CN104761516A - Method used for preparing epoxy compound via chlorohydrine intermediate cyclization catalyzed by supported solid base - Google Patents
Method used for preparing epoxy compound via chlorohydrine intermediate cyclization catalyzed by supported solid base Download PDFInfo
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- CN104761516A CN104761516A CN201410000122.0A CN201410000122A CN104761516A CN 104761516 A CN104761516 A CN 104761516A CN 201410000122 A CN201410000122 A CN 201410000122A CN 104761516 A CN104761516 A CN 104761516A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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Abstract
The invention discloses a method used for preparing an epoxy compound via chlorohydrine intermediate cyclization catalyzed by a supported solid base; wherein the chlorohydrine intermediate specifically refers to terephthalic acid-di(3-chloro-2-hydroxypropyl)ester which is obtained via esterification ring-opening of terephthalic acid with epoxy chloropropane, and the epoxy compound refers to p-phthalic diglycidyl ester. The invention belongs to the technical field of green chemistry. The method comprises following steps: the chlorohydrine intermediate obtained via ring-opening of terephthalic acid with epoxy chloropropane is subjected to cyclization reaction in the presence of the supported solid base catalyst; after reaction, the supported solid base catalyst is removed via filteration; and the epoxy compound is obtained by removing solvents via distillation. Advantages of the method are that: liquid base catalysis in the cyclization reaction is avoided, generation of a large amount of saline wastewater is avoided, the solvents can be recycled, and the technology is simple. And in addition, the supported solid base catalyst is simple to prepare, is simple to separate, and is friendly to the environment; and the method belongs to a green chemical technology.
Description
Technical field
The present invention relates to Green Chemical Technology field, be specifically related to the method that epoxy compounds is prepared in the cyclisation of a kind of supported solid base catalysis chlorohydrin intermediate.
Background technology
On current domestic and international market, weather-resistance powder coatings solidifying agent principal item is isocyanuric acid three-glycidyl ester (TGIC), but it has been found to have ecological toxicity, is limited gradually to use on Europe, Australia and other places.Meanwhile researcher is also at the surrogate that active development is suitable with its performance, and the hydroxy alkyl amide curing agents Primid XL552 wherein released by Rohm & Hass company and the polynary glycidyl benzoate PT910/912 developed by Huntsman company is topmost kind.But for Primid XL552 solidifying agent, can micromolecular compound be generated in its solidification process, occur pin-hole phenomena, and its yellowing resistance is also poor.And for PT910/912 solidifying agent, its be by terephthalic acid diglycidyl ester and trimellitic acid three-glycidyl ester in mass ratio 3:1 and 3:2 interworking form.Its weathering resistance is close to TGIC level, and ecological toxicity reduces greatly, although comparatively Primid XL552 is poor for its reactive behavior, can add promotor adjustment.
Synthetic method at present for the benzoic acid type glycidyl ester of PT910/912 curing agent component mainly contains chloride method, carboxylate salt single stage method, esterification-closed loop two-step approach, oxidation style, ester-interchange method etc.
US3073804 reports and utilizes benzene to make solvent, and p-phthaloyl chloride and R-GLYCIDOL low temperature under the alkaline condition such as triethylamine or pyridine is obtained by reacting terephthalic acid diglycidyl ester.The method is due to R-GLYCIDOL easy self-polymerization polluted product in the basic conditions, and acyl chlorides activity is very large, reacts bad control, and temperature of reaction requires lower, is not suitable for suitability for industrialized production.
US2940986 reports the synthesis of long-chain fat acid glycidyl ester, utilizes hard soap and epoxy chloropropane in anhydrous conditions, and reacting by heating obtains long-chain fat acid glycidyl ester product; CN1746150 also reports and utilizes Sodium Benzoate and epoxy chloropropane in a suitable solvent, through phase-transfer catalysis esterification, and obtained glycidyl benzoate.The method is mainly used in prepares aliphatic glycidyl ester, and for the more difficult preparation of polynary benzoate, and reaction requires strict anhydrous condition, requires comparatively harsh to reaction system.
US4667044 reports the glycidyl ester utilizing corresponding aromatic carboxylic acid alkyl ester and R-GLYCIDOL obtained corresponding under the catalysis such as sodiumazide, potassium cyanate or Potassium Selenocyanate.Adopt ester-interchange method to prepare glycidyl ester and need adopt specific catalyst, and these catalyzer also have certain toxicity, are not suitable for suitability for industrialized production.
