CN110467563A - A kind of a kind of fluorine-containing continuous refining process containing nitroxyl oxides of free radical inhibitor and preparation method thereof He 4- hy-droxybutyl - Google Patents
A kind of a kind of fluorine-containing continuous refining process containing nitroxyl oxides of free radical inhibitor and preparation method thereof He 4- hy-droxybutyl Download PDFInfo
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- CN110467563A CN110467563A CN201910762239.5A CN201910762239A CN110467563A CN 110467563 A CN110467563 A CN 110467563A CN 201910762239 A CN201910762239 A CN 201910762239A CN 110467563 A CN110467563 A CN 110467563A
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- C07—ORGANIC CHEMISTRY
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
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Abstract
The present invention relates to a kind of a kind of fluorine-containing continuous refining process containing nitroxyl oxides of free radical inhibitor and preparation method thereof He 4- hy-droxybutyl.The fluorine-containing nitroxyl oxides of free radical inhibitor that contains of the present invention is colourless number a kind of, higher boiling polymerization inhibitor, the polymerization inhibitor is added in the distillation light component of 4- hy-droxybutyl process for refining and product process, in conjunction with three step continuous extractions of the invention, rectifying removes light component, the operation such as short-path distillation, it can be realized the operation that continuous treating is carried out to 4- hy-droxybutyl, distillation process contains nitroxyl oxides of free radical inhibitor using the present invention is fluorine-containing, avoid influence of the product clip with polymerization inhibitor and to product color number in product distillation process, a whole set of separating technology operation labor intensity is small simultaneously, obtained product purity is high, color number is low, easily realize serialization industrial production.
Description
Technical field
The invention belongs to field of organic compound preparation, are related to the process for refining of crylic acid hydroxy ester, and in particular to a kind of
It is fluorine-containing to contain nitroxyl oxides of free radical inhibitor and preparation method thereof and a kind of continuous refining process of 4- hy-droxybutyl.
Background technique
4- hy-droxybutyl (4-HBA) is mainly used in the surface covering baking vanish of automobile metal coating, auto industry
It advances by leaps and bounds and has driven the rapid development of car paint industry, wherein by Hydroxylated acrylic resin (HAR) and cured with isocyanates
The bi-component acrylic polyurethane coating of agent composition is even more can room temperature or the spies such as low-temperature bake solidifies, polishing grinding performance is good with it
Property become car repair industry in coating varnish principal item.
Have related process report, the direct ester of blue monarch's treasure etc. using extraction and rectification process purification 4- hy-droxybutyl
Selection hydroquinone is mentioned in the research and optimization of change method synthesis 4- hy-droxybutyl technique and p-hydroxyanisole compounds resistance
Polymerization inhibitor of the poly- agent as reaction, extractant of the hexamethylene as 1,4-butanediol diacrylate, methylene chloride are used as from water
The extractant of 4- hy-droxybutyl is extracted in phase, extraction temperature is selected as 20 DEG C, and by Aspen Plus to reaction and separation
Process flow is simulated, and 4- propylene hydroxy butyl ester product purity is up to 99.4%.In the technique reaction system be added to benzene two
Phenol and p-hydroxyanisole will not remove in extraction process, can be evaporated in product in stage of rectification, influence the downstream of product
Aggregated application, while hydroquinone and p-hydroxyanisole are oxidized to quinones in stage of rectification, entrainment influences product into product
Color number, in addition, the stage of reaction and the remaining acrylic acid of extraction stages accelerate 4- hy-droxybutyl in the polymerization of stage of rectification and
It decomposes, this process flow is in actual production and infeasible.
Wang Wei's text etc. 4- hy-droxybutyl synthesis and application study, synthesis material aging and application, 2018,47
(3): being mentioned in 110-114. and can remove acid homogeneous catalyst and polymerization inhibitor using the method for washing and alkali cleaning, polymerization inhibitor can
To remove by the method for activated carbon adsorption, Isosorbide-5-Nitrae-is removed using nonpolar solvent, such as hexamethylene, benzene, n-hexane or toluene
Butanediol diacrylate separates 1,4-butanediol by intensive polar solvent, such as methylene chloride, butyl acetate, chloroform
With 4- hy-droxybutyl, polymerization inhibitor uses activated carbon adsorption, and party's law theory is feasible, and practical application effect is unsatisfactory, together
When the technique do not consider the unusual service condition that product in distillation process polymerize.
CN109053449A provides a kind of production technology and equipments for being separated by extraction and preparing 4- hy-droxybutyl,
1,4- butanediol and acrylic acid are reacted under catalyst p-methyl benzenesulfonic acid, hydroquinone of polymerization retarder and p-hydroxyanisole and obtained
Primary product 4- hy-droxybutyl and 1,4-butanediol diacrylate first extract 1,4-butanediol with hexamethylene from water phase
Diacrylate, then 4- hy-droxybutyl is extracted from water phase with methylene chloride, most afterwards through being evaporated under reduced pressure finished product, the work
There is the acrylic acid of remained unreacted in gained reaction solution in skill, and exist in vacuum distillation process and accelerate product polymerization and decompose
The problems such as.
CN109053450A provide it is a kind of preparation-hy-droxybutyl method is separated by extraction, by Isosorbide-5-Nitrae-fourth two
The reaction under catalyst and the effect of hydroquinone of polymerization retarder and p-hydroxyanisole of pure and mild acrylic acid obtains esterification reaction solution, with extraction
It takes agent hexamethylene first to extract 1,4-butanediol diacrylate from water phase, then extracts 4- propylene from water phase with methylene chloride etc.
Sour hydroxy butyl ester, most afterwards through being evaporated under reduced pressure finished product, which equally exists the acrylic acid of remained unreacted in reaction solution, and
The problems such as accelerating product polymerization in vacuum distillation process and decomposing.
Summary of the invention
It is an object of the present invention to provide a kind of fluorine-containing containing nitroxyl oxides of free radical inhibitor and preparation method thereof and a kind of using this
The continuous refining process of the 4- hy-droxybutyl of polymerization inhibitor.The fluorine-containing nitroxyl oxides of free radical inhibitor that contains of the present invention is a kind of colourless
Number, higher boiling polymerization inhibitor, the polymerization inhibitor is added in the distillation light component of 4- hy-droxybutyl process for refining and product process,
In conjunction with operations such as three step continuous extractions of the invention, rectifying removing light component, short-path distillations, can be realized to 4- acrylic acid hydroxyl fourth
Ester product carries out the operation of continuous treating, and labor intensity is small, and obtained product purity is high, color number is low, and acid content is low, easily the company of realization
Continuous chemical industry production.
To realize the above goal of the invention, The technical solution adopted by the invention is as follows:
The present invention provides a kind of fluorine-containing containing nitroxyl oxides of free radical inhibitor, is as follows at least one of structural formula:
Wherein m, n value are separately 5~50, preferably 8~15；
It is described fluorine-containing to be preferably containing nitroxyl oxides of free radical inhibitor in the present invention
In the present invention, the fluorine-containing number-average molecular weight containing nitroxyl oxides of free radical inhibitor is 2000~4000, preferably
2500~3000；
In the present invention, it is described it is fluorine-containing containing fluorine content in nitroxyl oxides of free radical inhibitor be 3~62wt%, preferably 14~
35wt%；
In the present invention, it is described it is fluorine-containing containing NO free radical content in nitroxyl oxides of free radical inhibitor be 2~13wt%, preferably
7~11wt%；
In the present invention, the fluorine-containing boiling point containing nitroxyl oxides of free radical inhibitor is 500~800 DEG C, preferably 550~700 DEG C.
In the present invention, the fluorine-containing nitroxyl oxides of free radical inhibitor that contains is white solid, and color number is 0.
It is of the present invention it is fluorine-containing containing nitroxyl oxides of free radical inhibitor be a kind of 4- hy-droxybutyl polymerization inhibitor, it can also be used to
The polymerization inhibitor of other dihydroxypropyl esters.
The present invention also provides a kind of above-mentioned fluorine-containing preparation method containing nitroxyl oxides of free radical inhibitor, step includes:
(1) methyl acrylate and 2,2,6,6- tetramethylpiperidinols occur ester exchange reaction, obtain 2,2,6,6- tetramethyls
Piperidines acrylate；
(2) perfluoroolefine is added into step (1) reaction solution, and 2,2,6,6- tetramethyl piperidine acrylate are copolymerized
Polymerization reaction；
(3) sodium tungstate is added into step (2) reaction solution and hydrogen peroxide carries out oxidation reaction, it is free to obtain fluorine-containing nitrogenous oxygen
Base polymerization inhibitor.
