CN103582655A - Synergistic polymerization inhibitor composition and method - Google Patents
Synergistic polymerization inhibitor composition and method Download PDFInfo
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- CN103582655A CN103582655A CN201280012225.8A CN201280012225A CN103582655A CN 103582655 A CN103582655 A CN 103582655A CN 201280012225 A CN201280012225 A CN 201280012225A CN 103582655 A CN103582655 A CN 103582655A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
Please be informed that the "follow up required item" does not work properly. For TOC and SL indication there is a follow-up required item although there is no warning in Bibadmin. See following example : A vinyl monomer polymerization inhibitor composition comprising a liquid mixture comprising a vinyl monomer and a polymerization inhibiting effective amount of a captive polymerization inhibitor, wherein the composition lacks a fugitive polymerization inhibitor of polymerization of the vinyl monomer and the captive polymerization inhibitor independently is characterizable as being an inhibitor of polymerization of the vinyl monomer and polymerization of the vinyl monomer is inhibited by the captive polymerization inhibitor, and wherein the captive polymerization inhibitor is a compound of formula (I): or a first acid addition salt thereof, wherein R1 is hydrogen or (C1-C3)alkyl.
Description
the cross reference of related application
The application requires the right of priority of the provisional application that the sequence number of submission on March 9th, 2011 is 61/450,734, and described provisional application is incorporated to herein by reference with its full content.
Technical field
The present invention relates to the method for polymerization of vinyl monomer inhibitor combination and inhibition therein ethylene base monomer polymerization.
Background technology
Vinyl monomer comprises vinyl alcohol and ester class and acrylic monomer.Vinyl monomer is widely used in chemical industry.For example, acrylic monomer is used for preparing polyacrylate polymkeric substance (for example poly-(vinylformic acid) and poly-(methacrylic acid)), polyacrylate polymkeric substance can be used as additive (for example,, for rubber, coating and tackiness agent) and the composition in fiber and other goods in addition.The subject matter of vinyl monomer is premature polymerization.In the situation that there is no enough polymerization retarders, vinyl monomer can undesirably polymerization during manufacture, purifying, processing and storing operation.Unique terms of settlement to this problem is mentioned in WO2010/096512A1, and described document relates to the monomer polymerization inhibitor combination that comprises trap-type (captive) polymerization retarder and loss type (fugitive) polymerization retarder.Described loss type polymerization retarder be characterised in that can be together with retortable monomer from first location (for example still kettle) vaporization and together with described retortable monomer for example, in the second position (distillation tower) condensation.
The problem that the present invention is devoted to solve comprises provides the polymerization of vinyl monomer that comprises trap-type polymerization retarder inhibitor combination, the polymerization of described composition ethene suppressing base monomer is better than unexpectedly thiodiphenylamine and suppresses such polymerization, and wherein said composition lacks the loss type polymerization retarder of vinyl monomer.
invention summary
In the first embodiment, the invention provides polymerization of vinyl monomer inhibitor combination, the liquid mixture that it comprises the trap-type polymerization retarder that contains vinyl monomer and polymerization retardation significant quantity, wherein said composition lacks the loss type polymerization retarder of polymerization of vinyl monomer, and described trap-type polymerization retarder be characterised in that can be independently as collaborative (synergistically) of polymerization of vinyl monomer effective inhibitor, and the polymerization of described vinyl monomer is by the collaborative inhibition of described trap-type polymerization retarder, and wherein said trap-type polymerization retarder is the compound of formula (I), or its first acid salt:
Under the certain situation of the first embodiment, vinyl monomer is Acrylic Acid Monomer, the acrylic type monomer of preferred formula (M):
In the second embodiment, the invention provides the method for collaborative ethene suppressing base monomer polymerization, described method comprises together with the trap-type polymerization retarder of vinyl monomer and polymerization retardation significant quantity and contacting, thereby produces the present composition.
The present composition is the composition that can work in the method for the second embodiment.The present composition be for example used in container as the polymerization retarder as vinyl monomer in still kettle, storage vessel and transport container is manufactured, purifying, processing and storage ethylene base monomer (for example vinyl alcohol and ester class and acrylic monomer).