GB862588 reports under Zeo-karb existence condition, and terephthaldehyde's allyl propionate and Peracetic Acid are reacted, Direct Epoxidation, obtained terephthaldehyde's acid glycidyl ester.US5036154 reports polycarboxylic acid allyl ester and under basic metal or alkaline-earth tungstate, phosphoric acid and phase-transfer catalyst existence condition, is obtained by reacting corresponding glycidyl ester product to hydrogen peroxide oxidant for a long time.Utilize oxidation style to prepare polynary glycidyl benzoate, Perfect Ring oxidation is more difficult, can generate mono-epoxide impurity, affect yield and the purity of product.
Current industrial production mainly adopts esterification-closed loop two-step approach, and US3859314 reports terephthalic acid and epoxy chloropropane esterification by ring opening under quaternary ammonium salt catalyst effect, and then under the 50%NaOH aqueous solution exists, closed loop generates terephthalic acid diglycidyl ester.Wherein in closed loop procedure, use liquid alkali catalyst, it is more loaded down with trivial details that reaction terminates rear aftertreatment, can produce a large amount of trade effluent, cause very large impact to ecotope.
Summary of the invention
The object of the invention is to the deficiency improving existing technique, thering is provided the cyclisation of a kind of supported solid base catalysis chlorohydrin intermediate to prepare the method for epoxy compounds, is the method adopting terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) the ester cyclisation of supported solid base catalysis chlorohydrin intermediate to prepare terephthalic acid diglycidyl ester.This method production technique is simple, and reaction terminates rear catalyst and is easy to and product separation, convenient post-treatment, and avoids producing a large amount of trade effluent, and environmental pollution is little, is a kind of Technology of green economy.
Realize concrete technical scheme of the present invention as follows:
The cyclisation of load type solid body base catalyst catalysis chlorohydrin intermediate generates a method for epoxy compounds, and concrete steps are as follows:
The first step, esterification: by phthalic acid, epoxy chloropropane, quaternary ammonium salt hybrid reaction, steams excess epoxy chloropropane after reaction terminates, obtains chlorohydrin intermediate;
Second step, cyclization: the chlorohydrin intermediate obtained to the first step adds load type solid body base catalyst, solvent, heated and stirred is reacted, and filters out load type solid body base catalyst and recycle after reaction terminates, filtrate steaming removal solvent, obtains terephthalic acid diglycidyl ester.
Wherein in step one, the mol ratio of terephthalic acid and epoxy chloropropane is 1:16, and the one in palmityl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetramethyl ammonium chloride selected by quaternary ammonium salt.。
In step 2, the active ingredient of load type solid body base catalyst is sodium hydroxide or salt of wormwood, and the carrier of load active component is titanium dioxide, magnesium oxide, aluminium sesquioxide or gac, and the charge capacity of active ingredient is 10 ~ 50%.
Described load type solid body base catalyst selects NaOH/TiO
2, K
2cO
3/ TiO
2, NaOH/Al
2o
3, K
2cO
3/ Al
2o
3, NaOH/C, K
2cO
3/ C, K
2cO
3one in/MgO, NaOH/MgO.
In step 2, load type solid body base catalyst reclaims maturing temperature when using is 500 DEG C, and roasting time is 5h.
In step 2, load type solid body base catalyst and chlorohydrin intermediate mass ratio are 0.25 ~ 1:1.Wherein preferred mass ratio is 0.65 ~ 0.7:1.
In step 2, solvent is methylene dichloride, ethyl acetate, tetrahydrofuran (THF), the one in epoxy chloropropane.Wherein preferred solvent is methylene dichloride, recyclablely recycles.
In step 2, stirring reaction temperature is 20 ~ 60 DEG C, and wherein preferable temperature is 40 DEG C.Reaction times is 4 ~ 10h, and wherein preferably the time is 6h.
In the present invention, described load type solid body base catalyst adopts equi-volume impregnating preparation: take a certain amount of carrier, with the NaOH aqueous solution or K
2cO
3aqueous solution room temperature incipient impregnation 24h, at 100 ~ 110 DEG C, dry removing moisture, then roasting 5h under 500 DEG C of conditions in retort furnace, is cooled to grinding at room temperature and get final product.