In step (1) of the present invention, the ester exchange reaction, temperature is 90~120 DEG C, preferably 100~110 DEG C；Time
For 6~12h, preferably 8~10h；
The methyl acrylate and 2,2,6,6- tetramethylpiperidinol molar ratios are 1.5~5:1, preferably 2~3:1；
Preferably, after the completion of the ester exchange reaction, further include the last handling processes such as distillation, remove the propylene in reaction solution
Sour methyl esters and reaction by-product methanol etc.；
In step (2) of the present invention, the co-polymeric reaction, reaction temperature is 30~60 DEG C, preferably 40~50 DEG C；Instead
It is 5~15h, preferably 7~10h, 4~8MPaG of reaction pressure, preferably 5~7MPaG between seasonable, pressure release is extremely after the reaction was completed
Normal pressure；
The perfluoroolefine and 2,2,6,6- tetramethyl piperidine acrylate molar ratios be 0.5~3:1, preferably 1~2.5:
1。
The perfluoroolefine is at least one of tetrafluoroethene and/or hexafluoropropene, preferably tetrafluoroethene.
In step (3) of the present invention, the oxidation reaction, temperature is 100~110 DEG C, and the time is 36~48h；
The sodium tungstate and 2,2,6,6- tetramethyl piperidine acrylate mass ratioes be 0.05~0.5:1, preferably 0.08~
0.15:1；
The hydrogen peroxide and 2,2,6,6- tetramethylpiperidinol molar ratios are 0.8~2:1, preferably 1~1.5:1.
Preferably, the reaction of step (2) co-polymeric and/or step (3) described oxidation reaction, in nitrogen environment into
Row.
It preferably, further include the last handling processes such as washing, extraction, distillation or drying after the completion of the oxidation reaction；Washing
It is 20~30 DEG C with extraction temperature, distillation or drying temperature are 80~90 DEG C.The tool used in some embodiments of the present invention
Body method are as follows: sequentially add hot water and toluene into reaction solution and extracted in 20~30 DEG C of progress water-washing desaltings and toluene, stand and divide
It takes oily phase to carry out distillation at 80~90 DEG C except solvent after phase, it is fluorine-containing containing nitroxyl oxides of free radical inhibitor to obtain white solid.
The object of the invention also reside in provide it is a kind of using the above-mentioned fluorine-containing 4- acrylic acid hydroxyl fourth containing nitroxyl oxides of free radical inhibitor
The continuous refining process of ester, comprising the following steps:
1) the three step continuous extraction of 4- hy-droxybutyl crude reaction liquid separate the hy-droxybutyl containing 4- extract liquor；
2) step 1) extract liquor carries out lye neutralization, washing, oily phase after must washing；
3) it is added fluorine-containing containing nitroxyl oxides of free radical inhibitor after step 2) washing in oily phase, rectifying removes light component, then passes through
Short-path distillation obtains 4- hy-droxybutyl.
Further, in step 1), the 4- hy-droxybutyl crude reaction liquid, with 4- hy-droxybutyl crude reaction liquid
Gross mass is 100% meter, and composition includes: 0.5~5wt% of acrylic acid, 40~60wt% of 1,4-butanediol, 4- acrylic acid hydroxyl fourth
40~50wt% of ester, 1~10wt% of 1,4 butanediol diacrylate, 0.5~2wt% of catalyst, 0.1~1wt% of polymerization inhibitor；
The catalyst is at least one of the concentrated sulfuric acid, p-methyl benzenesulfonic acid and methanesulfonic acid；
The polymerization inhibitor is phenthazine, hydroquinone, p methoxy phenol, ZJ-701, ZJ-705, N, N- di-n-butyl two
At least one of thiocarbamic acid copper.
Further, in step 1), the three steps continuous extraction separation, including tower separation or centrifugation separation, it adopts
Equipment is at least one of packed extraction tower, perforated-plate extraction tower, turntable extracting tower and centrifugal extractor, preferably centrifugation extraction
Take machine；
The three steps continuous extraction comprising: 1,4-butanediol diacrylate (BDDA) removes extraction cells, 4- propylene
Sour hydroxy butyl ester (4-HBA) extracts extraction cells, 1,4- butanediol (BDO) removes extraction cells；In some specific implementations of the present invention
Three step continuous extraction described in mode is followed successively by 1,4-butanediol diacrylate (BDDA) removing extraction cells, 4- acrylic acid
Hydroxy butyl ester (HBA) extracts extraction cells, 1,4- butanediol (BDO) removes extraction cells；
Extractant used in 1,4 butanediol diacrylate removing extraction cells is hexamethylene, n-hexane, just
At least one of heptane, pentane, dimethylbenzene, toluene or a variety of mixtures, preferably n-hexane；
It is methylene chloride, butyl acetate, trichlorine that the 4- hy-droxybutyl, which extracts extractant used in extraction cells,
At least one of methane, carbon tetrachloride or a variety of mixtures, preferably methylene chloride；
Extractant used in 1,4- butanediol removing extraction cells be water, 5~10wt%NaCl aqueous solution, 5~
At least one or more of mixture of 10wt%KCl aqueous solution, preferably water.
Further, in step 1), the 1,4-butanediol diacrylate removes extraction cells, 4- hy-droxybutyl
The mass ratio of crude reaction liquid and extractant is 1:2~3, and extraction series is 5~10 grades, and temperature is 20~30 DEG C；
The 4- hy-droxybutyl extracts extraction cells, the mass ratio of 4- hy-droxybutyl crude reaction liquid and extractant
For 1:1~3, extracting series is 2~5 grades, and temperature is 20~30 DEG C；
The mass ratio of the 1,4-butanediol removing extraction cells, 4- hy-droxybutyl crude reaction liquid and extractant is 1:
1~3, extraction series is 5~10 grades, and temperature is 20~30 DEG C.
Further, in step 1), the extract liquor of the hy-droxybutyl containing 4-, with disregard extractant quality containing 4-
The extract liquor gross mass of hy-droxybutyl is 100% calculating, and composition includes 0.1~0.5wt% of acrylic acid, 1,4-butanediol
0.1~0.5wt%, it 99.0~99.5wt% of 4- hy-droxybutyl, 0.1~0.5wt% of 1,4 butanediol diacrylate, urges
0.2~0.5wt% of agent, 0.05~0.1wt% of polymerization inhibitor.
Further, in step 2), the lye is neutralized, the lye used be selected from 1~10wt%NaOH aqueous solution, 1~
At least one of 10wt%KOH aqueous solution；It is preferred that NaOH aqueous solution；
The lye neutralizes, and the range of pH control is 7~10, preferably 8~9；
The lye neutralizes, and temperature is 15~40 DEG C, preferably 20~35 DEG C, more preferable 20~30 DEG C.
Further, in step 2), the washing is 1~8 grade to the cleaning series of gained neutralizer with water, preferably 2~
4 grades；
The washing, the dosage of water and the mass ratio of neutralizer are 0.1~2:1, preferably 0.3~1:1；
The washing, temperature are 15~40 DEG C, preferably 20~35 DEG C, more preferable 20~30 DEG C.
Further, in step 2), oily phase after the washing, to disregard the oily phase gross mass of extractant quality for 100%
It calculates, composition includes 0.01~0.05wt% of acrylic acid, 0.1~0.5wt% of 1,4-butanediol, 4- hy-droxybutyl 99.0
~99.5wt%, 0.1~0.5wt% of 1,4 butanediol diacrylate, 0.01~0.05wt% of catalyst, polymerization inhibitor 0.01~
0.05wt%.
Further, in step 3), the fluorine-containing additional amount containing nitroxyl oxides of free radical inhibitor is oily phase total amount after washing
0.1~5wt%, preferably 1~2wt%.
Further, in step 3), the rectifying, the theoretical number of plates of rectifying tower used is 10~20, preferably 12~18；
The rectifying column uses continuous feed mode；The tower top temperature of rectifying column is 15~35 DEG C, preferably 20~30 DEG C；Tower
Pressure on top surface is 40~85KPa (A), preferably 45~70KPa (A).