Other embodiment has been described in the rest part of specification sheets.
detailed Description Of The Invention
The embodiments of the present invention of summarizing above and summary are incorporated to herein by reference.While using in this article, term " vinyl monomer " refers to containing structure fragment H
2c=C (H)-and molecular weight <1, the molecule of 000 gram/mol (g/mol).Term " Acrylic Acid Monomer " refers to have structure fragment
vinyl monomer, wherein
represent covalent linkage part.Term " trap-type polymerization retarder " for example refers to, during vinyl monomer (Acrylic Acid Monomer) distills from still kettle, can not evaporate the material that leaves still kettle.Term " loss type polymerization retarder " refers to and can vaporize together with vinylformic acid and the material of condensation with polymerization retardation amount.Term " inhibition " refer to postpone the behavior that will suppress starting, reduce its degree or preferably stop it.Phrase " collaborative effective polymerization retarder " refers to and prevents that vision from occurring that solid gather (vinyl monomer) (for example poly-(Acrylic Acid Monomer)) and reaches value mean time of at least 70 hours, and this is approximately the twice of use thiodiphenylamine obtainable mean time of value itself.The following program determination of described time utilization: the vial of the liquid mixture that sealing contains described material that vinyl monomer (for example Acrylic Acid Monomer) and the gross weight based on liquid mixture are 100ppm or the described material of 100ppm and the inhibitor conditioning agent (modifier) of 20ppm.Described bottle is put into constant temperature the mineral oil bath of 113 ℃.Record in bottle (on the bottle wall in liquid mixture or above liquid mixture) vision Anywhere and occur that solid gathers time of (vinyl monomer) (for example poly-(Acrylic Acid Monomer)).Repeat 4 times.By described five times on average to obtain value mean time.Term " inhibitor conditioning agent " for example refers to, from the material (manganese salt) of its derivative generation or the described compound of regenerating.Term " shortage " etc. (for example not having) refers to completely not.Term " polymerization retardation significant quantity " refers to is enough to postpone polymerization starting, reduce extent of polymerization or preferably stop polymerization material absolute weight (for example, gram) or relative weight (for example, representing with PPM (ppm) or weight percent (wt%)).Phrase " inhibition is worked in coordination with in polymerization " etc. refers in the situation that polymerisable monomer is exposed to polymerizing condition (cause between the molecule of two or more polymerisable monomers bonding to produce the chemical process of its organic oligomer or polymkeric substance) and described polymerisable monomer contacts with described trap-type polymerization retarder, the speed of the chemical process under existing with at comparison inhibitor thiodiphenylamine is compared, and the speed of described chemical process obviously reduces.
Conflict solves: conflict with any of written contents in the patent being incorporated to by reference, patent application or public announcement of a patent application or its part, with the written contents in this specification sheets, be as the criterion.Conflict with any of compound title, with structure, be as the criterion.With any conflict of International System of Units (SI) value, with any non SI units value processed, be as the criterion.Conflict with any of its written explanation, with accompanying drawing, be as the criterion.
Numerical range: any lower limit of numerical range or any preferred lower limit of described scope, can combine with any upper limit of described scope or any preferred upper limit of described scope, to limit preferable case or the embodiment of described scope.Unless otherwise noted, each numerical range comprises all numerical value that comprise within the scope of this, rational number and irrational number the two (for example " from 1 to 5 " for example comprise 1,1.5,2,2.75,3,3.81,4 and 5).
Term " (C
1-C
18) alkyl " refer to unsubstituted saturated straight chain or the branched hydrocarbyl of 1 to 18 carbon atom.(C
1-C
18) example of alkyl is (C
9-C
18) alkyl (for example, (C
18) alkyl is as CH
3(CH
2)
17-) and (C
1-C
8) alkyl, it comprises (C
1-C
3) alkyl, comprise methyl, ethyl, 1-propyl group and 2-propyl group; (C
4-C
8) alkyl, comprise 1-butyl (also claiming normal-butyl or n-butyl), 2-butyl, 2-methyl-propyl, 1,1-dimethyl ethyl, 1-amyl group, 1-hexyl, 1-heptyl and 1-octyl group.Term " (C
1-C
3) alkyl-O-" refer to (C of bonded oxygen atomic radical
1-C
3) alkyl.