The present invention carries out according to following chemical reaction:
The present invention compared with prior art has the following advantages: (1) reported first utilizes load type solid body base catalyst catalysis to prepare terephthalic acid diglycidyl ester; (2) present invention improves over the deficiency of existing technique, avoid adopting liquid base to produce a large amount of trade effluent, environmental pollution is little, and closed loop solvent is capable of circulation reuses, and is a kind of chemical technology method of green economy.
Accompanying drawing explanation
Fig. 1 is terephthalic acid diglycidyl ester product
1h NMR spectrogram.
Fig. 2 is embodiment 1 gained load type solid body base catalyst NaOH/TiO
2fT-IR spectrogram.
Fig. 3 is embodiment 2 gained load type solid body base catalyst NaOH/Al
2o
3fT-IR spectrogram.
Fig. 4 is the HPLC spectrogram of chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.
Fig. 5 is the HPLC spectrogram of embodiment 1 gained terephthalic acid diglycidyl ester.
Fig. 6 is the HPLC spectrogram of terephthalic acid diglycidyl ester standard specimen.
Embodiment
The present invention's following examples illustrate, but the present invention is not limited to following embodiment, and under the scope not departing from the described aim in front and back, change is included in technical scope of the present invention.
Embodiment 1:
Take 5gNaOH solid, add a small amount of water configuration NaOH aqueous solution.Separately take 5gTiO
2be placed in beaker, add the above-mentioned NaOH aqueous solution room temperature condition volumetric dipping 24h configured wherein.Under 100 ~ 110 DEG C of conditions, dry removing moisture subsequently, be placed in crucible, then roasting 5h under 500 DEG C of conditions in retort furnace, is cooled to grinding at room temperature and namely obtains NaOH/TiO
2solid base catalyst, wherein NaOH charge capacity is 50%.Hammett indicator method is adopted to record its base strength H
-be 15.0 ~ 18.4.
Fig. 2 is made NaOH/TiO
2the FT-IR spectrogram of solid base catalyst, as seen from Figure 2, NaOH/TiO
2after solid alkali roasting, at 517cm
-1place TiO
2absorption peak disappears, at 670 cm
-1, 876cm
-1there is absorption peak in place, can judge that NaOH loads to TiO thus
2on.
1.66g terephthalic acid, 14.8g epoxy chloropropane, 0.083g palmityl trimethyl ammonium chloride is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.Methylene dichloride makes closed loop solvent, adds the above-mentioned NaOH/TiO of 2.5g
2solid base catalyst, stirring reaction 6h at 40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product, liquid-phase chromatographic analysis product, as shown in Fig. 4 ~ Fig. 6, in Fig. 4, the chlorohydrin intermediate absorption peak of about 27min is after reaction, and major part is converted into the terephthalic acid diglycidyl ester absorption peak of about 22min, chlorohydrin intermediate transformation efficiency is 92.7%, yield 93.2%.
Embodiment 2 ~ 6:
Except solid base catalyst type difference, all the other operations are identical with embodiment 1, and experimental result is in table one:
Table one:
Fig. 3 is made NaOH/Al
2o
3the FT-IR spectrogram of solid base catalyst, as seen from Figure 3, NaOH/Al
2o
3after solid alkali roasting, at 470 cm
-1there is O-Na-O absorption peak in place, 560cm
-1, 617cm
-1there is Al-O absorption peak in place, 818cm
-1there is O-O absorption peak in place, can judge thus to generate NaAlO
2; 1630 cm
-1, 3000 ~ 3500 cm
-1place is OH
-absorption peak; 1450 cm
-1for CO
2absorption peak, and after roasting, this peak obviously weakens.
Embodiment 7 ~ 10:
The solid base catalyst NaOH/TiO that charge capacity is respectively 10%, 20%, 30%, 40% is prepared by solid alkali preparation method described in embodiment 1
2, preparing in terephthalic acid diglycidyl ester product process, adding above-mentioned different loads amount solid base catalyst respectively, all the other operations are identical with embodiment 1, and experimental result is in table two:
Table two:
Embodiment 11 ~ 13:
The solid base catalyst K that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1
2cO
3/ MgO, is preparing in terephthalic acid diglycidyl ester product process, is adding the above-mentioned solid base catalyst of 1.0g, 1.6g, 3.2g respectively, and all the other operations are identical with embodiment 1, and experimental result is in table three:
Table three
Embodiment 14 ~ 16:
The solid base catalyst NaOH/Al that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1
2o
3, prepare terephthalic acid diglycidyl ester product respectively at adding system reaction under 20 DEG C, 30 DEG C, 60 DEG C conditions, all the other operations are identical with embodiment 1, and experimental result is in table four:
Table four:
Embodiment 17 ~ 18:
The solid base catalyst K that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1
2cO
3/ MgO, add system reaction and prepare terephthalic acid diglycidyl ester product, the reaction times is respectively 4h, 10h, and all the other operations are identical with embodiment 1, and experimental result is in table five:
Table five:
Embodiment 19:
The solid base catalyst NaOH/C that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1.