Further, in step 3), the light component is the three remaining extractions of step continuous extraction lock out operation in step 1)
Agent, it is preferable that the light component is the mixture of n-hexane, methylene chloride and water.
Further, in step 3), the short-path distillation, pressure is 0.01~1KPa (A), preferably 0.02~0.1KPa
(A), temperature is 70~180 DEG C, preferably 90~150 DEG C.
The short-path distillation carries out in short-path evaporator, and short-path evaporator includes built-in condenser, built-in condenser
Tube side temperature is -60~10 DEG C, preferably -25~5 DEG C；
Condensed in two stages device is arranged in the gaseous phase outlet of the short-path evaporator, and the tube side temperature of first order condenser is 28~40
DEG C, preferably 30~38 DEG C；The tube side temperature of second level condenser is -60~10 DEG C, preferably -25~5 DEG C.
Preferably, in the tube side of the first order condenser be recirculated water refrigerant, temperature be 28~40 DEG C, preferably 30~38
DEG C, in the tube side of second level condenser be 30~60wt% glycol water, temperature be -60~10 DEG C, preferably -25~5
℃。
The continuous refining process of 4- hy-droxybutyl of the present invention, 4- hy-droxybutyl purity obtained reach 99% with
On, purification yield up to 90% or more, color number for 5 (APHA) hereinafter, acid value is extremely low, less than 0.05mgKOH/g；4- third obtained
The content for the polymerization inhibitor carried secretly in olefin(e) acid hydroxy butyl ester product is lower than 10ppm, leads to after the polymerization inhibitor purification that wherein crude reaction liquid band enters
Lye is crossed to neutralize, wash and can remove completely.
Technical solution of the present invention, the beneficial effect is that:
1, using multi-stage continuous extraction equipment and technique, the removal efficiency and 1,4-butanediol of 1,4-butanediol diacrylate
Removal efficiency and product 4- hy-droxybutyl recovery rate it is higher, reach 99% or more, ensure that product purity simultaneously,
Personnel's manipulation strength is reduced, human cost is lowered；
2, using in lye and technique is stripped of after extraction remaining acrylic acid and acidic catalyst in oily phase, there is meeting
Accelerate decomposition and polymerization of the 4- hy-droxybutyl product in distillation process, further ensures available low acid value, height
The 4- hy-droxybutyl product of purity；
3, it is neutralized to extraction and is added fluorine-containing containing nitroxyl oxides of free radical inhibitor in the oily phase after washing, boiling point height is (compared with 4- third
High 200 DEG C of olefin(e) acid hydroxy butyl ester boiling point or more), colourless number, molecular weight it is larger, can avoid by Vapor Entrainment into product, thus
To low color product (color < 5)；
4, the recombination of higher degree 4- hy-droxybutyl is obtained using rectification process, removed overhead extractant, while tower bottom
Point, condition is provided to prepare the 4- hy-droxybutyl product of high-purity；
5, according to molecular distillation principle, using short-path distillation 4- hy-droxybutyl, heat sensitive material 4- hy-droxybutyl
Heated time is short, and operating procedure is simple, and equipment is few, and product energy consumption is small, and product purity can reach 99% or more；
6, entire subtractive process can be used for 4- hy-droxybutyl using serialization extraction and rectifying and distillation equipment
Scale continuous production.
Detailed description of the invention
Fig. 1 is the fluorine-containing spectrogram of GPC containing nitroxyl oxides of free radical inhibitor prepared by embodiment 1；
Fig. 2 is the fluorine-containing spectrogram of GPC containing nitroxyl oxides of free radical inhibitor prepared by embodiment 2；
Fig. 3 is the fluorine-containing spectrogram of GPC containing nitroxyl oxides of free radical inhibitor prepared by embodiment 3；
Fig. 4 is the fluorine-containing spectrogram of GPC containing nitroxyl oxides of free radical inhibitor prepared by embodiment 4；
Fig. 5 is fluorine-containing infrared spectrum containing nitroxyl oxides of free radical inhibitor prepared by embodiment 1；
Fig. 6 is fluorine-containing infrared spectrum containing nitroxyl oxides of free radical inhibitor prepared by embodiment 4；
Fig. 7 is the continuous refining process flow diagram of 4- hy-droxybutyl of the present invention.
Specific embodiment
Below by embodiment, the present invention is further elaborated, and the present invention is not limited to the following examples.This hair
It is bright to expand to any new feature disclosed in the description or any new combination, and any new method or process that disclose
The step of or any new combination.
One, primary raw material source in embodiment:
1, methyl acrylate, Shanghai Aladdin biochemical technology limited liability company analyze pure；
2,2,2,6,6- tetramethylpiperidinols, Alfa Aesar is analyzed pure；
3, toluene, Sinopharm Chemical Reagent Co., Ltd. analyze pure；
4, dimethylbenzene, western Gansu Province science limited liability company analyze pure；
5, benzene, Shanghai Aladdin biochemical technology limited liability company analyze pure；
6, tetrafluoroethene, Dalian great Te gas Co., Ltd analyze pure；
7, hexafluoropropene, lark prestige Science and Technology Ltd. analyze pure；
8, anhydrous wolframic acid sodium, lark prestige Science and Technology Ltd., 99%；
9, hydrogen peroxide, Sinopharm Chemical Reagent Co., Ltd. analyze pure.
Two, product analysis method in embodiment:
1, gas-chromatography is for analyzing reaction solution and product component, content, using corrector factor method, instrument producer and type
Number: Shimadzu 1020-plus；
2, the fluorine-containing structure containing nitroxyl oxides of free radical inhibitor, instrument producer and model are measured with Fourier infrared spectrograph:
Thermo (U.S.) 470FTIR.
3, the fluorine-containing molecular weight containing nitroxyl oxides of free radical inhibitor, instrument producer and model are measured with gel permeation chrommatograph (GPC):
Shimadzu (Japan) LC-20AD；
4, the fluorine-containing boiling point containing nitroxyl oxides of free radical inhibitor, instrument producer and model are measured with thermogravimetric analyzer (TGA):
METTLER (Switzerland) TGA/DSC 1；
5, the fluorine-containing content containing fluorine in nitroxyl oxides of free radical inhibitor, instrument producer are measured with Atomic Absorption Spectrometer (AAS)
And model: Perkin Elmer (U.S.) PinAAcle900T；
6,4- hy-droxybutyl product color number, instrument producer and model: Hash HACH LICO620 are measured with color instrument.
Embodiment 1:
It prepares fluorine-containing containing nitroxyl oxides of free radical inhibitor, step are as follows:
1) by methyl acrylate and 2,2,6,6- tetramethylpiperidinols are added in reaction kettle according to the amount of 2:1 (mol), temperature
It spends 102 DEG C of reaction 9h, after the completion of ester exchange reaction, methyl acrylate therein and reaction by-product first is distilled under 20KPaA pressure
Alcohol obtains the reaction solution containing 2,2,6,6- tetramethyl piperidine acrylate；
2) step (1) reaction solution is cooled to 45 DEG C using 28 DEG C of recirculated waters, tetrafluoroethene, tetrafluoro is added into reaction kettle
The additional amount of ethylene: 2,2,6,6- tetramethyl piperidine acrylate are 2:1 (mol), then pour high pressure nitrogen, guarantee reaction kettle
Interior pressure is 5.5MPaG, is terminated after reacting 8h, by reaction kettle pressure release, and three times using nitrogen replacement reaction kettle；
3) sodium tungstate and hydrogen peroxide, the additional amount of hydrogen peroxide: 2,2,6,6- tetramethyl piperidines are added into reaction kettle
Alcohol is 1.2:1 (mol), and sodium tungstate additional amount: 2,2,6,6- tetramethyl piperidine acrylate are 0.1:1 (wt), increases reaction temperature
Degree terminates to after reacting 40h after 105 DEG C；
4) reaction solution is cooled to room temperature, and is sequentially added hot water and toluene to reaction solution and is washed and extracted at 20~30 DEG C
Take, stand 1h after shaking up, take 80~90 DEG C of oily phase be evaporated under reduced pressure (, remove solvent toluene therein, gained white heavy constituent
It is as fluorine-containing to contain nitroxyl oxides of free radical inhibitor.