Described trap-type polymerization retarder is especially used in the polymerization of for example, in distil container (still), storage vessel or pipeline (pipe and tube of material) ethene suppressing base monomer (for example Acrylic Acid Monomer).
The polymerization retardation significant quantity of described trap-type polymerization retarder (being formula (I) compound) can for example, according to concrete vinyl monomer for example to be suppressed (Acrylic Acid Monomer) and amount thereof, condition temperature and pressure and exist or do not exist other trap-type polymerization retarders to change for example.Process of the present invention starts can be with than thinking the larger polymerization retardation significant quantity of amount needing.Then, can allow described polymerization retardation significant quantity (for example reduce, along with polymerization retarder is reacted), for example, until obtain under the described conditions the polymerization retardation dosage of desirable stable state (proving by reach the timed interval needing between cleaning container).Those of ordinary skill in the art just can determine polymerization retardation significant quantity suitable under particular case by the test without excessive.Preferred the first polymerization retardation significant quantity of formula (I) compound is that about 5ppm is to about 500ppm, more preferably from about 10ppm is to about 250ppm, also more preferably from about 20ppm to about 200ppm, and even more preferably from about 40ppm to about 100ppm, all gross weight based on liquid mixture.
Described trap-type polymerization retarder does not comprise the derivative of vinyl monomer (for example Acrylic Acid Monomer).
In some embodiments, described trap-type polymerization retarder is the compound of formula (I), wherein R
1hydrogen.In some embodiments, R
1(C
1-C
3) alkyl.In some embodiments, R
1ethyl, 1-propyl group or 2-propyl group, and more preferably, R
1it is methyl.In some embodiments, the compound of formula (I) is N-benzyl-thiodiphenylamine, in other embodiments, is N-(1-styroyl) thiodiphenylamine, in other embodiment again, is its first acid salt.
Formula (I) compound synthetic is not key of the present invention, and can consider that all successes are synthetic.In some embodiments, as shown in below graphic 1, the compound of formula (I) is by synthesizing the corresponding intermediate aminocompound alkylation of formula (IA).
Graphic 1.
R wherein
1as the description to formula (I), and LG is leavings group.In graphic 1, in nucleophilic substitution temperature, preferably from approximately 0 ℃ to approximately 100 ℃, the aminocompound of formula (IA) contacts under non-nucleophilic strong base and aprotic solvent existence with formula (IB) compound with leavings group, the compound of production (I).The example of aprotic solvent is tetrahydrofuran (THF), 1, and 2-glycol dimethyl ether is with diox.The example of non-nucleophilic base is sodium hydride, potassium hydride KH, the silica-based potassium amide of hexamethyl two (KHMDS) and lithium diisopropylamine (LDA).The example of leavings group is iodine, bromine, chlorine, activation hydroxyl, trifluoromethayl sulfonic acid root, trifluoroacetic acid root and tosylate.In some embodiments, this activation hydroxyl is to be formula (IB) compound of HO-and coupling agent for example triphenylphosphine and di-isopropyl azodicarboxylate (DIAD), 1-(3-dimethyl aminopropyl)-3-ethyl-carbodiimide hydrochloride (EDC from LG wherein, EDCI, or EDAC), N, N '-carbonyl dimidazoles (CDI) or N, N '-dicyclohexylcarbodiimide (DCC), and optionally have I-hydroxybenzotriazole (HOBt) and (benzotriazole-1-base oxygen) tripyrrole alkyl phosphonium hexafluorophosphate to prepare.