Carry out ring-opening reaction by described in embodiment 1, after ring-opening reaction stops, not steaming epoxy chloropropane, directly add above-mentioned solid base catalyst, stirring reaction 6h at 40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product, liquid-phase chromatographic analysis product, and chlorohydrin intermediate transformation efficiency is 78.4 %, yield 26.5%.
Embodiment 20:
The solid base catalyst K that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1
2cO
3/ TiO
2.
Carry out ring-opening reaction by described in embodiment 1, after ring-opening reaction stops, steaming except excess epoxy chloropropane, ethyl acetate makes closed loop solvent, adds above-mentioned solid base catalyst, stirring reaction 6h at 40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product, liquid-phase chromatographic analysis product, and chlorohydrin intermediate transformation efficiency is 90.1 %, yield 61.1%.
Embodiment 21:
The solid base catalyst NaOH/TiO that charge capacity is 50% is prepared by solid alkali preparation method described in embodiment 1
2.
Epoxy chloropropane, the 0.083g palmityl trimethyl ammonium chloride of 1.66g terephthalic acid, 14.8g recovery is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.The methylene dichloride reclaimed makes closed loop solvent, adds the above-mentioned NaOH/TiO of 2.5g
2solid base catalyst, stirring reaction 6h at 40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product.Liquid-phase chromatographic analysis product, chlorohydrin intermediate transformation efficiency is 95.6%, yield 86.0%.
Embodiment 22:
Get the solid base catalyst NaOH/TiO using and reclaim
2, grind and be placed in crucible, then roasting 5h under 500 DEG C of conditions in retort furnace, is cooled to grinding at room temperature stand-by, is designated as reuse 1.
1.66g terephthalic acid, 14.8g epoxy chloropropane, 0.083g palmityl trimethyl ammonium chloride is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.Methylene dichloride makes closed loop solvent, adds stirring reaction 6h at 2.5g above-mentioned solid base catalyst reuse Isosorbide-5-Nitrae 0 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product.Liquid-phase chromatographic analysis product, chlorohydrin intermediate transformation efficiency is 84.2%, yield 52.2%.
Embodiment 23:
Get the solid base catalyst NaOH/TiO using secondary recovery
2reuse 1, grinds and is placed in crucible, and then roasting 5h under 500 DEG C of conditions in retort furnace, is cooled to grinding at room temperature stand-by, is designated as reuse 2.
1.66g terephthalic acid, 14.8g epoxy chloropropane, 0.083g palmityl trimethyl ammonium chloride is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.Methylene dichloride makes closed loop solvent, adds stirring reaction 6h at the above-mentioned solid base catalyst reuse of 2.5g 2,40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product.Liquid-phase chromatographic analysis product, chlorohydrin intermediate transformation efficiency is 85.3%, yield 57.5%.
Embodiment 24:
The filter cake that Example 21 reclaims, as carrier, prepares by solid alkali preparation method described in embodiment 1 the solid base catalyst NaOH/TiO that charge capacity is 50%
2, be designated as new 1.
1.66g terephthalic acid, 14.8g epoxy chloropropane, 0.083g palmityl trimethyl ammonium chloride is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.Methylene dichloride makes closed loop solvent, adds stirring reaction 6h at 2.5g above-mentioned solid base catalyst new Isosorbide-5-Nitrae 0 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product.Liquid-phase chromatographic analysis product, chlorohydrin intermediate transformation efficiency is 90.9%, yield 63.3%.
Embodiment 25
Example 24 reclaim filter cake as carrier, prepare by solid alkali preparation method described in embodiment 1 the solid base catalyst NaOH/TiO that charge capacity is 50%
2, be designated as new 2.
