-pentyl phenol, paraldehyde is raw material, containing emulsifying agent, mineral acid catalyst, the aqueous solution of dispersion agent is made reaction solvent, adopt two-stage reaction process, the method of inserting ageing process in the middle of two-stage reaction process is prepared bis-phenol-H product, with this, improved the crystalline state of bisphenol synthesis-H product in reaction solution.
With paraldehyde and 2,4-di-tert-pentyl phenol is raw material, mineral acid is catalyzer, in water miscible liquid, carrying out phenol formaldehyde condensation reaction prepares in bis-phenol-H product process, according to Ostwald-Lussac rule, ageing process comprises the dissolving of the particle that is less than a critical size, and then mass transfer is to being greater than on the particle of this critical size.Reaction solution is in ageing process, the dissolving of the relative small-particle bis-phenol-H being generated by one section of reaction process is accompanied by the growth of relative macroparticle bis-phenol-H, in system, be under certain saturation degree condition, select suitable Aging Temperature and digestion time, affect the nucleation of bis-phenol-H product in nonhomogeneous system; In ageing process, the effect of bis-phenol-H product nucleation and crystallization can be extended to second-stage reaction end of processing, and both end reaction finished bis-phenol-H product crystal habit of rear formation.
The method of two (4,6-di-tert-pentyl phenol) the product crystalline states of synthetic 2, the 2 '-ethylene of a kind of improvement of the present invention, according to
Following step is carried out:
By 2,4-di-tert-pentyl phenol, paraldehyde, emulsifying agent, catalyzer, dispersion agent, water join in airtight reactor in proportion, nitrogen replacement, adopts two-stage reaction process, in the middle method of inserting ageing process of two-stage reaction process, prepares bis-phenol-H product; After reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-75% for filter cake, obtains bis-phenol-H crystalline product after being dried.
The add-on of wherein said paraldehyde is measured by itself and the mol ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: paraldehyde (mol ratio)=1:0.167 ~ 0.255; The add-on of emulsifying agent is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: emulsifying agent (mass ratio)=1:0.05 ~ 0.15; The add-on of catalyzer is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: catalyzer (mass ratio)=1:0.19 ~ 0.23; The add-on of dispersion agent is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: dispersion agent (mass ratio)=1:0.03 ~ 0.08; The add-on of water is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: water (mass ratio)=1:2.0 ~ 4.0.
Wherein said emulsifying agent refers to Sodium dodecylbenzene sulfonate; Catalyzer refers to hydrochloric acid, sulfuric acid, phosphoric acid; Dispersion agent refers to C
6～C
8aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon.
Wherein said employing two-stage reaction process, insert ageing process in the middle of the two-stage reaction process and refer to: from reaction, start to be made as one section of reaction process to for some time is carried out in reaction, cool to Aging Temperature, stop stirring, the processing parameter of one section of described reaction process is: 90 ~ 97 ℃ of temperature of reaction; Reaction times 2 ~ 4h; Reaction system enters a constant temperature ageing process stage, after completing ageing process, is warming up to temperature of reaction, starts stirring, and both second-stage reaction started, and insulation reaction completes second-stage reaction process; The processing parameter of constant temperature ageing process is: 15 ~ 30 ℃ of constant temperature Aging Temperatures; Digestion time 12 ~ 24h; The processing parameter of second-stage reaction process is: 90 ~ 97 ℃ of temperature of reaction; Reaction times 3 ~ 5h.
advantage of the present invention
(1), the present invention adopts two-stage reaction process, in the middle of two-stage reaction process, the method for insertion ageing process is prepared bis-phenol-H product, with this, improved and take paraldehyde as the crystalline state of raw material bisphenol synthesis-H product in reaction solution, solved the solid-liquid separation of reaction solution and the difficulty that product purification is purified and brought.
(2), with processing method of the present invention, prepare in bis-phenol-H product process, thick product formation oarse-grained crystal, the finished product purity is high, quality good; This processing method has been simplified production process, has improved production efficiency, has been reduced raw materials consumption, energy consumption and production cost, is convenient to large-scale industrial and produces.
