CN100355713C - Prepn of glycol antimony - Google Patents
Prepn of glycol antimony Download PDFInfo
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- CN100355713C CN100355713C CNB02116519XA CN02116519A CN100355713C CN 100355713 C CN100355713 C CN 100355713C CN B02116519X A CNB02116519X A CN B02116519XA CN 02116519 A CN02116519 A CN 02116519A CN 100355713 C CN100355713 C CN 100355713C
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- antimony
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- entrainer
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Abstract
The preparation method of glycol antimony relates to a preparation method of glycol antimony. In the prior art, antimony acetate, antimony trioxide, etc. are used; because acetate radical and oxide radical are introduced, the color and the quality of a product are influenced. The preparation method of glycol antimony is characterized in that a mode that glycol reacts with antimony trioxide, and raw materials are excessive, and water is continuously removed out in the reaction process is used so that reaction is carried out to right side. Esterification and water generation reaction in the process are carried out in a rectifying tower, and the method is called as a reaction distillation method. The preparation method of glycol antimony has the advantage that the base group does not have adverse effects on a product by a substituting system. The glycol antimony has good solubility, high purity and good color, and the activity of the glycol antimony is higher than that of antimony acetate. The preparation method is widely used for the polymerization reaction process of polyphenyl glycol diformate.
Description
Technical field
The present invention relates to gather to Preparation of Catalyst used in the ethylene glycol dibenzoate polyreaction, specifically the preparation method of antimony glycol.
Background technology
Polyethylene terephthalate (PET) is the polyester material with potential application foreground, its output occupies the 5th in engineering plastics, be mainly used in the component etc. of parts, automobile and the precision instrument of electronic apparatus, mechanical means, to replace metallic substance such as copper, aluminium and cast iron.Along with the continuous expansion of Application Areas, the consumption of PET is increasing year by year.Because the fierceness of market competition in order to reduce cost, gets the mastery in competition, some enterprises enlarge the throughput of PET on the one hand as far as possible, study effective catalyst on the other hand, in the hope of producing the fine product.
Prior art adopts antimony acetate and antimonous oxide, because acetate and oxygen root are arranged, influences the color and luster and the quality of product.And antimony glycol is a kind of novel polycondensation catalyst of production of polyester, and it is antimony series polycondensation catalyst, and is the same with antimonous oxide and antimony acetate, also belongs to antimonious active catalytic category.Compare with other antimony-based catalyst, his characteristics are that the secondary group of substitution system is an ethylene glycol, and the product of system is had no adverse effects, and its specific activity antimony acetate height may be dissolved in the ethylene glycol solution.
Summary of the invention
The objective of the invention is to overcome above-mentioned weak point of the prior art, provide a kind of higher, the preparation method of the antimony glycol of white crystals than antimony acetate catalyst activity.
The object of the invention can reach by following measure, the preparation method of antimony glycol adopts the method for reactive distillation, at temperature of reaction 160-200 ℃, reaction times 30-200min, under ethylene glycol and the antimonous oxide proportioning raw materials condition, carry out the esterification dehydration reaction, form azeotrope with water, sieve plate or filler are adopted in rectifying, and number of theoretical plate is at the 1-5 plate of determining, and the material feeding position is a 0-2 piece theoretical stage, generate thick antimony glycol, from the discharging of tower still,, finally obtain pure antimony glycol product through conventional method purifying.Entrainer is a benzene, toluene, ethylbenzene, ethanol, materials such as propyl alcohol.Entrainer cools off at cat head, layering, and entrainer refluxes, and regulates reflux ratio simultaneously, with control reaction temperature.Washing used solvent is anhydrous methanol, dehydrated alcohol, anhydrous propyl alcohol etc.
Reaction of the present invention is reversible reaction, and as shown in Figure 1, the positive reaction velocity constant is very little, carries out to the right in order to make reaction, and the mode that need to adopt the excessive and reactive distillation of raw material to shift out water is carried out building-up reactions.Ordinary method is to adopt commercial runs such as filtration, washing, crystallization; Recrystallization adopts ethylene glycol, and drying process adopts vacuum-drying.
The present invention has following advantage compared to existing technology: because the secondary group of substitution system is an ethylene glycol, system has no adverse effects to product, and is dissolved in the ethylene glycol solution, and it is good to have solubleness, the purity height, and color and luster is good, than characteristics such as the active height of antimony acetate.
Description of drawings
Fig. 1 is the reaction equation of preparation antimony glycol
Fig. 2 is the infrared absorpting light spectra of antimony glycol
Specific embodiments
With 7 embodiment, the invention will be further described below.
Embodiment 1, antimonous oxide 10g, and ethylene glycol 254g is heated to 180 ℃, stuffing rectification column, number of theoretical plate is the 2-3 piece, theoretical stage backflow benzene, and behind the reaction 100min, water to be flowed out reaches 4.2ml-4.3ml (theoretical aquifer yield is 4.4ml). stop heating, filter, crystallisation by cooling filters recrystallization.The crystallisate absolute ethanol washing.After vacuum-drying, obtain the white crystals thing.Ethylene glycol is determined by infrared spectra and analyzes water content that concrete analytical results is as follows:
Product comes qualitative analysis by infrared spectrometer (Nicolet 750).The infrared absorption spectrum of product as shown in Figure 2.1085cm
-1, 1038cm
-1Be stretching vibration peak, 2939cm
-1, 2872cm
-1Be CH
2The C-H stretching vibration peak of base, 1461cm
-1Be CH
2The flexural vibration peak of base illustrates to have ethylene glycol in the product.With reactant Sb
2O
3Infrared absorption spectra contrast can prove Sb
2O
3Be converted into antimony glycol.And 3369cm in the product infrared spectrum
-1Near strong and wide peak can belong to the stretching vibration for O-H...O, shows the easy hydrolysis of product, generates (HO-CH
2-CH
2-O)
3Sb.This analyzes and has proved the antimony glycol product.
