CN117924135A - Synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate - Google Patents
Synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate Download PDFInfo
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- CN117924135A CN117924135A CN202410084970.8A CN202410084970A CN117924135A CN 117924135 A CN117924135 A CN 117924135A CN 202410084970 A CN202410084970 A CN 202410084970A CN 117924135 A CN117924135 A CN 117924135A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007670 refining Methods 0.000 title claims abstract description 18
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 title claims description 21
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- IXDAOYYROAXYLL-UHFFFAOYSA-N tert-butyl 2-ethylhexoxy carbonate Chemical compound CCCCC(CC)COOC(=O)OC(C)(C)C IXDAOYYROAXYLL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical compound CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000004793 Polystyrene Substances 0.000 claims description 26
- 229920002223 polystyrene Polymers 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 24
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000002274 desiccant Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- RQHGZNBWBKINOY-PLNGDYQASA-N (z)-4-tert-butylperoxy-4-oxobut-2-enoic acid Chemical compound CC(C)(C)OOC(=O)\C=C/C(O)=O RQHGZNBWBKINOY-PLNGDYQASA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000011066 ex-situ storage Methods 0.000 claims description 3
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 125000002081 peroxide group Chemical group 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 239000002313 adhesive film Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YOEYNURYLFDCEV-UHFFFAOYSA-N tert-butyl hydroxy carbonate Chemical compound CC(C)(C)OC(=O)OO YOEYNURYLFDCEV-UHFFFAOYSA-N 0.000 description 3
- BDKLWUHLMPLXCK-UHFFFAOYSA-N 6-methylheptyl carbonochloridate Chemical compound CC(C)CCCCCOC(Cl)=O BDKLWUHLMPLXCK-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-M tert-butyl carbonate Chemical compound CC(C)(C)OC([O-])=O XKXIQBVKMABYQJ-UHFFFAOYSA-M 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, in particular to a synthetic reaction and refining method of tert-butyl peroxycarbonate-2-ethylhexyl ester; the invention adopts the 2-ethylhexyl chloroformate to directly react with the sodium salt of tert-butyl hydroperoxide under the action of the cocatalyst, and the reaction condition is mild and easy to control; the method does not need hydrogen peroxide and concentrated sulfuric acid, and the catalyst can be filtered out, so that the catalyst cannot enter products, and the process of the synthesis reaction can be safely and effectively controlled; meanwhile, liquid alkali loss and production waste of the waste sulfuric acid neutralization treatment in the later stage are avoided, and environmental protection benefits are improved; the peroxide group has good compatibility with tert-butyl hydroperoxide, and is favorable for the increase of the reaction area of the cocatalyst, thereby improving the catalytic effect; the polysilsesquioxane improves the antioxidation capability of the cocatalyst framework, can slow down the degradation of the resin framework caused by oxidization, and prolongs the service life of the catalyst.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthetic reaction and refining method of tert-butyl peroxycarbonate-2-ethylhexyl ester.
Background
Tert-butyl peroxy-2-ethylhexyl carbonate (TBEC) is a special organic peroxide, and is mainly used as polymerization initiator for ethylene, styrene, acrylic ester and methacrylic ester, and cross-linking agent for thermosetting resin (such as EVA adhesive film for solar cell).
The solar photovoltaic power generation industry has continued to develop at a high rate since the 80 s of the 20 th century, and solar panels, also referred to as "photovoltaic modules", are one of the core parts in solar photovoltaic power generation systems. The solar cell panel is formed by installing and fixing a plurality of groups of photovoltaic modules on the frame through sealant (EVA adhesive film), so that the sealant (EVA adhesive film) is an important auxiliary material indispensable in the solar photovoltaic modules. The unmodified EVA adhesive film has poor heat resistance and elasticity, is easy to expand with heat and contract with cold to generate fragmentation, is easy to yellow under severe weather conditions, and influences light transmittance, so that the photoelectric conversion efficiency of the solar module is reduced. Therefore, the EVA adhesive film needs to be modified, and the general method is to adopt chemical crosslinking, namely adding an organic peroxide crosslinking curing agent (tert-butyl peroxycarbonic acid-2-ethylhexyl ester TBEC) and the like into EVA, and when the EVA adhesive film is heated to a certain temperature, the crosslinking agent automatically decomposes to generate free radicals to initiate the combination of EVA molecules to form a three-dimensional network, so that the EVA adhesive layer is crosslinked and cured, and when the crosslinking degree reaches more than 60%, the EVA adhesive film can bear the change of weather, has better heat resistance and does not generate thermal expansion and cold contraction.