Other synthesis methods of formula (I) compound have also been considered.For example, work as R
1while being hydrogen, formula (I) compound can the compound of through type (IA) and the acid anhydrides coupling of the carboxylic acid halides of formula halogen-C (=O)-phenyl or formula phenyl-C (=O)-O-C (=O)-phenyl synthesize, the front terminal group methane amide of production (IC):
The present invention has also considered the acid salt of use formula (I) compound.Term " acid salt " refers to the ionic species that comprises organic cation and organic or preferred inorganic anion.The protonated form that organic cation comprises thiodiphenylamine or formula (I) compound.The residue that described negatively charged ion comprises the organic or preferred mineral compound with at least one proton, described compound characteristic is that (pKa value is less than 7
the residue of acid).Simple substance that preferred acid salt comprises 0.9 to 1.1 molar equivalent
two protons of acid, 0.45 to 0.55 molar equivalent
three protons of acid or 0.3 to 0.37 molar equivalent
acid, all according to thiodiphenylamine or formula (I) compound of every mole.Preferably
acid comprises hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, Hydrogen bromide, hydroiodic acid HI, phosphorous acid, formic acid and acetic acid.
In some embodiments, the present composition also comprises other trap-type polymerization retarders of at least one vinyl monomer (for example Acrylic Acid Monomer).In some embodiments, described other trap-type polymerization retarders are manganese salt, i.e. Mn (HCO
2 -)
2, Mn ((C
1-C
8) alkyl CO
2 -)
2, or potassium permanganate.In some embodiments, described manganese salt is used as inhibitor conditioning agent and the combination of described trap-type polymerization retarder in the method for described the second embodiment.In some embodiments, described manganese salt is Mn (HCO
2 -)
2.In some embodiments, described manganese salt is Mn ((C
1-C
8) alkyl CO
2 -)
2, be more preferably manganous acetate (II), comprise manganous acetate (II) (Mn (O
2cCH
3)
2) and manganous acetate (II) tetrahydrate (Mn (O
2cCH
3)
24H
2o).In some embodiments, described manganese salt is potassium permanganate.In some embodiments, described other trap-type polymerization retarders are quinhydrones.In some embodiments, described other trap-type polymerization retarders are second mixtures of thiodiphenylamine or molecular oxygen and thiodiphenylamine (or its second acid salt).Term " thiodiphenylamine " and " thiodiphenylamine itself " refer to the compound of following formula separately:
Described other trap-type polymerization retarders, in use, are used with the polymerization retardation significant quantity of its oneself independence.The polymerization retardation significant quantity of manganese salt, quinhydrones or thiodiphenylamine can for example, according to for example temperature and pressure, the existence or do not have other trap-type polymerization retarders and the amount of the inhibitor conditioning agent (if any) that exists changes of concrete vinyl monomer for example to be suppressed (Acrylic Acid Monomer) and amount thereof, condition.Those of ordinary skill in the art just can determine polymerization retardation significant quantity suitable under particular case by the test without excessive.The preferred polymerization retardation significant quantity of described manganese salt, quinhydrones or thiodiphenylamine is that about 5ppm is to about 500ppm independently, more preferably from about 10ppm is to about 250ppm, also more preferably from about 20ppm to about 200ppm, and even more preferably from about 40ppm to about 100ppm, all gross weight based on liquid mixture.
In some embodiments, the present composition also comprises the first mixture of N-oxycompound and manganese salt, and described manganese salt is Mn (HCO
2 -)
2, Mn ((C
1-C
8) alkyl CO
2 -)
2, or potassium permanganate.Term " N-oxycompound " refers to have structure fragment
chemical substance, wherein represent free radical (electronics) and each
represent the part with quaternary carbon atom covalent bonding.Preferably, described N-oxycompound is 2,2,5,5-tetramethyl--3-oxo-pyrrolidine-1-oxygen base; 2,2,6,6-tetramethyl piperidine-1-oxygen base; Three (2,2,6,6-tetramethyl piperidine-1-oxygen base-4-yl)-phosphorous acid ester; And, more preferably, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base.Term " 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base " and " 4-hydroxyl-TEMPO " are compounds synonym and that refer to separately following formula:
The present invention has also considered further to comprise the composition of the combination of any two or more aforementioned other trap-type polymerization retarders.