Embodiment 1 prepare fluorine-containing (GPC spectrogram is as shown in Figure 1, infrared spectrum such as Fig. 5 institute containing nitroxyl oxides of free radical inhibitor
Show), structure is
It is about 8~9 that wherein m about value, which is 8~9, n value, and fluorine content is about 25~26wt%, and NO free radical content is about
8.5~9.5wt%, molecular weight are about 2680 (Mn), and boiling point is 640 DEG C, and color number is 0.
Embodiment 2:
It prepares fluorine-containing containing nitroxyl oxides of free radical inhibitor, step are as follows:
1) by methyl acrylate and 2,2,6,6- tetramethylpiperidinols are added in reaction kettle according to the amount of 3:1 (mol), temperature
It spends 100 DEG C of reaction 8h, after the completion of ester exchange reaction, methyl acrylate therein and reaction by-product first is distilled under 20KPaA pressure
Alcohol obtains the reaction solution containing 2,2,6,6- tetramethyl piperidine acrylate；
2) step (1) reaction solution is cooled to 40 DEG C using 28 DEG C of recirculated waters, tetrafluoroethene, tetrafluoro is added into reaction kettle
The additional amount of ethylene: 2,2,6,6- tetramethyl piperidine acrylate are 1:1 (mol), then pour high pressure nitrogen, guarantee reaction kettle
Interior pressure is 5.0MPaG, is terminated after reacting 7h, by reaction kettle pressure release, and three times using nitrogen replacement reaction kettle；
3) sodium tungstate and hydrogen peroxide, the additional amount of hydrogen peroxide: 2,2,6,6- tetramethyl piperidines are added into reaction kettle
Alcohol is 1:1 (mol), and sodium tungstate additional amount: 2,2,6,6- tetramethyl piperidine acrylate are 0.15:1 (wt), increase reaction temperature
Terminate after reacting 36h after to 105 DEG C；
4) reaction solution is cooled to room temperature, and is sequentially added hot water and toluene to reaction solution and is washed and extracted at 20~30 DEG C
It takes, stands 1h after shaking up, 80~90 DEG C of oily phase is taken to be evaporated under reduced pressure, remove solvent toluene therein, gained white heavy constituent
It is as fluorine-containing to contain nitroxyl oxides of free radical inhibitor.
Fluorine-containing (GPC spectrogram is as shown in Figure 2) containing nitroxyl oxides of free radical inhibitor prepared by embodiment 2, m value is about in structural formula
8~9, n value is about 8~9, and fluorine content is about 23~24wt%, and NO free radical content is about 9~10wt%, and molecular weight is about
2540 (Mn), boiling point are 620 DEG C, and color number is 0.
Embodiment 3:
It prepares fluorine-containing containing nitroxyl oxides of free radical inhibitor, step are as follows:
1) by methyl acrylate and 2,2,6,6- tetramethylpiperidinols are added in reaction kettle according to the amount of 2:1 (mol), temperature
It spends 110 DEG C of reaction 9h, after the completion of ester exchange reaction, methyl acrylate therein and reaction by-product first is distilled under 20KPaA pressure
Alcohol obtains the reaction solution containing 2,2,6,6- tetramethyl piperidine acrylate；
2) step (1) reaction solution is cooled to 40 DEG C using 28 DEG C of recirculated waters, tetrafluoroethene, tetrafluoro is added into reaction kettle
The additional amount of ethylene: 2,2,6,6- tetramethyl piperidine acrylate are 1:1 (mol), then pour high pressure nitrogen, guarantee reaction kettle
Interior pressure is 7.0MPaG, is terminated after reacting 7h, by reaction kettle pressure release, and three times using nitrogen replacement reaction kettle；
3) sodium tungstate and hydrogen peroxide, the additional amount of hydrogen peroxide: 2,2,6,6- tetramethyl piperidines are added into reaction kettle
Alcohol is 1.5:1 (mol), and sodium tungstate additional amount: 2,2,6,6- tetramethyl piperidine acrylate are 0.08:1 (wt), increases reaction temperature
Degree terminates to after reacting 48h after 110 DEG C；
4) reaction solution is cooled to room temperature, and is sequentially added hot water and toluene to reaction solution and is washed and extracted at 20~30 DEG C
It takes, stands 1h after shaking up, 80~90 DEG C of oily phase is taken to be evaporated under reduced pressure, remove solvent toluene therein, gained white heavy constituent
It is as fluorine-containing to contain nitroxyl oxides of free radical inhibitor.
Fluorine-containing (GPC spectrogram is as shown in Figure 3) containing nitroxyl oxides of free radical inhibitor prepared by embodiment 3, m value is about in structural formula
8~9, n value is about 8~9, and fluorine content is about 21~22wt%, and NO free radical content is about 9~10wt%, and molecular weight is about
2800 (Mn), boiling point are 670 DEG C, and color number is 0.
Embodiment 4:
It prepares fluorine-containing containing nitroxyl oxides of free radical inhibitor, step are as follows:
1) by methyl acrylate and 2,2,6,6- tetramethylpiperidinols are added in reaction kettle according to the amount of 2.5:1 (mol),
105 DEG C of reaction 10h of temperature after the completion of ester exchange reactions, methyl acrylate therein are distilled under 20KPaA pressure and reaction is secondary
Methanol is produced, the reaction solution containing 2,2,6,6- tetramethyl piperidine acrylate is obtained；
2) step (1) reaction solution is cooled to 50 DEG C using 28 DEG C of recirculated waters, hexafluoropropene, hexafluoro is added into reaction kettle
The additional amount of propylene: 2,2,6,6- tetramethyl piperidine acrylate are 2.5:1 (mol), then pour high pressure nitrogen, guarantee reaction
Pressure in kettle is 7.0MPaG, is terminated after reacting 15h, by reaction kettle pressure release, and three times using nitrogen replacement reaction kettle；
3) sodium tungstate and hydrogen peroxide, the additional amount of hydrogen peroxide: 2,2,6,6- tetramethyl piperidines are added into reaction kettle
Alcohol is 1.2:1 (mol), and sodium tungstate additional amount: 2,2,6,6- tetramethyl piperidine acrylate are 0.15:1 (wt), increases reaction temperature
Degree terminates to after reacting 40h after 110 DEG C；
4) reaction solution is cooled to room temperature, and is sequentially added hot water and toluene to reaction solution and is washed and extracted at 20~30 DEG C
It takes, stands 1h after shaking up, 80~90 DEG C of oily phase is taken to be evaporated under reduced pressure, remove solvent toluene therein, gained white heavy constituent
It is as fluorine-containing to contain nitroxyl oxides of free radical inhibitor.
Embodiment 4 prepare fluorine-containing (GPC spectrogram is as shown in figure 4, infrared spectrum such as Fig. 6 institute containing nitroxyl oxides of free radical inhibitor
Show), infrared analysis structure is as follows,
Wherein m value is about 8~9, n value is about 8~9, and fluorine content is about 30~31wt%, and NO free radical content is about
7.5~8.5wt%, GPC spectrum analysis molecular weight, molecular weight are about 3000 (Mn), and boiling point is 660 DEG C, and color number is 0.
