CN117285406A - Novel environment-friendly styrene polymerization inhibitor and preparation method thereof - Google Patents
Novel environment-friendly styrene polymerization inhibitor and preparation method thereof Download PDFInfo
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 75
- 239000003112 inhibitor Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 7
- -1 quinone methyl compound Chemical class 0.000 claims abstract description 109
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000003254 radicals Chemical group 0.000 claims abstract description 60
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000006078 metal deactivator Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 41
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 10
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWGJJEBPCVMBIG-UHFFFAOYSA-N 2-methyl-2-[2-[(2-methylpropan-2-yl)oxy]ethoxy]propane Chemical compound CC(C)(C)OCCOC(C)(C)C KWGJJEBPCVMBIG-UHFFFAOYSA-N 0.000 claims description 9
- NAPYSZKXFNWXEM-UHFFFAOYSA-N 2,3,5,6-tetratert-butylcyclohexa-2,5-dien-1-one Chemical group CC(C)(C)C1=C(C(C)(C)C)C(=O)C(C(C)(C)C)=C(C(C)(C)C)C1 NAPYSZKXFNWXEM-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 17
- 229920001223 polyethylene glycol Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 229920001732 Lignosulfonate Polymers 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000000178 monomer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
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Abstract
The invention discloses a novel environment-friendly styrene polymerization inhibitor and a preparation method thereof, which relate to the technical field of styrene polymerization inhibitors and comprise the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator and solvent, wherein the weight portions of the components are as follows: 4-7 parts of quinone methyl compound, 5-12 parts of ethylbenzene, 4-8 parts of 2, 6-di-tert-butylphenol, 3-12 parts of free radical substituent and 2-5 parts of ether compound. The invention has novel design and simple operation, the free radical compound and the quinone compound are added in raw material components, in the preparation process, the free radical compound has the property of a true inhibitor, the quinone compound has the property of a retarder, and the two compounds are matched to ensure that the compound polymerization inhibitor has the properties of both the retarder and the true inhibitor, and not only can generate an induction period but also can reduce the polymerization inhibition rate in the polymerization inhibition process, thereby improving the polymerization inhibition effect.
Description
Technical Field
The invention relates to the technical field of styrene polymerization inhibitors, in particular to a novel environment-friendly styrene polymerization inhibitor and a preparation method thereof.
Background
Styrene is widely used as a monomer in the fields of synthesizing high polymer materials, coatings, pesticides, medicines, dyes and the like. In the production process, styrene monomer with high purity is prepared by ethylbenzene dehydrogenation and rectification, and the styrene monomer is active and can be polymerized at normal temperature, so that the higher the temperature is, the easier the polymerization is. In order to avoid polymerization of vinyl monomers during storage, transportation and the like, a small amount of polymerization inhibitor is often added into the monomers, and the vinyl monomers are removed before use. Polymerization inhibitors are industrial auxiliaries which are generally used to prevent the polymerization from proceeding, and the polymerization inhibitor molecules react with chain radicals to form non-radical substances or low-activity free radicals which cannot be initiated, so that the polymerization is terminated. In general, the polymerization inhibitor is a solid substance, has small volatility, and can be removed when distilling the monomer.
Polymerization inhibitors developed at home and abroad are mainly divided into two types of true polymerization inhibitors and polymerization inhibitors, wherein the true polymerization inhibitors such as nitroxide free radical compounds have high polymerization inhibition efficiency, can generate a long induction period, almost have no polymer generation during the induction period, but have the defects of easy consumption by free radicals and short service life; the polymerization retarder such as nitrophenol has stable chemical property, little failure in polymerization inhibition process, can reduce polymerization rate, but can not generate obvious induction period, so that the content of the polymer is slowly increased all the time. In order to combine the advantages of the retarder and the true polymerization inhibitor and overcome the defects of independent use, research on the compound polymerization inhibitor is started at home and abroad.