The organic peroxide crosslinking curing agent is an important formula component of the EVA adhesive film, and tert-butyl peroxycarbonate-2-ethylhexyl ester (trade name of enterprise is DONG DL-P14) is used as the crosslinking curing agent to rapidly cure the EVA adhesive film, so that a good photovoltaic EVA adhesive film product is obtained.
Chinese patent CN116178234a: belongs to the technical field of chemical synthesis, and in particular relates to a preparation method of solvent type peroxy-2-ethylhexyl tert-butyl carbonate. And (3) adding the mixture of tert-butyl hydroperoxide and alkane and isooctyl chloroformate into a potassium hydroxide solution simultaneously, reacting, standing for layering, and carrying out aftertreatment on an upper organic oil phase to obtain solvent type tert-butyl peroxy-2-ethylhexyl carbonate. According to the invention, the mixture of tert-butyl hydroperoxide and alkane and isooctyl chloroformate are simultaneously added into potassium hydroxide solution for reaction, so that the reaction time is shortened, and the production efficiency is improved; the addition of alkane solvent makes the heat release in the reaction process more stable and controllable, greatly improves the production safety coefficient, omits the subsequent preparation process and simplifies the production process flow.
Chinese patent CN112300044a: belongs to the fields of peroxidation, organic synthesis and peroxide purification, in particular to a method for synthesizing and purifying tert-butyl peroxy-2-ethylhexyl carbonate, which comprises the steps of peroxidation, substitution synthesis, peroxide purification and the like. The invention reduces the discharge of waste liquid and the treatment cost of subsequent waste liquid, the reaction condition is easy to control, the product yield is high, and the purity of the product can reach more than 99 percent.
Chinese patent CN113292470B: the synthesis process is carried out in an integrated continuous flow reactor, reaction raw materials of tert-butyl peroxide, alkali liquor and 2-ethylhexyl chloroformate are continuously added into the feed inlet of the integrated continuous flow reactor, and the discharge outlet of the integrated continuous flow reactor is continuously used for obtaining the tert-butyl peroxy-2-ethylhexyl carbonate without amplification effect, and the total reaction time is not more than 180s. Compared with the traditional production process, the temperature is greatly improved, the total reaction time is greatly shortened, the amplification effect is avoided, the product index is stable, and the reproducibility is good.
At present, the general synthesis method of tert-butyl peroxycarbonate is that tert-butyl alcohol and high-concentration hydrogen peroxide are adopted to generate tert-butyl hydroperoxide through oxidation reaction under the catalysis of concentrated sulfuric acid, and then the tert-butyl hydroperoxide reacts with organic lipid compounds under the catalysis of alkali, so that the corresponding tert-butyl peroxycarbonate is obtained.
The above patents and the prior art have several significant drawbacks:
1. The concentration of the raw materials hydrogen peroxide and concentrated sulfuric acid is high, and the method has great potential safety hazards in the storage and production processes, and can also cause the problem that the temperature is not easy to control in the production process, so that safety production accidents are caused;
2. The oxidation reaction generates tert-butyl hydroperoxide TBHP, and simultaneously generates a large amount of high-concentration waste acid solution, and in addition, the waste liquid treatment causes larger alkali liquid consumption and environmental pollution;
3. The whole reaction has a plurality of unreacted byproducts, the byproducts are directly subjected to the next synthetic reaction without separation, the yield of the target product tert-butyl peroxycarbonate can be reduced, and impurities are introduced; the product purity is low and the product quality is poor without refining, washing and drying processes.