Embodiment
Experimental raw 2 used in the present invention, 4-di-tert-pentyl phenol, paraldehyde, emulsifying agent, catalyzer, dispersion agent are commercially available prod, specification is industrial top grade product.
Following non-limiting example 1～7 is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all belong to protection scope of the present invention.
embodiment 1
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 9.4 grams of paraldehydes, 200 grams, water, 5 grams of 10% Sodium dodecylbenzene sulfonatees, 19.0 grams of 37% hydrochloric acid, 6.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 95 ~ 97 ℃, insulation reaction 2h, then be cooled to 15 ~ 18 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 12h, after ageing finishes, stirring is warming up to 95 ~ 97 ℃, insulation reaction 5h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-70% for filter cake, obtain bis-phenol-H white crystals product, fusing point 118.3-119.5 ℃, product yield 83.4%.
embodiment 2
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 14.4 grams of paraldehydes, 300 grams, water, 10 grams of 10% Sodium dodecylbenzene sulfonatees, 23 grams of 37% hydrochloric acid, 5.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 90 ~ 92 ℃, insulation reaction 3h, then be cooled to 20 ~ 22 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 18h, after ageing finishes, stirring is warming up to 90 ~ 92 ℃, insulation reaction 4h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 70-75% for filter cake, obtain bis-phenol-H white crystals product, 118.5 ~ 119.4 ℃ of fusing points, product yield 92.3%.
embodiment 3
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 12.2 grams of paraldehydes, 400 grams, water, 15 grams of 10% Sodium dodecylbenzene sulfonatees, 22 grams of 37% hydrochloric acid, 3.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 95 ~ 97 ℃, insulation reaction 4h, then be cooled to 28 ~ 30 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 24h, after ageing finishes, stirring is warming up to 95 ~ 97 ℃, insulation reaction 4h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-70% for filter cake, obtain bis-phenol-H white crystals product, 118.3 ~ 119.6 ℃ of fusing points, product yield 90.6%.
embodiment 4
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 12.2 grams of paraldehydes, 300 grams, water, 15 grams of 10% Sodium dodecylbenzene sulfonatees, 19.5 grams of 37% hydrochloric acid, 8.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 94 ~ 96 ℃, insulation reaction 3h, then be cooled to 20 ~ 22 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 18h, after ageing finishes, stirring is warming up to 94 ~ 96 ℃, insulation reaction 5h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 70-75% for filter cake, obtain bis-phenol-H white crystals product, 118.2 ~ 119.8 ℃ of fusing points, product yield 94.1%.
embodiment 5
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 14.4 grams of paraldehydes, 400 grams, water, 10 grams of 10% Sodium dodecylbenzene sulfonatees, 22 grams of 37% hydrochloric acid, 5.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 92-93 ℃, insulation reaction 3h, then be cooled to 15 ~ 18 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 12h, after ageing finishes, stirring is warming up to 92-93 ℃, insulation reaction 5h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 70-75% for filter cake, obtain bis-phenol-H white crystals product, 118.7 ~ 119.6 ℃ of fusing points, product yield 93.5%.
embodiment 6
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 9.4 grams of paraldehydes, 400 grams, water, 10 grams of 10% Sodium dodecylbenzene sulfonatees, 23 grams of 37% hydrochloric acid, 5.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 95 ~ 97 ℃, insulation reaction 2h, then be cooled to 20 ~ 22 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 24h, after ageing finishes, stirring is warming up to 95 ~ 97 ℃, insulation reaction 5h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-70% for filter cake, obtain bis-phenol-H white crystals product, 118.2 ~ 119.1 ℃ of fusing points, product yield 86.7%.
embodiment 7
In the GSHB type 1000mL glass reaction still with magnetic stirring apparatus, add 2, 100 grams of 4-di-tert-pentyl phenols, 12.5 grams of paraldehydes, 300 grams, water, 15 grams of 10% Sodium dodecylbenzene sulfonatees, 21.5 grams of 37% hydrochloric acid, 5.0 grams of dispersion agents, nitrogen replacement, stir and heat up, when in system, temperature rises to 92 ~ 93 ℃, insulation reaction 3h, then be cooled to 28 ~ 30 ℃ of Aging Temperatures, stop stirring, constant temperature digestion time 14h, after ageing finishes, stirring is warming up to 92 ~ 93 ℃, insulation reaction 4h, after reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-70% for filter cake, obtain bis-phenol-H white crystals product, 117.8 ~ 119.3 ℃ of fusing points, product yield 85.2%.