Through retrieval, patent document (application publication number is CN 111689832A) discloses a styrene green polymerization inhibitor, which comprises a first component, a second component and a third component, wherein the first component is a quinone methyl compound, the second component is ethylbenzene, and the third component is 2, 6-di-tert-butylphenol. Further, the mass percentage of the first component is 30-60%, the mass percentage of the second component is 30-60%, and the mass percentage of the third component is 1-10%.
When the styrene green polymerization inhibitor is used, a large amount of polymerization inhibitor needs to be added to achieve the effect, and meanwhile, the polymerization inhibition rate cannot be reduced during use, so that the polymerization inhibition effect is poor, and the actual use requirement cannot be met.
Disclosure of Invention
(one) solving the technical problems
The styrene green polymerization inhibitor in the prior art can not reduce polymerization inhibition rate when in use because a large amount of polymerization inhibitor is added when in use, so that the polymerization inhibition effect is poor and the actual use requirement cannot be met.
(II) technical scheme
In order to solve the problems, the invention provides the following technical scheme:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 4-7 parts of quinone methyl compound, 5-12 parts of ethylbenzene, 4-8 parts of 2, 6-di-tert-butylphenol, 3-12 parts of free radical substituent, 2-5 parts of ether compound, 0.1-0.3 part of metal deactivator and 75-85 parts of solvent;
wherein: the molecular structural formula of the I is as follows:
wherein n=1, 2.
As a further scheme of the invention: and 0.6-1.2 parts of dispersing agent.
As a further scheme of the invention: the metal deactivator is benzotriazole or 2, 5-amphiphobic thiadiazole.
As a further scheme of the invention: the free radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-tolueneoxy free radical.
As a further scheme of the invention: the mass ratio of the quinone methyl compound to the free radical substituent is 1:3.
As a further scheme of the invention: the dispersing agent is polyethylene glycol.
As a further scheme of the invention: the dispersing agent is lignin sulfonate.
As a further scheme of the invention: the ether compound is glycol di-tert-butyl ether or glycol monobutyl ether.
As a further scheme of the invention: the solvent is one or more of ethanol, propylene glycol, 2-methyl-2, 4-pentanediol and ethylene glycol.
Meanwhile, the invention also provides a preparation method of the novel environment-friendly styrene polymerization inhibitor, which comprises the following steps:
step 1: fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A;
step 2: mixing the free radical substituent with a solvent, and stirring to obtain a mixed solution B;
step 3: firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C;
step 4: sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture;
step 5: and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
(III) beneficial effects
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the free radical compound and the quinone compound are added into the raw material components, and in the preparation process, the free radical compound has the property of a true inhibitor, and the quinone compound has the property of a retarder, so that the compound polymerization inhibitor has the properties of both the retarder and the true inhibitor, and in the polymerization inhibition process, the induction period can be generated, the polymerization inhibition rate can be reduced, the polymerization inhibition effect can be improved, and the actual production requirement can be met;
the unique surface activity of the dipropylene glycol solution containing the tetramethyl alkynediol compound with the molecular formula I promotes the solubility of two substances with different polarities in the same system, so that the free radical substituent and the quinone methyl compound can stably exist in the same system.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 4 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 3 parts of free radical substituent, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the mass ratio of quinone methyl compound to radical substituent is 1:3, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
Example 2:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 4 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 12 parts of free radical substituent, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the mass ratio of quinone methyl compound to radical substituent is 1:3, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
Example 3:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 5 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 8 parts of free radical substituent, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the mass ratio of quinone methyl compound to radical substituent is 1:3, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
It is to be noted that in examples 1 to 3: the molecular structural formula of the I is as follows:
wherein n=1, 2.