Disclosure of Invention
In order to solve the problems, the invention provides a synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate, which comprises the following operation steps:
S1: according to parts by weight, 100-120 parts of tert-butyl hydroperoxide aqueous solution with the mass concentration of 60-70% is metered into a reactor, and is fully stirred, and the temperature is kept at 20-30 ℃;
s2: dropwise adding 300-400 parts of NaOH solution with the mass concentration of 10-20% under the stirring state, and finishing the dropwise adding after 20-30 min; rapidly stirring for 40-60 minutes, and keeping the temperature at 25-30 ℃ to obtain sodium salt solution of TBHP;
S3: 110-130 parts of 2-ethylhexyl chloroformate is added into a metering tank, and the temperature is kept at 8-15 ℃; after the dripping is completed within 50-60min, 10-15 parts of cocatalyst is added, the synthesis reaction is started, the mixture is fully stirred, the temperature is kept at 30-35 ℃ and the reaction lasts for 1-4h;
s4: stopping stirring, standing and layering for 30-60min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, namely starting stirring, and adding 500-700 parts of dilute H 2SO4 aqueous solution with the mass percentage of 40-60%; maintaining the water temperature at 30-35deg.C, stirring for 10-20min, stopping stirring, standing and layering for 10-20min; discharging the water phase at the bottom of the reactor;
S6: washing II, starting stirring, adding 500-700 parts of brine, keeping the water temperature at 30-50 ℃, stirring for 10-20min, stopping stirring, and standing for layering for 10-20min; discharging the water phase at the bottom of the reactor;
S7: washing three, starting stirring, adding 500-700 parts of pure water, maintaining the water temperature at 30-50 ℃, stirring for 10-20min, stopping stirring, and standing for layering for 10-20min; discharging the water phase at the bottom of the reactor;
s8: drying, adding 200-300 parts of inorganic dehydration drying agent, controlling the temperature of the materials at 30-50 ℃ to obtain the high-purity tert-butyl peroxycarbonate-2-ethylhexyl ester.
The saline water is sodium acetate water solution with the mass percentage of 20-40%.
The inorganic dehydration drying agent is one of anhydrous magnesium sulfate, active alumina and anhydrous sodium sulfate.
The preparation method of the cocatalyst comprises the following steps:
K1: adding 3-7 parts of tert-butyl peroxymaleate, 0.08-0.2 part of octavinyl cage-type oligomeric silsesquioxane, 1-3 parts of potassium ethoxide, 200-300 parts of toluene and 20-40 parts of polystyrene macroporous sulfonic resin with mercapto groups into a closed stirring reaction kettle, introducing nitrogen, stirring at 60-70 ℃ for reaction for 100-150 minutes, filtering after the reaction is finished, and spin-drying;
K2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing hydrochloric acid with the mass percent concentration of 20-30% by volume of 4-8 times through the column, washing until effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
The preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
According to the parts by weight, 100-200 parts of polystyrene macro Kong Huangsuan resin (sodium base in the ex-situ form) is placed in plasma equipment, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 30-60min, so that the polystyrene macro-pore sulfonic resin with the mercapto group is obtained.
The plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source has the frequency of 10-20MHz; the gas flow is 5-10ml/min.
Reaction mechanism:
1. Adopts 2-ethylhexyl chloroformate to directly react with sodium salt of tert-butyl hydroperoxide (TBHP for short), has mild reaction condition and easily controlled temperature;
2. The preparation mechanism of the cocatalyst is as follows:
Tert-butyl peroxymaleate and polystyrene macroporous sulfonic acid resin with sulfhydryl are subjected to sulfhydryl-olefin addition reaction; carrying out a sulfhydryl-olefin addition reaction on octavinyl cage-type oligomeric silsesquioxane and sulfhydryl-containing polystyrene macroporous sulfonic acid resin; to obtain the cocatalyst with peroxidic groups, polysilsesquioxane groups and sulfonic acid groups.
Drawings
FIG. 1 is a schematic flow diagram of a process for tert-butyl peroxy-2-ethylhexyl carbonate.