Claims (2)
1. one kind is improved synthetic 2,2 '-ethylene two (4,6-di-tert-pentyl phenol) method of product crystalline state, it is characterized in that carrying out according to following step: by 2,4-di-tert-pentyl phenol, paraldehyde, emulsifying agent, catalyzer, dispersion agent, water join in airtight reactor in proportion, nitrogen replacement, adopts two-stage reaction process, in the middle method of inserting ageing process of two-stage reaction process, prepares bis-phenol-H product; After reaction finishes, be cooled to 25 ~ 28 ℃, filter reaction mixture, the ethanolic soln washing of 65-75% for filter cake, obtains bis-phenol-H crystalline product after being dried; Described employing two-stage reaction process, insert ageing process in the middle of the two-stage reaction process and refer to: from reaction, start to be made as one section of reaction process to for some time is carried out in reaction, cool to Aging Temperature, stop stirring, the processing parameter of one section of described reaction process is: 90 ~ 97 ℃ of temperature of reaction; Reaction times 2 ~ 4h; Reaction system enters a constant temperature ageing process stage, after completing ageing process, is warming up to temperature of reaction, starts stirring, and second-stage reaction starts, and insulation reaction completes second-stage reaction process; The processing parameter of constant temperature ageing process is: 15 ~ 30 ℃ of constant temperature Aging Temperatures; Digestion time 12 ~ 24h; The processing parameter of second-stage reaction process is: 90 ~ 97 ℃ of temperature of reaction; Reaction times 3 ~ 5h;
The add-on of wherein said paraldehyde is measured by itself and the mol ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: paraldehyde=1:0.167 ~ 0.233; The add-on of emulsifying agent is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: emulsifying agent=1:0.05 ~ 0.15; The add-on of catalyzer is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: catalyzer=1:0.019 ~ 0.023; The add-on of dispersion agent is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: dispersion agent=1:0.03 ~ 0.08; The add-on of water is measured by itself and the mass ratio of 2,4-di-tert-pentyl phenol, 2,4-di-tert-pentyl phenol: water=1:2.0 ~ 4.0.
2. the method for two (4,6-di-tert-pentyl phenol) the product crystalline states of synthetic 2, the 2 '-ethylene of a kind of improvement according to claim 1, is characterized in that wherein said emulsifying agent is Sodium dodecylbenzene sulfonate; Catalyzer is hydrochloric acid, sulfuric acid, phosphoric acid; Dispersion agent is C
6～C
8aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239204A (en) * | 1998-12-22 | 2000-09-05 | Sumitomo Chem Co Ltd | Production of bisphenols |
| CN1994993A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Cleaning production method for preparing bisphenol compound antioxidant product |
| CN101638356A (en) * | 2009-08-18 | 2010-02-03 | 江苏工业学院 | Preparation method of bisphenol compound antioxidant product |
| CN101704728A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Method for preparing bisphenol compound antioxidant product by using organic acid catalyst |
-
2012
- 2012-07-30 CN CN201210267488.5A patent/CN102816053B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239204A (en) * | 1998-12-22 | 2000-09-05 | Sumitomo Chem Co Ltd | Production of bisphenols |
| CN1994993A (en) * | 2006-11-24 | 2007-07-11 | 江苏工业学院 | Cleaning production method for preparing bisphenol compound antioxidant product |
| CN101638356A (en) * | 2009-08-18 | 2010-02-03 | 江苏工业学院 | Preparation method of bisphenol compound antioxidant product |
| CN101704728A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Method for preparing bisphenol compound antioxidant product by using organic acid catalyst |
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Effective date of registration: 20210122 Address after: 226600 No. 2, C District, Chengbei Industrial Park, Haian County, Nantong, Jiangsu province (Dagong industrial concentration area, Haian county) Patentee after: NANTONG HAILITE RUBBER & PLASTIC MACHINERY Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
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Granted publication date: 20141029 Termination date: 20210730 |