The polymerization retardation significant quantity of 4-hydroxyl-TEMPO can for example, according to for example temperature and pressure, the existence or do not have other trap-type polymerization retarders and the amount of the amount of the manganese salt that exists changes of concrete vinyl monomer for example to be suppressed (Acrylic Acid Monomer) and amount thereof, condition.Those of ordinary skill in the art just can determine polymerization retardation significant quantity suitable under particular case by the test without excessive.The N-oxycompound for example preferred polymerization retardation significant quantity of 4-hydroxyl-TEMPO is that about 5ppm is to about 500ppm, more preferably from about 10ppm is to about 250ppm, also more preferably from about 20ppm to about 200ppm, and even more preferably from about 40ppm to about 100ppm, all gross weight based on liquid mixture.
The present invention has also considered further to comprise the composition of inhibitor conditioning agent.The example of inhibitor conditioning agent be molecular oxygen and described manganese salt (for example, when not using other trap-type polymerization retarders or when the present composition, also comprise N-oxycompound (4-hydroxyl-2 for example, 2,6,6-tetramethyl piperidine-1-oxygen base) time).
As mentioned before, preferred described Acrylic Acid Monomer is the acrylic type monomer of formula (M).R wherein preferably
11to R
14one of be (C
1-C
8) alkyl, R
11to R
14in all the other are acrylic type monomers of the formula (M) of hydrogen.In some embodiments, R
11(C
1-C
18) alkyl.In some embodiments, R
11(C
9-C
18) alkyl.In some embodiments, R
11(C
1-C
8) alkyl.In some embodiments, R
11(C
1-C
8) alkyl and R
12to R
14each is hydrogen.In some embodiments, R
12(C
1-C
8) alkyl, and R
11, R
13and R
14each is hydrogen.In some embodiments, R
13(C
1-C
8) alkyl and R
11, R
12and R
14each is hydrogen.In some embodiments, R
14(C
1-C
8) alkyl and R
11to R
13each is hydrogen.In some embodiments, R
11to R
14each is hydrogen, that is, the acrylic type monomer of formula (M) is vinylformic acid itself.R wherein further preferably
11to R
14in two be (C
1-C
8) alkyl and R
11to R
14in all the other be in the acrylic type monomer of formula (M) of hydrogen.More preferably, R
11r
11to R
14middle conduct (C
1-C
8one of) two of alkyl.R wherein further preferably
11to R
14in three be (C
1-C
8) alkyl and R
11to R
14in all the other be in formula (M) the acrylic type monomer of hydrogen.Preferably, in the acrylic type monomer of formula (M), each (C
1-C
8) alkyl is all (C
1-C
3) alkyl, and more preferably methyl.
In some embodiments, the loss type polymerization retarder lacking in the present composition is the nitroso compound of formula (II):
wherein m is 1 to 3 integer, and each R
ahydrogen, (C independently
1-C
3) alkyl, (C
1-C
3) alkyl-O-, fluorine-based or chloro.
The loss type inhibitor that can be used for formula (I) in the present invention and compound (M), 4-hydroxyl-TEMPO, manganese salt, acid salt, inhibitor conditioning agent etc. and lack, comprises solvate, and described solvate comprises its hydrate.
In the method for described the second embodiment, vinyl monomer (for example Acrylic Acid Monomer) is exposed to polymerizing condition and therefore becomes and be easily aggregated (for example easily forming oligopolymer or homopolymer), and by trap-type polymerization retarder, suppresses any polymerization of retortable monomer in the inventive method.The example of polymerizing condition is to be exposed to polymerizing agent (for example oxygen, water or free radical or initiator) or condition (for example free radical formation condition is as ultraviolet ray or high-temperature zone).
The preferred method of described the second embodiment has been used preferred acrylic type monomer any of any of preferred acrylic type monomer polymerization inhibitor combination described herein and formula described herein (M).The another kind of the second embodiment has preferably been used formula described herein (M) preferably any two or more mixture of acrylic type monomer, for example mixture of vinylformic acid and ethyl propenoate or n-butyl acrylate.