The technical effects are as follows:
compared with the prior art, the synthetic reaction and refining method of the tert-butyl peroxycarbonate-2-ethylhexyl ester has the following remarkable effects:
1. The invention adopts the 2-ethylhexyl chloroformate to directly react with sodium salt of tert-butyl hydroperoxide (TBHP for short) under the action of a cocatalyst, the reaction condition is mild, and the temperature is easy to control; the hydrogen peroxide and the concentrated sulfuric acid are not needed in the synthesis reaction process, the catalyst can be filtered out, and the catalyst can not enter products, so that the process of the synthesis reaction can be safely and effectively controlled, and the production safety and the quality stability are ensured;
2. Concentrated sulfuric acid is not needed in the synthetic reaction process, so that liquid alkali loss and production waste of the waste sulfuric acid neutralization treatment in the later period are avoided, and the environmental protection benefit is improved; the peroxide group has good compatibility with tert-butyl hydroperoxide, and is favorable for the increase of the reaction area of the cocatalyst, thereby improving the catalytic effect; the polysilsesquioxane improves the antioxidation capability of the cocatalyst framework, can slow down the degradation of the resin framework caused by oxidization, and prolongs the service life of the catalyst;
3. after the synthesis reaction, various impurities in the crude product are removed through refining, washing and drying, so that a high-purity tert-butyl peroxycarbonate-2-ethylhexyl ester (TBEC) product can be obtained, the production process is optimized, and the product quality is improved.
Detailed Description
The invention is further illustrated by the following examples:
the content of tert-butyl peroxy-2-ethylhexyl carbonate was detected by gas chromatography.
Example 1
A synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate comprises the following operation steps:
S1: 100g of tert-butyl hydroperoxide aqueous solution with the mass concentration of 60% is metered into a reactor, and is fully stirred, and the temperature is kept at 20 ℃;
s2: dropwise adding 300g of NaOH solution with the mass concentration of 10% under the stirring state, and finishing the dropwise adding after 20 min; rapidly stirring for 40 minutes, and keeping the temperature at 25 ℃ to obtain a sodium salt solution of TBHP;
S3: 110g of 2-ethylhexyl chloroformate were charged to a metering tank and kept at 8 ℃; after the dripping is completed within 50min, adding 10g of cocatalyst, starting the synthesis reaction, fully stirring, keeping the temperature at 30 ℃ and reacting for 1h;
s4: stopping stirring, standing and layering for 30min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, namely starting stirring, and adding 500g of dilute H 2SO4 aqueous solution with the mass percentage of 40%; maintaining the water temperature at 30deg.C, stirring for 10min, stopping stirring, standing and layering for 10min; discharging the water phase at the bottom of the reactor;
S6: washing II, starting stirring, adding 500g of saline, keeping the water temperature at 30 ℃, stirring for 10min, stopping stirring, and standing for layering for 10min; discharging the water phase at the bottom of the reactor;
s7: washing three, starting stirring, adding 500g of pure water, maintaining the water temperature at 30 ℃, stirring for 10min, stopping stirring, and standing for layering for 10min; discharging the water phase at the bottom of the reactor;
S8: drying, adding 200g of inorganic dehydration drying agent, controlling the temperature of the material at 30 ℃ to obtain high-purity tert-butyl peroxy-2-ethylhexyl carbonate.
The brine is 20% sodium acetate aqueous solution by mass percent.
The inorganic dehydration drying agent is anhydrous magnesium sulfate.
The preparation method of the cocatalyst comprises the following steps:
K1: 3g of tert-butyl peroxymaleate, 0.08g of octavinyl cage-type oligomeric silsesquioxane, 1g of potassium ethoxide, 200g of toluene and 20g of polystyrene macroporous sulfonic acid resin with mercapto groups are added into a closed stirring reaction kettle, nitrogen is introduced, stirring reaction is carried out for 100 minutes at 60 ℃, and the reaction is finished, filtered and dried;
k2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing 4 times of hydrochloric acid with the mass percent concentration of 20% through the column, washing with water until the effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
The preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
100g of polystyrene macro Kong Huangsuan resin (sodium base in the out-field form) is placed in a plasma device, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 30min, so that the polystyrene macro-pore sulfonic resin with the mercapto group is obtained.
The plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source is at the frequency of 10MHz; the gas flow rate was 5ml/min.