Embodiment 5
A kind of continuous refining process (as shown in Figure 7) of 4- hy-droxybutyl, steps are as follows:
Raw material 4- hy-droxybutyl crude reaction liquid, consisting of: acrylic acid 1.2wt%, 1,4-butanediol 42.5wt%,
4- hy-droxybutyl 48.2wt%, 1,4 butanediol diacrylate 6.7wt%, catalyst p-methyl benzenesulfonic acid 0.8wt% and
Hydroquinone of polymerization retarder 0.6wt%；
1) 1,4-butanediol diacrylate removes extraction cells, using Pyatyi centrifugal extractor to 4- hy-droxybutyl
Crude reaction liquid is extracted, and removes 1,4-butanediol diacrylate by-product therein, 4- hy-droxybutyl crude reaction liquid: extraction
Agent hexamethylene=1:2.1 (wt) is taken, extraction temperature is 25 DEG C, and the removal efficiency of 1,4-butanediol diacrylate is 99.3%；
4- hy-droxybutyl extracts extraction cells, is extracted using two-stage centrifugal extracter to water phase obtained by step 1)
Take, reaction solution: extractant methylene chloride=1:1.2 (wt), extraction temperature are 25 DEG C, and the recovery rate of 4- hy-droxybutyl is
99.1%；
1,4-butanediol removes extraction cells, is mutually extracted using Pyatyi centrifugal extractor to oil obtained by step 2), instead
Answer liquid: extractant water=1:1.3 (wt), extraction temperature are 25 DEG C, and the removal efficiency of 1,4-butanediol is 99.1%；
The extract liquor for the hy-droxybutyl containing 4- that step 1) obtains, to disregard the hydroxyl fourth of acrylic acid containing 4- of extractant quality
The extract liquor gross mass of ester is 100% calculating, and composition includes acrylic acid 0.14wt%, 1,4-butanediol 0.15wt%, 4- third
Olefin(e) acid hydroxy butyl ester 99.2wt%, 1,4 butanediol diacrylate 0.2wt%, catalyst p-methyl benzenesulfonic acid 0.25wt%, polymerization inhibitor
Agent hydroquinone 0.06wt%；
2) lye neutralisation unit mutually neutralizes oil after extraction obtained by step 1) using 2wt%NaOH aqueous solution, neutralizes
Temperature is 20 DEG C, and titration end-point PH is 8.1；
Unit is washed, gained neutralizer is washed using water, washing temperature is 20 DEG C, and series is 2 grades, the dosage of water
Mass ratio with neutralizer is 0.4:1, oily phase after washing, and the oily phase gross mass to disregard extractant is composition in terms of 100%
Are as follows: two propylene of acrylic acid 0.02wt%, 1,4- butanediol 0.35wt%, 4- hy-droxybutyl 99.1wt%, 1,4- butanediol
Acid esters 0.45wt%, catalyst 0.04wt%, polymerization inhibitor 0.04wt%；
3) the fluorine-containing of the addition preparation of embodiment 1 in the oily phase of gained is washed to step 2) and contain nitroxyl oxides of free radical inhibitor, add
Enter the 1.5wt% that amount is oily phase total amount after washing, using rectifying column, the number of plates 16,28 DEG C of tower top temperature, tower top pressure is
50KPaA, the content of light component hexamethylene is 0.47wt% in obtained bottom liquid, this bottom liquid is turned by the way that pump is continuous
Entering in short-path evaporator, condenser built in short-path evaporator, is the glycol water of 45wt% in tube side, temperature is -10 DEG C,
The temperature of recirculated water is 30 DEG C in the tube side of first order condenser at the top of short-path evaporator, in the tube side of second level condenser
The temperature of the glycol water of 45wt% is -15 DEG C, and control product separating pressure is 0.05KPaA, and separation temperature is 105 DEG C,
4- hy-droxybutyl after being refined, purity 99.17%, color number are 3, and purification yield is 91.7%, acid value
0.009mgKOH/g, the fluorine-containing content containing nitroxyl oxides of free radical inhibitor carried secretly in product are 4ppm, hydroquinone of polymerization retarder
0ppm。
Embodiment 6
A kind of continuous refining process of 4- hy-droxybutyl, steps are as follows:
Raw material 4- hy-droxybutyl crude reaction liquid, consisting of: acrylic acid 1.2wt%, 1,4-butanediol 42.5wt%,
4- hy-droxybutyl 48.2wt%, 1,4 butanediol diacrylate 6.7wt%, catalyst p-methyl benzenesulfonic acid 0.8wt% and
Hydroquinone of polymerization retarder 0.6wt%；
1) 1,4-butanediol diacrylate removes extraction cells, using Pyatyi centrifugal extractor to 4- hy-droxybutyl
Crude reaction liquid is extracted, and removes 1,4-butanediol diacrylate by-product therein, 4- hy-droxybutyl crude reaction liquid: extraction
Agent hexamethylene=1:3 (wt) is taken, extraction temperature is 20 DEG C, and the removal efficiency of 1,4-butanediol diacrylate is 99.8%；
4- hy-droxybutyl extracts extraction cells, is extracted using two-stage centrifugal extracter to water phase obtained by step 1)
Take, reaction solution: extractant methylene chloride=1:2 (wt), extraction temperature are 20 DEG C, and the recovery rate of 4- hy-droxybutyl is
99.5%；
1,4-butanediol removes extraction cells, is mutually extracted using Pyatyi centrifugal extractor to oil obtained by step 2), instead
Answer liquid: extractant water=1:2 (wt), extraction temperature are 20 DEG C, and the removal efficiency of 1,4-butanediol is 99.3%；
The extract liquor for the hy-droxybutyl containing 4- that step 1) obtains, to disregard the hydroxyl fourth of acrylic acid containing 4- of extractant quality
The extract liquor gross mass of ester is 100% calculating, and composition includes acrylic acid 0.15wt%, 1,4-butanediol 0.11wt%, 4- third
Olefin(e) acid hydroxy butyl ester 99.33wt%, 1,4 butanediol diacrylate 0.15wt%, catalyst 0.21wt%, polymerization inhibitor
0.05wt%；
2) lye neutralisation unit mutually neutralizes oil after extraction obtained by step 1) using 2wt%NaOH aqueous solution, neutralizes
Temperature is 20 DEG C, and titration end-point PH is 8.3；
Unit is washed, gained neutralizer is washed using water, washing temperature is 20 DEG C, and series is 2 grades, the dosage of water
Mass ratio with neutralizer is 0.4:1, oily phase after washing, and the oily phase gross mass to disregard extractant is composition in terms of 100%
Are as follows: acrylic acid 0.02wt%, 1,4- butanediol 0.3wt%, 4- hy-droxybutyl 99.3wt%, 1,4- butanediol diacrylate
Ester 0.3wt%, catalyst 0.04wt%, polymerization inhibitor 0.04wt%；
3) the fluorine-containing of the addition preparation of embodiment 2 in the oily phase of gained is washed to step 2) and contain nitroxyl oxides of free radical inhibitor, add
Enter the 1.5wt% that amount is oily phase total amount after washing, using rectifying column, the number of plates 16,28 DEG C of tower top temperature, tower top pressure is
50KPaA, the content of light component hexamethylene is 0.41wt% in obtained bottom liquid, this bottom liquid is turned by the way that pump is continuous
Entering in short-path evaporator, condenser built in short-path evaporator, is the glycol water of 45wt% in tube side, temperature is -10 DEG C,
The temperature of recirculated water is 30 DEG C in the tube side of first order condenser at the top of short-path evaporator, in the tube side of second level condenser
The temperature of the glycol water of 45wt% is -15 DEG C, and control product separating pressure is 0.05KPaA, and separation temperature is 105 DEG C,
4- hy-droxybutyl after being refined, purity 99.31%, color number are 2, and purification yield is 91.1%, acid value
0.005mgKOH/g, the fluorine-containing content containing nitroxyl oxides of free radical inhibitor carried secretly in product are 3ppm, hydroquinone of polymerization retarder
0ppm。
Embodiment 7
A kind of continuous refining process of 4- hy-droxybutyl, steps are as follows:
Raw material 4- hy-droxybutyl crude reaction liquid, consisting of: acrylic acid 1.2wt%, 1,4-butanediol 42.5wt%,
4- hy-droxybutyl 48.2wt%, 1,4 butanediol diacrylate 6.7wt%, catalyst p-methyl benzenesulfonic acid 0.8wt% and
Hydroquinone of polymerization retarder 0.6wt%；
1) 1,4-butanediol diacrylate removes extraction cells, using Pyatyi centrifugal extractor to 4- hy-droxybutyl
Crude reaction liquid is extracted, and removes 1,4-butanediol diacrylate by-product therein, 4- hy-droxybutyl crude reaction liquid: extraction
Agent hexamethylene=1:2.5 (wt) is taken, extraction temperature is 25 DEG C, and the removal efficiency of 1,4-butanediol diacrylate is 99.4%；
4- hy-droxybutyl extracts extraction cells, is extracted using two-stage centrifugal extracter to water phase obtained by step 1)
Take, reaction solution: extractant methylene chloride=1:1.5 (wt), extraction temperature are 25 DEG C, and the recovery rate of 4- hy-droxybutyl is
99.2%；
1,4-butanediol removes extraction cells, is mutually extracted using Pyatyi centrifugal extractor to oil obtained by step 2), instead
Answer liquid: extractant water=1:1.5 (wt), extraction temperature are 25 DEG C, and the removal efficiency of 1,4-butanediol is 99.3%；