Example 4:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent and dispersant, wherein the weight portions of the components are as follows: 7 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 12 parts of free radical substituent, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle, heating to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the mass ratio of quinone methyl compound to radical substituent is 1:3, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
Example 5:
the novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent and dispersant, wherein the weight portions of the components are as follows: 6 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 7 parts of free radical substituent, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle, heating to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the mass ratio of quinone methyl compound to radical substituent is 1:3, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
The novel environment-friendly styrene polymerization inhibitor comprises the following components: ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 3 parts of a free radical substituent, 2 parts of an ether compound, 0.1 part of a metal deactivator, 75 parts of a solvent and 0.6 part of a dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, ethylbenzene, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this example, the metal deactivator is benzotriazole, the radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-toluyloxy radical, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
This comparative example differs from example 1 in that 4 parts of the quinone methyl compound was not added in this comparative example, and the other components and parameters were the same.
The novel environment-friendly styrene polymerization inhibitor comprises the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, ether compound, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 4 parts of quinone methyl compound, 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A; firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, solvent and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this embodiment, the metal deactivator is benzotriazole, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
This comparative example differs from example 2 in that 12 parts of radical substituent are not added in this comparative example, and the other components and parameters are the same.
The novel environment-friendly styrene polymerization inhibitor comprises the following components: ethylbenzene, 2, 6-di-tert-butylphenol, ether compounds, metal deactivator, solvent, dispersant and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 5 parts of ethylbenzene, 4 parts of 2, 6-di-tert-butylphenol, 2 parts of ether compound, 0.1 part of metal deactivator, 75 parts of solvent and 0.6 part of dispersing agent, wherein the dispersing agent can be any one of polyethylene glycol and lignosulfonate;
firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C; sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, ethylbenzene, solvent and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture; and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
In this embodiment, the metal deactivator is benzotriazole, the dispersant is polyethylene glycol, the ether compound is ethylene glycol di-tert-butyl ether, and the solvent is ethanol.
The present comparative example differs from any of the above examples in that the quinone methyl compound and the radical substituent are not added thereto, and the other components and parameters are the same.
The styrene polymerization inhibitors in examples 1 to 5 and comparative examples 1 to 3 were subjected to the following performance tests: carrying out alkali washing and distillation on the commercial styrene to obtain a styrene pure agent without any polymerization inhibitor; adding 500ppm of styrene polymerization inhibitor into the styrene purifying agent respectively, reacting for 30min under the condition of nitrogen protection and 120 ℃, separating out a styrene polymer by using methanol or ethanol, filtering, drying, weighing, and calculating the mass percent of the styrene polymer corresponding to the styrene purifying agent as the polymer content, wherein the adding amount of the styrene polymerization inhibitor is in parts per million (ppm). Wherein the units of the polymer content are percent (%), and the test results are shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Reaction time (min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Polymer content (%) | 0.23 | 0.25 | 0.27 | 0.26 | 0.31 | 0.45 | 0.54 | 0.68 |
| Radical substituent and quinone methyl compound inventory (%) | 45 | 51 | 48 | 24 | 28 | 12 | 14 | 0 |
From table 1, it can be seen that the polymer contents of examples 1 to 5 are smaller than those of comparative examples 1 to 3, and it can be inferred that the styrene polymerization inhibitors produced in examples 1 to 5 have a remarkable polymerization inhibiting effect. Meanwhile, as can be seen from comparison of examples 1 to 5, in the case of adding a 50% dipropylene glycol solution containing a tetramethyleneglycol compound having a molecular formula I, its unique surface activity can promote the solubility of two different polar substances in the same system, so that the radical substituent and the quinone methyl compound can exist stably in the same system; since in comparative examples 1 to 3, the radical substituent and the quinone methyl compound were present in comparative examples 1 and 2, respectively, whereas in comparative example 3, either one of the radical substituent and the quinone methyl compound was not added, and the remaining amount thereof was zero.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The novel environment-friendly styrene polymerization inhibitor is characterized by comprising the following components: quinone methyl compound, ethylbenzene, 2, 6-di-tert-butylphenol, free radical substituent, ether compound, metal deactivator, solvent and 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, wherein the weight portions of the components are as follows: 4-7 parts of quinone methyl compound, 5-12 parts of ethylbenzene, 4-8 parts of 2, 6-di-tert-butylphenol, 3-12 parts of free radical substituent, 2-5 parts of ether compound, 0.1-0.3 part of metal deactivator and 75-85 parts of solvent;
wherein: the molecular structural formula of the I is as follows:
wherein n=1, 2.