Example 2
A synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate comprises the following operation steps:
s1: 105g of a 65% mass concentration aqueous solution of tert-butyl hydroperoxide is metered into a reactor and stirred sufficiently, the temperature being kept at 25 ℃;
s2: under the stirring state, dropwise adding 340g of NaOH solution with the mass concentration of 15%, and finishing the dropwise adding after 25 minutes; rapidly stirring for 45 minutes, and keeping the temperature at 25 ℃ to obtain a sodium salt solution of TBHP;
S3: 115g of 2-ethylhexyl chloroformate were charged to a metering tank and kept at 10 ℃; after the dripping is completed within 55min, adding 12g of cocatalyst, starting the synthesis reaction, fully stirring, keeping the temperature at 30 ℃ and reacting for 2h;
S4: stopping stirring, standing and layering for 40min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, starting stirring, and adding 550g of 45% by mass of dilute H 2SO4 aqueous solution; maintaining the water temperature at 30deg.C, stirring for 15min, stopping stirring, standing and layering for 15min; discharging the water phase at the bottom of the reactor;
S6: washing two, starting stirring, adding 550g of saline, keeping the water temperature at 35 ℃, stirring for 15min, stopping stirring, and standing for layering for 15min; discharging the water phase at the bottom of the reactor;
s7: washing three, starting stirring, adding 550g of pure water, keeping the water temperature at 35 ℃, stirring for 15min, stopping stirring, and standing for layering for 15min; discharging the water phase at the bottom of the reactor;
S8: drying, adding 240g of inorganic dehydration drying agent, controlling the temperature of the material at 35 ℃ to obtain high-purity tert-butyl peroxy-2-ethylhexyl carbonate.
The brine is 25% sodium acetate aqueous solution by mass percent.
The inorganic dehydration drying agent is activated alumina.
The preparation method of the cocatalyst comprises the following steps:
k1: adding 4g of tert-butyl peroxymaleate, 0.1g of octavinyl cage-type oligomeric silsesquioxane, 2g of potassium ethoxide, 240g of toluene and 25g of polystyrene macroporous sulfonic acid resin with mercapto groups into a closed stirring reaction kettle, introducing nitrogen, stirring at 65 ℃ for reaction for 110 minutes, filtering after the reaction is finished, and spin-drying;
K2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing 5 times of hydrochloric acid with the mass percent concentration of 25% through the column, washing with water until the effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
The preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
140g of polystyrene macro Kong Huangsuan resin (sodium base in the out-field form) is placed in a plasma device, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 40min, so that the polystyrene macro-porous sulfonic resin with the mercapto group is obtained.
The plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source is of frequency 15MHz; the gas flow rate was 6ml/min.
Example 3
A synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate comprises the following operation steps:
s1: 115g of a 65% mass concentration aqueous solution of tert-butyl hydroperoxide is metered into a reactor and stirred thoroughly, the temperature being kept at 25 ℃;
S2: under the stirring state, 380g of NaOH solution with the mass concentration of 15% is dropwise added, and the dropwise addition is completed within 25 minutes; rapidly stirring for 55 minutes, and keeping the temperature at 30 ℃ to obtain a sodium salt solution of TBHP;
S3: 125g of 2-ethylhexyl chloroformate were charged to a metering tank and maintained at 13 ℃; after the dripping is completed within 55min, adding 14g of cocatalyst, starting the synthesis reaction, fully stirring, keeping the temperature at 35 ℃ and reacting for 3h;
s4: stopping stirring, standing and layering for 50min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, starting stirring, and adding 650g of 55% by mass of dilute H 2SO4 aqueous solution; maintaining the water temperature at 35 ℃, stirring for 15min, stopping stirring, and standing and layering for 15min; discharging the water phase at the bottom of the reactor;
S6: washing two, starting stirring, adding 650g of saline, keeping the water temperature at 45 ℃, stirring for 15min, stopping stirring, and standing for layering for 15min; discharging the water phase at the bottom of the reactor;
s7: washing three, starting stirring, adding 650g of pure water, keeping the water temperature at 45 ℃, stirring for 15min, stopping stirring, and standing for layering for 15min; discharging the water phase at the bottom of the reactor;
S8: drying, adding 280g of inorganic dehydration drying agent, controlling the temperature of the material at 45 ℃ to obtain high-purity tert-butyl peroxy-2-ethylhexyl carbonate.
The brine is 35% sodium acetate aqueous solution by mass percent.
The inorganic dehydration drying agent is activated alumina.