The extract liquor for the hy-droxybutyl containing 4- that step 1) obtains, to disregard the hydroxyl fourth of acrylic acid containing 4- of extractant quality
The extract liquor gross mass of ester is 100% calculating, and composition includes acrylic acid 0.2wt%, 1,4-butanediol 0.12wt%, 4- propylene
Sour hydroxy butyl ester 99.3wt%, 1,4 butanediol diacrylate 0.13wt%, catalyst 0.2wt%, polymerization inhibitor 0.05wt%；
2) lye neutralisation unit mutually neutralizes oil after extraction obtained by step 1) using 2wt%NaOH aqueous solution, neutralizes
Temperature is 20 DEG C, and titration end-point PH is 8.5；
Unit is washed, gained neutralizer is washed using water, washing temperature is 20 DEG C, and series is 2 grades, the dosage of water
Mass ratio with neutralizer is 0.4:1, oily phase after washing, and the oily phase gross mass to disregard extractant is composition in terms of 100%
Are as follows: two propylene of acrylic acid 0.01wt%, 1,4- butanediol 0.33wt%, 4- hy-droxybutyl 99.17wt%, 1,4- butanediol
Acid esters 0.43wt%, catalyst 0.03wt%, polymerization inhibitor 0.03wt%；
3) the fluorine-containing of the addition preparation of embodiment 3 in the oily phase of gained is washed to step 2) and contain nitroxyl oxides of free radical inhibitor, add
Enter the 1.5wt% that amount is oily phase total amount after washing, using rectifying column, the number of plates 16,28 DEG C of tower top temperature, tower top pressure is
50KPaA, the content of light component hexamethylene is 0.42wt% in obtained bottom liquid, this bottom liquid is turned by the way that pump is continuous
Entering in short-path evaporator, condenser built in short-path evaporator, is the glycol water of 45wt% in tube side, temperature is -10 DEG C,
The temperature of recirculated water is 30 DEG C in the tube side of first order condenser at the top of short-path evaporator, in the tube side of second level condenser
The temperature of the glycol water of 45wt% is -15 DEG C, and control product separating pressure is 0.05KPaA, and separation temperature is 105 DEG C,
4- hy-droxybutyl after being refined, purity 99.34%, color number are 2, and purification yield is 90.9%, acid value
0.008mgKOH/g, the fluorine-containing content containing nitroxyl oxides of free radical inhibitor carried secretly in product are 3ppm, hydroquinone of polymerization retarder
0ppm。
Embodiment 8
A kind of continuous refining process of 4- hy-droxybutyl, steps are as follows:
Raw material 4- hy-droxybutyl crude reaction liquid, consisting of: acrylic acid 1.2wt%, 1,4-butanediol 42.5wt%,
4- hy-droxybutyl 48.2wt%, 1,4 butanediol diacrylate 6.7wt%, catalyst p-methyl benzenesulfonic acid 0.8wt% and
Hydroquinone of polymerization retarder 0.6wt%；
1) 1,4-butanediol diacrylate removes extraction cells, using Pyatyi centrifugal extractor to 4- hy-droxybutyl
Crude reaction liquid is extracted, and removes 1,4-butanediol diacrylate by-product therein, 4- hy-droxybutyl crude reaction liquid: extraction
Agent hexamethylene=1:3 (wt) is taken, extraction temperature is 25 DEG C, and the removal efficiency of 1,4-butanediol diacrylate is 99.5%；
4- hy-droxybutyl extracts extraction cells, is extracted using two-stage centrifugal extracter to water phase obtained by step 1)
Take, reaction solution: extractant methylene chloride=1:3 (wt), extraction temperature are 25 DEG C, and the recovery rate of 4- hy-droxybutyl is
99.5%；
1,4-butanediol removes extraction cells, is mutually extracted using Pyatyi centrifugal extractor to oil obtained by step 2), instead
Answer liquid: extractant water=1:3 (wt), extraction temperature are 25 DEG C, and the removal efficiency of 1,4-butanediol is 99.4%；
The extract liquor for the hy-droxybutyl containing 4- that step 1) obtains, to disregard the hydroxyl fourth of acrylic acid containing 4- of extractant quality
The extract liquor gross mass of ester is 100% calculating, and composition includes acrylic acid 0.1wt%, 1,4-butanediol 0.1wt%, 4- propylene
Sour hydroxy butyl ester 99.45wt%, 1,4 butanediol diacrylate 0.15wt%, catalyst 0.15wt%, polymerization inhibitor 0.05wt%；
2) lye neutralisation unit mutually neutralizes oil after extraction obtained by step 1) using 2wt%NaOH aqueous solution, neutralizes
Temperature is 20 DEG C, and titration end-point PH is 8.0；
Unit is washed, gained neutralizer is washed using water, washing temperature is 20 DEG C, and series is 2 grades, the dosage of water
Mass ratio with neutralizer is 0.4:1, oily phase after washing, and the oily phase gross mass to disregard extractant is composition in terms of 100%
Are as follows: two propylene of acrylic acid 0.01wt%, 1,4- butanediol 0.20wt%, 4- hy-droxybutyl 99.5wt%, 1,4- butanediol
Acid esters 0.25wt%, catalyst 0.02wt%, polymerization inhibitor 0.02wt%；
3) the fluorine-containing of the addition preparation of embodiment 4 in the oily phase of gained is washed to step 2) and contain nitroxyl oxides of free radical inhibitor, add
Enter the 1.5wt% that amount is oily phase total amount after washing, using rectifying column, the number of plates 16,28 DEG C of tower top temperature, tower top pressure is
50KPaA, the content of light component hexamethylene is 0.40wt% in obtained bottom liquid, this bottom liquid is turned by the way that pump is continuous
Entering in short-path evaporator, condenser built in short-path evaporator, is the glycol water of 45wt% in tube side, temperature is -10 DEG C,
The temperature of recirculated water is 30 DEG C in the tube side of first order condenser at the top of short-path evaporator, in the tube side of second level condenser
The temperature of the glycol water of 45wt% is -15 DEG C, and control product separating pressure is 0.05KPaA, and separation temperature is 105 DEG C,
4- hy-droxybutyl after being refined, purity 99.39%, color number are 1, and purification yield is 92.74%, acid value
0.004mgKOH/g, the fluorine-containing content containing nitroxyl oxides of free radical inhibitor carried secretly in product are 2ppm, hydroquinone of polymerization retarder
0ppm。
Comparative example 1
The process for refining (intermittent) of 4- hy-droxybutyl, raw material 4- hy-droxybutyl crude reaction liquid with embodiment 5,
Steps are as follows:
1) 1,4-butanediol diacrylate removes extraction cells, is extracted using separatory funnel to reaction solution, removes
1,4-butanediol diacrylate by-product therein, reaction solution: extractant hexamethylene=1:2.1 (wt), extraction temperature are 25 DEG C,
The removal efficiency of 1,4 butanediol diacrylate is 71.1%；
2) 4- hy-droxybutyl extracts extraction cells, is extracted using separatory funnel to water phase obtained by step 1), instead
Answer liquid: extractant methylene chloride=1:1.2 (wt), extraction temperature are 25 DEG C, and the recovery rate of 4- hy-droxybutyl is 89.3%；
3) 1,4-butanediol removes extraction cells, is mutually extracted using separatory funnel to oil obtained by step 2), reaction solution:
Extractant water=1:1.3 (wt), extraction temperature are 25 DEG C, and the removal efficiency of 1,4-butanediol is 73.4%；
4) lye neutralisation unit mutually neutralizes oil obtained by step 3) using 2wt%NaOH aqueous solution, and neutralization temperature is
20 DEG C, titration end-point 8.2；
5) unit to be washed, neutralizer obtained by step 4) is washed using water, washing temperature is 20 DEG C, and series is 2 grades,
The mass ratio of the dosage of water and neutralizer is 0.4:1, oily phase after washing, and the oily phase gross mass to disregard extractant is in terms of 100%,
Consisting of: acrylic acid 0.02wt%, 1,4- butanediol 11.8wt%, 4- hy-droxybutyl 86.2wt%, 1,4- butanediol
Diacrylate 1.9wt%, catalyst 0.04wt%, polymerization inhibitor 0.04wt%；
6) be added that embodiment 1 is prepared into the oily phase of washing gained is fluorine-containing containing nitroxyl oxides of free radical inhibitor, in an amount of from
The 1.5wt% of oily phase total amount after washing, using rectifying column, the number of plates 16,28 DEG C of tower top temperature, tower top pressure 50KPaA,
The content of light component hexamethylene is 0.47wt% in obtained bottom liquid, this bottom liquid is continuously transferred to short distance by pump and is steamed
It sends out in device, condenser built in short-path evaporator, is the glycol water of 45wt% in tube side, temperature is -10 DEG C, short distance evaporation
The temperature of recirculated water is 30 DEG C in the tube side of first order condenser at the top of device, the second of 45wt% in the tube side of second level condenser
The temperature of two alcohol solutions is -15 DEG C, and control product separating pressure is 0.05KPaA, and separation temperature is 105 DEG C, after obtaining purification
4- hy-droxybutyl, purity 87.3%, color number are 4, and purification yield is 68.2%, acid value 0.019mgKOH/g.