2. The novel environment-friendly styrene polymerization inhibitor according to claim 1, further comprising 0.6-1.2 parts of dispersant.
3. The novel environment-friendly styrene polymerization inhibitor according to claim 2, wherein the metal deactivator is benzotriazole or 2, 5-amphiphobic thiadiazole.
4. The novel environment-friendly styrene polymerization inhibitor according to claim 3, wherein the free radical substituent is 2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -p-tolueneoxy free radical.
5. The novel environmentally friendly styrene polymerization inhibitor according to claim 4, wherein the mass ratio of said quinone methyl compound to said radical substituent is 1:3.
6. The novel environment-friendly styrene polymerization inhibitor according to claim 5, wherein the ether compound is ethylene glycol di-tert-butyl ether or ethylene glycol monobutyl ether.
7. The novel environment-friendly styrene polymerization inhibitor according to claim 6, wherein the solvent is one or more of ethanol, propylene glycol, 2-methyl-2, 4-pentanediol and ethylene glycol.
8. A method for preparing a novel environment-friendly styrene polymerization inhibitor by using the method as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
step 1: fully mixing the quinone methyl compound with ethylbenzene for 2h, then heating to 65-95 ℃, and stirring to remove surface floating liquid to obtain a mixed liquid A;
step 2: fully mixing the free radical substituent with the solvent for 1h, then heating to 100-125 ℃, and stirring to remove precipitated impurities at the bottom to obtain a mixed solution B;
step 3: firstly, putting an ether compound, a metal deactivator and a dispersing agent into a stirrer to be fully stirred for 30min, then adding 3L of water, continuously stirring for 40min, and standing for 10min to obtain a mixed solution C;
step 4: sequentially adding 2, 6-di-tert-butylphenol, 50% dipropylene glycol solution containing tetramethyl alkyne diol compound with molecular formula I, mixed solution A, mixed solution B and mixed solution C into a reaction kettle, gradually heating the reaction kettle to 10 ℃ each time until the temperature of the reaction kettle is raised to 120 ℃, preserving heat for 25min, and uniformly stirring the mixture;
step 5: and filtering impurities after uniformly stirring to obtain the styrene polymerization inhibitor.
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| WO2004083156A1 (en) * | 2003-03-17 | 2004-09-30 | Hakuto Co., Ltd. | Polymerization inhibitor for aromatic vinyl compounds and method for inhibiting the polymerization of the compounds |
| CN110878209A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Environment-friendly polymerization inhibitor for styrene rectification system and application thereof |
| CN112645789A (en) * | 2020-12-26 | 2021-04-13 | 中海油天津化工研究设计院有限公司 | Compound polymerization inhibitor for styrene rectification and preparation method thereof |
| CN114751805A (en) * | 2022-05-07 | 2022-07-15 | 广东耀辉新材料有限公司 | Green environment-friendly styrene polymerization inhibitor and preparation method thereof |
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| WO2004083156A1 (en) * | 2003-03-17 | 2004-09-30 | Hakuto Co., Ltd. | Polymerization inhibitor for aromatic vinyl compounds and method for inhibiting the polymerization of the compounds |
| CN110878209A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Environment-friendly polymerization inhibitor for styrene rectification system and application thereof |
| CN112645789A (en) * | 2020-12-26 | 2021-04-13 | 中海油天津化工研究设计院有限公司 | Compound polymerization inhibitor for styrene rectification and preparation method thereof |
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