The preparation method of the cocatalyst comprises the following steps:
K1: adding 6g of tert-butyl peroxymaleate, 0.15g of octavinyl cage-type oligomeric silsesquioxane, 2g of potassium ethoxide, 280g of toluene and 35g of polystyrene macroporous sulfonic acid resin with mercapto groups into a closed stirring reaction kettle, introducing nitrogen, stirring at 65 ℃ for reaction for 140 minutes, filtering after the reaction is finished, and spin-drying;
K2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing through the column by using hydrochloric acid with the mass percent concentration of 25% which is 7 times of the volume, washing with water until the effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
The preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
180g of polystyrene macro Kong Huangsuan resin (the out-field form is sodium base) is placed in a plasma device, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 50min, so that the polystyrene macro-pore sulfonic resin with the mercapto group is obtained.
The plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source is of frequency 15MHz; the gas flow rate was 8ml/min.
Example 4
A synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate comprises the following operation steps:
S1: 120g of tert-butyl hydroperoxide aqueous solution with the mass concentration of 70% is metered into a reactor, and is fully stirred, and the temperature is kept at 30 ℃;
s2: under the stirring state, 400g of NaOH solution with the mass concentration of 20% is dropwise added, and the dropwise addition is completed after 30 min; rapidly stirring for 60 minutes, and keeping the temperature at 30 ℃ to obtain a sodium salt solution of TBHP;
S3: 130g of 2-ethylhexyl chloroformate are introduced into a metering tank, maintained at 15 ℃; after the dripping is completed within 60min, adding 15g of cocatalyst, starting the synthesis reaction, fully stirring, keeping the temperature at 35 ℃ and reacting for 4h;
s4: stopping stirring, standing and layering for 60min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, namely starting stirring, and adding 700g of 60% by mass of dilute H 2SO4 aqueous solution; maintaining the water temperature at 35 ℃, stirring for 20min, stopping stirring, and standing and layering for 20min; discharging the water phase at the bottom of the reactor;
S6: washing II, starting stirring, adding 700g of saline, keeping the water temperature at 50 ℃, stirring for 20min, stopping stirring, and standing for layering for 20min; discharging the water phase at the bottom of the reactor;
s7: washing three, starting stirring, adding 700g of pure water, keeping the water temperature at 50 ℃, stirring for 20min, stopping stirring, and standing for layering for 20min; discharging the water phase at the bottom of the reactor;
s8: drying, adding 300g of inorganic dehydration drying agent, controlling the temperature of the material at 50 ℃ to obtain high-purity tert-butyl peroxy-2-ethylhexyl carbonate.
The brine is 40% sodium acetate aqueous solution by mass percent.
The inorganic dehydration drying agent is anhydrous sodium sulfate.
The preparation method of the cocatalyst comprises the following steps:
k1: 7g of tert-butyl peroxymaleate, 0.2g of octavinyl cage-type oligomeric silsesquioxane, 3g of potassium ethoxide, 300g of toluene and 40g of polystyrene macroporous sulfonic acid resin with mercapto groups are added into a closed stirring reaction kettle, nitrogen is introduced, stirring reaction is carried out for 150 minutes at 70 ℃, and filtering and spin-drying are carried out after the reaction is finished;
k2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing 8 times of hydrochloric acid with the mass percent concentration of 30% through the column, washing with water until the effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
The preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
200g of polystyrene macro Kong Huangsuan resin (the ex-situ form is sodium base) is placed in a plasma device, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 60min, so that the polystyrene macro-pore sulfonic resin with the mercapto group is obtained.
The plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source is 20MHz; the gas flow rate was 10ml/min.
Comparative example 1
The procedure of example 1 was followed except that no cocatalyst was added.
Comparative example 2
T-butyl peroxymaleate was not added, otherwise as in example 1.
Comparative example 3
Eight vinyl cage oligomeric silsesquioxanes were not added, as in example 1.
| Content/% | |
| Example 1 | 99.26 |
| Example 2 | 99.91 |
| Example 3 | 99.95 |
| Example 4 | 99.98 |
| Comparative example 1 | 85.45 |
| Comparative example 2 | 92.32 |
| Comparative example 3 | 97.55 |
Through the data analysis of the above examples and comparative examples, the cocatalyst of the present invention improves the catalytic effect, optimizes the production process and improves the product quality.