Comparative example 2
Prepare it is fluorine-containing containing nitroxyl oxides of free radical inhibitor, in step 2), perfluoroolefine and 2,2,6,6- tetramethyl piperidine propylene
Acid esters molar ratio is not within the scope of 0.5~3:1 of the present invention, step are as follows:
1) by methyl acrylate and 2,2,6,6- tetramethylpiperidinols are added in reaction kettle according to the amount of 2.5:1 (mol),
105 DEG C of reaction 10h of temperature after the completion of ester exchange reactions, methyl acrylate therein are distilled under 20KPaA pressure and reaction is secondary
Methanol is produced, 2,2,6,6- tetramethyl piperidine acrylate are obtained；
2) step (1) reaction solution is cooled to 50 DEG C using 28 DEG C of recirculated waters, tetrafluoroethene, tetrafluoro is added into reaction kettle
The additional amount of ethylene: 2,2,6,6- tetramethyl piperidine acrylate are 1:3 (mol), then pour high pressure nitrogen, guarantee reaction kettle
Interior pressure is 2.0MPaG, is terminated after reacting 10h, by reaction kettle pressure release, and three times using nitrogen replacement reaction kettle；
3) sodium tungstate and hydrogen peroxide, the additional amount of hydrogen peroxide: 2,2,6,6- tetramethyl piperidines are added into reaction kettle
Acrylate is 1:1.2 (mol), and sodium tungstate additional amount: 2,2,6,6- tetramethylpiperidinols are 0.15:1 (wt), increases reaction temperature
Degree terminates to after reacting 40h after 110 DEG C；
4) reaction solution is cooled to room temperature, and hot water and toluene is added, stands 1h after shaking up, and oil is taken mutually to be evaporated under reduced pressure, and is taken off
Except solvent toluene therein, be made fluorine-containing containing nitroxyl oxides of free radical inhibitor, in structural formula m value be about 2~3, n value be about 55~
56, molecular weight is about 11800 (Mn), fluorine content is about 1.4~1.5wt%, NO free radical content be about 13.1~
13.2wt%, color number are 49, and boiling point is 635 DEG C；
Since this comparative example preparation process changes perfluoroolefine and 2,2,6,6- tetramethyl piperidine acrylate proportion is obtained
The fluorine-containing m containing nitroxyl oxides of free radical inhibitor that arrives, n value, molecular weight, fluorine content, NO free radical content have exceeded model of the present invention
It encloses, and polymerization inhibitor color number is higher.
The polymerization inhibitor being added in 5 step 3) of embodiment is replaced with fluorine-containing containing NO free radical obtained by 2 step 4 of this comparative example
Polymerization inhibitor, 4- hy-droxybutyl after purification, purity 99.05%, color number are 35, and purification yield is 90.5%, acid value
0.009mgKOH/g。
Comparative example 3
Change the sequence of three step continuous extractions, step are as follows:
Raw material 4- hy-droxybutyl crude reaction liquid, consisting of: acrylic acid 1.3wt%, 1,4-butanediol 41.8wt%,
4- hy-droxybutyl 47.9wt%, 1,4 butanediol diacrylate 7.4wt%, catalyst p-methyl benzenesulfonic acid 0.9wt% and
Hydroquinone of polymerization retarder 0.7wt%；
1) 4- hy-droxybutyl extracts extraction cells, is extracted using separatory funnel to reaction liquid phase, reaction solution: extraction
Agent methylene chloride=1:1.2 (wt) is taken, extraction temperature is 25 DEG C, and the recovery rate of 4- hy-droxybutyl is 68.1%, Isosorbide-5-Nitrae-fourth
The recovery rate of omega-diol diacrylate is 79.9%；
2) 1,4-butanediol diacrylate removes extraction cells, is mutually extracted using separatory funnel to oil obtained by step 1)
It takes, removes 1,4-butanediol diacrylate by-product therein, reaction solution: extractant hexamethylene=1:2.1 (wt), extraction temperature
It is 25 DEG C, two is miscible, cannot achieve continuation split-phase and obtains purpose.
Comparative example 4
Using nitrogenous oxygen but not fluorine-containing higher boiling radical polymerization inhibitor, the continuous refining process of 4- hy-droxybutyl,
Difference from Example 5 is: ZJ-701 polymerization inhibitor is used in step 3), light component hexamethylene in obtained bottom liquid
Content is 0.52wt%, and 4- hy-droxybutyl product purity is 99.01% after purification, and color number is 58.It is inhibited using ZJ-701
After agent replacement after the fluorine-containing higher boiling polymerization inhibitor containing NO free radical, although the product purity being refining to obtain is almost the same,
The product color number arrived is obvious higher, can not achieve refining effect of the invention.
Comparative example 5
The continuous refining process of 4- hy-droxybutyl, difference from Example 5 are: using to methoxy in step 3)
Base phenol polymerization inhibitor, the content of light component hexamethylene is 0.55wt%, 4- acrylic acid hydroxyl fourth after purification in obtained bottom liquid
Ester product purity is 98.98%, and color number is 52, and the content of p methoxy phenol is 0.22wt% in product.Using to methoxyl group
After the replacement of phenol polymerization inhibitor after the fluorine-containing higher boiling polymerization inhibitor containing NO free radical, product color number is higher, and the resistance of product clip band
Poly- agent content is higher, influences downstream use.
Claims (10)
1. it is a kind of fluorine-containing containing nitroxyl oxides of free radical inhibitor, it is as follows at least one of structural formula:
Wherein m, n value are separately 5~50, preferably 8~15；
Preferred structure is
2. according to claim 1 fluorine-containing containing nitroxyl oxides of free radical inhibitor, it is characterised in that: the fluorine-containing nitrogenous oxygen is free
The number-average molecular weight of base polymerization inhibitor is 2000~4000, preferably 2500~3000；And/or
It is described it is fluorine-containing containing fluorine content in nitroxyl oxides of free radical inhibitor be 3~62wt%, preferably 14~35wt%；And/or
It is described it is fluorine-containing containing NO free radical content in nitroxyl oxides of free radical inhibitor be 2~13wt%, preferably 7~11wt%；With/
Or
The fluorine-containing boiling point containing nitroxyl oxides of free radical inhibitor is 500~800 DEG C, preferably 550~700 DEG C；And/or
The fluorine-containing nitroxyl oxides of free radical inhibitor that contains is white solid, and color number is 0.
3. a kind of fluorine-containing preparation method containing nitroxyl oxides of free radical inhibitor as claimed in claim 1 or 2, step include:
(1) methyl acrylate and 2,2,6,6- tetramethylpiperidinols occur ester exchange reaction, obtain 2,2,6,6- tetramethyl piperidines
Acrylate；
(2) perfluoroolefine is added into step (1) reaction solution, and 2,2,6,6- tetramethyl piperidine acrylate carry out co-polymeric
Reaction；
(3) sodium tungstate is added into step (2) reaction solution and hydrogen peroxide carries out oxidation reaction, obtains fluorine-containing containing NO free radical resistance
Poly- agent.