The water yield that generates adopts HP5890II type gas-chromatography to analyze, and detector is TCD, and carrier gas is H
2, chromatogram is that (50m * 0.53mm), gasification temperature is 270 ℃ to SE-5, and detector is 270 ℃, and flow velocity is 39.5ml/min, thereby calculates the yield of product.
Embodiment 3, antimonous oxide 15g, and ethylene glycol 305g is heated to 160 ℃, and plate distillation column, number of theoretical plate are 1, backflow ethylbenzene, behind the reaction 120min, water to be flowed out reaches 6.6ml, stops heating, filters, and crystallisation by cooling filters recrystallization.Crystallisate washs with anhydrous methanol.After vacuum-drying, obtain the white crystals thing.The result is the same.
Embodiment 4, antimonous oxide 20g, and ethylene glycol 508g is heated to 180 ℃,, backflow ethanol, behind the reaction 150min, water to be flowed out reaches 8.8ml, stops heating, filters, and crystallisation by cooling filters recrystallization.Crystallisate washs with anhydrous propyl alcohol.After vacuum-drying, obtain the white crystals thing.The result is the same.
Embodiment 6, antimonous oxide 15g, and ethylene glycol 403g is heated to 180 ℃-200 ℃, and stuffing rectification column, number of theoretical plate are the 2-3 piece, backflow ethanol, behind the reaction 30min, water to be flowed out reaches 8.8ml, stops heating, filters, and crystallisation by cooling filters recrystallization.The crystallisate absolute ethanol washing.After vacuum-drying, obtain the white crystals thing.The result is the same.
Embodiment 7, antimonous oxide 10g, and ethylene glycol 254g is heated to 160 ℃, continuous plate distillation column, number of theoretical plate is 2, backflow benzene, behind the reaction 200min, water to be flowed out reaches 4.2ml, stops heating, filters, and crystallisation by cooling filters recrystallization.The crystallisate absolute ethanol washing.After vacuum-drying, obtain the white crystals thing.The result is the same.
Claims (4)
1, the preparation method of antimony glycol, it is characterized in that: with the method for reactive distillation, at temperature of reaction 160-200 ℃, reaction times 30-200min, under antimonous oxide and the ethylene glycol proportioning raw materials condition, carry out the esterification dehydration reaction, the form that adopts entrainer and water to form azeotrope shifts out water, sieve plate or filler are adopted in rectifying, and number of theoretical plate is at 1-5 piece plate, and the material feeding position is a 0-2 piece theoretical stage, generate thick antimony glycol, from the discharging of tower still,, finally obtain pure antimony glycol product through conventional method purifying.
2, antimony glycol preparation method according to claim 1, it is characterized in that: the entrainer of employing is a benzene, toluene, ethylbenzene, ethanol, propyl alcohol.
3, antimony glycol preparation method according to claim 1, it is characterized in that: entrainer cools off at cat head, entrainer and moisture flow, entrainer refluxes, and regulates reflux ratio simultaneously, with control reaction temperature.
4, antimony glycol preparation method according to claim 1 is characterized in that: the used solvent of purifying washing is an anhydrous methanol, dehydrated alcohol, anhydrous propyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02116519XA CN100355713C (en) | 2002-03-29 | 2002-03-29 | Prepn of glycol antimony |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02116519XA CN100355713C (en) | 2002-03-29 | 2002-03-29 | Prepn of glycol antimony |
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| Publication Number | Publication Date |
|---|---|
| CN1374285A CN1374285A (en) | 2002-10-16 |
| CN100355713C true CN100355713C (en) | 2007-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB02116519XA Expired - Fee Related CN100355713C (en) | 2002-03-29 | 2002-03-29 | Prepn of glycol antimony |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732327B (en) * | 2016-04-27 | 2018-03-06 | 锡矿山闪星锑业有限责任公司 | A kind of microwave reaction prepares the method and device of antimony glycol |
| CN112028745A (en) * | 2020-09-28 | 2020-12-04 | 锡矿山闪星锑业有限责任公司 | Method for recovering ethylene glycol from water generated by reaction of ethylene glycol antimony |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235148A (en) * | 1999-04-16 | 1999-11-17 | 无锡市正茂化工厂 | Preparation of high purity antimony glycol |
| CN1257076A (en) * | 1999-10-26 | 2000-06-21 | 郑立梅 | Glycol antimony catalyst and preparation process thereof |
| CN1270158A (en) * | 2000-01-12 | 2000-10-18 | 曹善文 | Process for preparing antimony compound of binary alcohol |
-
2002
- 2002-03-29 CN CNB02116519XA patent/CN100355713C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235148A (en) * | 1999-04-16 | 1999-11-17 | 无锡市正茂化工厂 | Preparation of high purity antimony glycol |
| CN1257076A (en) * | 1999-10-26 | 2000-06-21 | 郑立梅 | Glycol antimony catalyst and preparation process thereof |
| CN1270158A (en) * | 2000-01-12 | 2000-10-18 | 曹善文 | Process for preparing antimony compound of binary alcohol |
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| CN1374285A (en) | 2002-10-16 |
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Granted publication date: 20071219 Termination date: 20120329 |