1.66g terephthalic acid, 14.8g epoxy chloropropane, 0.083g palmityl trimethyl ammonium chloride is added in 50ml round-bottomed flask, stirring is warming up to 90 DEG C, stop after insulation reaction 3h, steam excess epoxy chloropropane, obtain chlorohydrin intermediate terephthalic acid-two (3-chlorine-2-hydroxyl propyl group) ester.Methylene dichloride makes closed loop solvent, adds stirring reaction 6h at the above-mentioned solid base catalyst new of 2.5g 2,40 DEG C.After reaction terminates, filter to isolate solid base catalyst, steaming desolventizes, and vacuumizes, and obtains terephthalic acid diglycidyl ester product.Liquid-phase chromatographic analysis product, chlorohydrin intermediate transformation efficiency is 86.3%, yield 41.7%.
Claims (9)
1. a method for epoxy compounds is prepared in the cyclisation of supported solid base catalysis chlorohydrin intermediate, it is characterized in that concrete steps are as follows:
The first step, esterification: by terephthalic acid, epoxy chloropropane, quaternary ammonium salt hybrid reaction, steams excess epoxy chloropropane after reaction terminates, obtains chlorohydrin intermediate;
Second step, cyclization: the chlorohydrin intermediate obtained to the first step adds load type solid body base catalyst, solvent, heated and stirred is reacted, and filters out load type solid body base catalyst and recycle after reaction terminates, filtrate steaming removal solvent, obtains terephthalic acid diglycidyl ester.
2. method according to claim 1, is characterized in that: in step one, the mol ratio of terephthalic acid and epoxy chloropropane is 1:16.
3. method according to claim 1, is characterized in that: in step one, the one in palmityl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, tetramethyl ammonium chloride selected by quaternary ammonium salt.
4. method according to claim 1, it is characterized in that: in step 2, the active ingredient of load type solid body base catalyst is sodium hydroxide or salt of wormwood, the carrier of load active component is titanium dioxide, magnesium oxide, aluminium sesquioxide or gac, and the charge capacity of active ingredient is 10 ~ 50%.
5. according to claim 4, it is characterized in that: described load type solid body base catalyst selects NaOH/TiO
2, K
2cO
3/ TiO
2, NaOH/Al
2o
3, K
2cO
3/ Al
2o
3, NaOH/C, K
2cO
3/ C, K
2cO
3one in/MgO, NaOH/MgO.
6. method according to claim 1, is characterized in that: in step 2, load type solid body base catalyst reclaims maturing temperature when using is 500 DEG C, and roasting time is 5h.
7. method according to claim 1, is characterized in that: in step 2, load type solid body base catalyst and chlorohydrin intermediate mass ratio are 0.25 ~ 1:1.
8. method according to claim 1, is characterized in that: in step 2, solvent is methylene dichloride, ethyl acetate, tetrahydrofuran (THF), the one in epoxy chloropropane
.
9. method according to claim 1, is characterized in that: in step 2, stirring reaction temperature is 20 ~ 60 DEG C, and the reaction times is 4 ~ 10h.
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| CN201410000122.0A CN104761516A (en) | 2014-01-02 | 2014-01-02 | Method used for preparing epoxy compound via chlorohydrine intermediate cyclization catalyzed by supported solid base |
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|---|---|---|---|
| CN201410000122.0A CN104761516A (en) | 2014-01-02 | 2014-01-02 | Method used for preparing epoxy compound via chlorohydrine intermediate cyclization catalyzed by supported solid base |
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Cited By (4)
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| CN109111412A (en) * | 2018-10-18 | 2019-01-01 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of terephthalic acid diglycidyl ester |
| CN109232479A (en) * | 2018-10-18 | 2019-01-18 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of trimellitic acid three-glycidyl ester |
| CN112645831A (en) * | 2020-12-14 | 2021-04-13 | 浙江鑫甬生物化工股份有限公司 | Synthesis and crystallization method of high-purity N-hydroxymethyl acrylamide |
| CN114507197A (en) * | 2021-12-28 | 2022-05-17 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111412A (en) * | 2018-10-18 | 2019-01-01 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of terephthalic acid diglycidyl ester |
| CN109232479A (en) * | 2018-10-18 | 2019-01-18 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of trimellitic acid three-glycidyl ester |
| CN112645831A (en) * | 2020-12-14 | 2021-04-13 | 浙江鑫甬生物化工股份有限公司 | Synthesis and crystallization method of high-purity N-hydroxymethyl acrylamide |
| CN114507197A (en) * | 2021-12-28 | 2022-05-17 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
| CN114507197B (en) * | 2021-12-28 | 2024-01-26 | 浙江豪邦化工有限公司 | Method for preparing epichlorohydrin by dichloropropanol solid base catalysis method |
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Application publication date: 20150708 |