Claims (6)
1. A synthetic reaction and refining method of tert-butyl peroxy-2-ethylhexyl carbonate comprises the following operation steps:
S1: according to parts by weight, 100-120 parts of tert-butyl hydroperoxide aqueous solution with the mass concentration of 60-70% is metered into a reactor, and is fully stirred, and the temperature is kept at 20-30 ℃;
s2: dropwise adding 300-400 parts of NaOH solution with the mass concentration of 10-20% under the stirring state, and finishing the dropwise adding after 20-30 min; rapidly stirring for 40-60 minutes, and keeping the temperature at 25-30 ℃ to obtain sodium salt solution of TBHP;
S3: 110-130 parts of 2-ethylhexyl chloroformate is added into a metering tank, and the temperature is kept at 8-15 ℃; after the dripping is completed within 50-60min, 10-15 parts of cocatalyst is added, the synthesis reaction is started, the mixture is fully stirred, the temperature is kept at 30-35 ℃ and the reaction lasts for 1-4h;
s4: stopping stirring, standing and layering for 30-60min; discharging the high-salinity water phase at the bottom of the reactor, wherein the upper oil phase is the crude product of tert-butyl peroxycarbonate-2-ethylhexyl ester,
S5: washing, namely starting stirring, and adding 500-700 parts of dilute H 2SO4 aqueous solution with the mass percentage of 40-60%; maintaining the water temperature at 30-35deg.C, stirring for 10-20min, stopping stirring, standing and layering for 10-20min; discharging the water phase at the bottom of the reactor;
S6: washing II, starting stirring, adding 500-700 parts of brine, keeping the water temperature at 30-50 ℃, stirring for 10-20min, stopping stirring, and standing for layering for 10-20min; discharging the water phase at the bottom of the reactor;
S7: washing three, starting stirring, adding 500-700 parts of pure water, maintaining the water temperature at 30-50 ℃, stirring for 10-20min, stopping stirring, and standing for layering for 10-20min; discharging the water phase at the bottom of the reactor;
s8: drying, adding 200-300 parts of inorganic dehydration drying agent, controlling the temperature of the materials at 30-50 ℃ to obtain the high-purity tert-butyl peroxycarbonate-2-ethylhexyl ester.
2. The method for synthesizing and refining 2-ethylhexyl tert-butylperoxycarbonate according to claim 1, wherein the method comprises the steps of: the saline water is sodium acetate water solution with the mass percentage of 20-40%.
3. The method for synthesizing and refining 2-ethylhexyl tert-butylperoxycarbonate according to claim 1, wherein the method comprises the steps of: the inorganic dehydration drying agent is one of anhydrous magnesium sulfate, active alumina and anhydrous sodium sulfate.
4. The method for synthesizing and refining 2-ethylhexyl tert-butylperoxycarbonate according to claim 1, wherein the method comprises the steps of: the preparation method of the cocatalyst comprises the following steps:
K1: adding 3-7 parts of tert-butyl peroxymaleate, 0.08-0.2 part of octavinyl cage-type oligomeric silsesquioxane, 1-3 parts of potassium ethoxide, 200-300 parts of toluene and 20-40 parts of polystyrene macroporous sulfonic resin with mercapto groups into a closed stirring reaction kettle, introducing nitrogen, stirring at 60-70 ℃ for reaction for 100-150 minutes, filtering after the reaction is finished, and spin-drying;
K2: according to the method for converting sodium type cation exchange resin into hydrogen type cation exchange resin known in the art, loading the resin obtained by K1 into an exchange column, passing hydrochloric acid with the mass percent concentration of 20-30% by volume of 4-8 times through the column, washing until effluent liquid is pH=7, taking out, and drying to obtain the cocatalyst.
5. The method for synthesizing and refining 2-ethylhexyl tert-butylperoxycarbonate according to claim 4, wherein the method comprises the steps of: the preparation method of the polystyrene macroporous sulfonic acid resin with mercapto group comprises the following steps:
According to the parts by weight, 100-200 parts of polystyrene macro Kong Huangsuan resin (sodium base in the ex-situ form) is placed in plasma equipment, thioglycollic acid is introduced to carry out plasma modification in a mercaptoethanol steam atmosphere, and the treatment time is 30-60min, so that the polystyrene macro-pore sulfonic resin with the mercapto group is obtained.
6. The method for synthesizing and refining 2-ethylhexyl tert-butylperoxycarbonate according to claim 5, wherein the method comprises the steps of: the plasma modification conditions are as follows: a 500W rf power source plasma device; the radio frequency power source has the frequency of 10-20MHz; the gas flow is 5-10ml/min.
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