4. preparation method according to claim 3, it is characterised in that: in step (1), the ester exchange reaction, temperature is
90~120 DEG C, preferably 100~110 DEG C；Time is 6~12h, preferably 8~10h；
The methyl acrylate and 2,2,6,6- tetramethylpiperidinol molar ratios are 1.5~5:1, preferably 2~3:1；And/or
In step (2), the co-polymeric reaction, reaction temperature is 30~60 DEG C, preferably 40~50 DEG C；Reaction time is 5
~15h, preferably 7~10h, 4~8MPaG of reaction pressure, preferably 5~7MPaG；
The perfluoroolefine and 2,2,6,6- tetramethyl piperidine acrylate molar ratios are 0.5~3:1, preferably 1~2.5:1；With/
Or
In step (3), the oxidation reaction, temperature is 100~110 DEG C, and the time is 36~48h；
The sodium tungstate and 2,2,6,6- tetramethyl piperidine acrylate mass ratioes be 0.05~0.5:1, preferably 0.08~0.15:
1；
The hydrogen peroxide and 2,2,6,6- tetramethyl piperidine alcohol ester molar ratios are 0.8~2:1, preferably 1~1.5:1.
5. a kind of continuous refining process of 4- hy-droxybutyl, which comprises the following steps:
1) the three step continuous extraction of 4- hy-droxybutyl crude reaction liquid separate the hy-droxybutyl containing 4- extract liquor；
2) step 1) extract liquor carries out lye neutralization, washing, oily phase after must washing；
3) oil is added to of any of claims 1 or 2 or fluorine-containing being contained by prepared by claim 3 or 4 methods after step 2) washing
Nitroxyl oxides of free radical inhibitor, rectifying removes light component, then obtains 4- hy-droxybutyl by short-path distillation.
6. continuous refining process according to claim 5, it is characterised in that: in step 1), the 4- hy-droxybutyl
Crude reaction liquid, by 4- hy-droxybutyl crude reaction liquid gross mass be 100% in terms of, composition include: 0.5~5wt% of acrylic acid,
40~60wt% of 1,4- butanediol, 40~50wt% of 4- hy-droxybutyl, 1~10wt% of 1,4 butanediol diacrylate,
0.5~2wt% of catalyst, 0.1~1wt% of polymerization inhibitor；
The catalyst is at least one of the concentrated sulfuric acid, p-methyl benzenesulfonic acid and methanesulfonic acid；
The polymerization inhibitor is phenthazine, hydroquinone, p methoxy phenol, ZJ-701, ZJ-705, N, and N- di-n-butyl two is thio
At least one of carbamic acid copper.
7. continuous refining process according to claim 5 or 6, it is characterised in that: in step 1), the three steps continuous extraction
Separation, including tower separation or centrifugation separation, the equipment used is packed extraction tower, perforated-plate extraction tower, turntable extracting tower
At least one of with centrifugal extractor, preferred centrifugal extractor；
The three steps continuous extraction comprising 1,4-butanediol diacrylate removing extraction cells, 4- hy-droxybutyl mention
Take extraction cells, 1,4- butanediol removing extraction cells；
Extractant used in 1,4 butanediol diacrylate removing extraction cells be hexamethylene, n-hexane, normal heptane,
At least one of pentane, dimethylbenzene, toluene or a variety of mixtures, preferably n-hexane；It is further preferred that the Isosorbide-5-Nitrae-
The mass ratio of butanediol diacrylate removing extraction cells, 4- hy-droxybutyl crude reaction liquid and extractant is 1:2~3,
Extracting series is 5~10 grades, and temperature is 20~30 DEG C；
The 4- hy-droxybutyl extract extractant used in extraction cells be methylene chloride, butyl acetate, chloroform,
At least one of carbon tetrachloride or a variety of mixtures, preferably methylene chloride；It is further preferred that the 4- acrylic acid hydroxyl fourth
The mass ratio of ester extraction extraction cells, 4- hy-droxybutyl crude reaction liquid and extractant is 1:1~3, and extraction series is 2~5
Grade, temperature are 20~30 DEG C；
Extractant used in 1,4- butanediol removing extraction cells be water, 5~10wt%NaCl aqueous solution, 5~
At least one or more of mixture of 10wt%KCl aqueous solution, preferably water；It is further preferred that the 1,4-butanediol is de-
Except extraction cells, the mass ratio of 4- hy-droxybutyl crude reaction liquid and extractant is 1:1~3, and extraction series is 5~10 grades,
Temperature is 20~30 DEG C.
8. according to the described in any item continuous refining process of claim 5-7, it is characterised in that: in step 2), in the lye
With at least one of the lye used selected from NaOH aqueous solution and KOH aqueous solution, preferably NaOH aqueous solution；The lye neutralizes,
The range of pH control is 7~10, preferably 8~9；Temperature is 15~40 DEG C, preferably 20~35 DEG C, more preferable 25~30 DEG C；And/or
The washing, the dosage of water and the mass ratio of neutralizer are 0.1~2:1, preferably 0.3~1:1；Temperature is 15~40 DEG C,
It is preferred that 20~35 DEG C, more preferable 25~30 DEG C.
9. according to the described in any item continuous refining process of claim 5-8, it is characterised in that: described fluorine-containing to contain in step 3)
The additional amount of nitroxyl oxides of free radical inhibitor is the 0.1~5wt%, preferably 1~2wt% of oily phase total amount after washing.
10. according to the described in any item continuous refining process of claim 5-9, it is characterised in that: in step 3), the rectifying,
The theoretical number of plates of rectifying tower used is 10~20, preferably 12~18；The rectifying column uses continuous feed mode；Rectifying column
Tower top temperature is 15~35 DEG C, preferably 20~30 DEG C；Tower top pressure is 40~85KPa (A), preferably 45~70KPa (A)；And/or
The light component is the three remaining extractants of step continuous extraction lock out operation in step 1), it is preferable that the light component is
The mixture of n-hexane, methylene chloride and water；And/or
The short-path distillation, pressure are 0.01~1KPa (A), and preferably 0.02~0.1KPa (A), temperature is 70~180 DEG C, preferably
90~150 DEG C；The short-path distillation carries out in short-path evaporator, and short-path evaporator includes built-in condenser, built-in condenser
Tube side temperature be -60~10 DEG C, preferably -25~5 DEG C；Preferably, the gaseous phase outlet setting two-stage of the short-path evaporator is cold
Condenser, the tube side temperature of first order condenser are 28~40 DEG C, preferably 30~38 DEG C；The tube side temperature of second level condenser be-
60~10 DEG C, preferably -25~5 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903422A (en) * | 2019-12-09 | 2020-03-24 | 万华化学集团股份有限公司 | Polymerization inhibitor and preparation method and application thereof |
| CN110937997A (en) * | 2019-12-09 | 2020-03-31 | 东营海德新材料有限公司 | Production process for improving purity of butyl acrylate |
| CN116536003A (en) * | 2023-07-06 | 2023-08-04 | 深圳海辰储能控制技术有限公司 | Adhesive and preparation method thereof, pole piece, battery and power utilization device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220413A (en) * | 2012-04-21 | 2014-12-17 | 大阪有机化学工业株式会社 | Process for preparing 4-hydroxybutyl acrylate |
| CN109053450A (en) * | 2018-07-03 | 2018-12-21 | 青岛科技大学 | A kind of preparation method for the 4- hy-droxybutyl being separated by extraction |
-
2019
- 2019-08-19 CN CN201910762239.5A patent/CN110467563B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220413A (en) * | 2012-04-21 | 2014-12-17 | 大阪有机化学工业株式会社 | Process for preparing 4-hydroxybutyl acrylate |
| CN109053450A (en) * | 2018-07-03 | 2018-12-21 | 青岛科技大学 | A kind of preparation method for the 4- hy-droxybutyl being separated by extraction |
Non-Patent Citations (2)
| Title |
|---|
| 朱力知等: "大分子氮氧自由基的合成及其阻聚作用", 《高分子通讯》 * |
| 王伟文等: "4-丙烯酸羟丁酯的合成与应用研究", 《合成材料老化与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903422A (en) * | 2019-12-09 | 2020-03-24 | 万华化学集团股份有限公司 | Polymerization inhibitor and preparation method and application thereof |
| CN110937997A (en) * | 2019-12-09 | 2020-03-31 | 东营海德新材料有限公司 | Production process for improving purity of butyl acrylate |
| CN116536003A (en) * | 2023-07-06 | 2023-08-04 | 深圳海辰储能控制技术有限公司 | Adhesive and preparation method thereof, pole piece, battery and power utilization device |
| CN116536003B (en) * | 2023-07-06 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Adhesive and preparation method thereof, pole piece, battery and power utilization device |
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