Preferably, for example, in the method for the second embodiment of using vinyl monomer (Acrylic Acid Monomer) and trap-type polymerization retarder, described step is included in the pressure of the reduction that is less than 90kPa and is for example greater than, at 50 ℃ and the liquid mixture temperature (still kettle temperature) more preferably greater than the rising of 90 ℃ vaporization at least a portion vinyl monomer (for example Acrylic Acid Monomer).
In pilot plant or manufacturing environment, the container (for example still kettle or reactor) that holds the present composition is communicated with distillation tower fluid.Preferred distillation tower is the distillation tower that contains double fluid (dual flow) plate or tower tray.The example of this double-current tray-type column is described in and is numbered US7, in the United States Patent (USP) of 306,204B2.Preferably, distillation tower comprises bottom zone, intermediate zone and upper zone, and described liquid mixture and described district series fluid communication, and wherein said intermediate zone optionally limits opening for feed.In the method for described the second embodiment, preferably, during steady state operation, the liquid mixture temperature of the temperature of bottom zone and rising differs within the scope of approximately 5 ℃ and the pressure reducing in the pressure of the reduction in top region and bottom zone differs within the scope of about 30kPa.In order to illustrate, during steady state operation, production-scale double-current 40-tower disc type tower is characterized as approximately 111 ℃ of in its bottom zone temperature and the pressure that reduces is about 35kPa, the about 21kPa of pressure of approximately 46 ℃ of temperature and reduction in its top region, in its intermediate zone, temperature is approximately 56 ℃.
The present invention has considered batch-wise (disposable interpolation vinyl monomer (for example Acrylic Acid Monomer)) and continuous (continuous adding or repeatedly separately add vinyl monomer (for example Acrylic Acid Monomer)) for the container that holds the present composition.In method, especially continuation method in batches or continuously, preferably for example, to the vinyl monomer (Acrylic Acid Monomer) in container, add the trap-type polymerization retarder of one or more extra polymerization retardation significant quantities.For example, for example, in using the continuation method of distil container (still kettle) and tower, can for example, to the distil container that holds vinyl monomer (Acrylic Acid Monomer), add such a or a plurality of extra polymerization retardation significant quantity, so that the loss part when replacing described trap-type polymerization retarder and reacting in distil container.Add trap-type polymerization retarder and comprise independently continuously or repeatedly separately add, and can for example add funnel or have the feeding line of valve to complete by conventional means.
Material: vinylformic acid, thiodiphenylamine, 4-hydroxyl-TEMPO and much manganese salt can be purchased from each supplier, and described supplier comprises Sigma-Aldrich Company, St.Louis, Missouri, USA.
Preparation 1: synthetic N-benzyl thiodiphenylamine (1)
Preparation 2: synthetic N-(1-styroyl)-thiodiphenylamine (2)
except using (1-monobromethane) benzene replacement bromotoluene, in preparation 1 similar program, preparation N-(1-styroyl)-thiodiphenylamine.Utilize normal hexane: the solvent mixture of ethyl acetate (50:1), as elutriant, by column chromatography on neutral alumina, carrys out purified product.Evaporating solvent produces N-(1-styroyl)-thiodiphenylamine, is white solid, and yield is 65%.
1h NMR spectrum is consistent with N-(1-styroyl)-thiodiphenylamine.
1H?NMR(CDCl
3)(ppm)：7.30-7.45(m，5H，
Ar-CH-)；7.14(d，2H，J=7.5Hz，
Ar-PTZ)；6.85-7.05(m，4H，
Ar-PTZ)；6.74(d，2H，J=7.0Hz，
Ar-PTZ)；5.42(q，1H，Ar-
CH-CH
3)；1.98(d，3H，J=7.0Hz，CH-
CH 3 )。
Some embodiments of the present invention are described in the following embodiments in more detail.
Embodiment 1 and 2: the composition of vinylformic acid and compound (1) or (2)
At two independently in bottle, by 5 milliliters of (mL) vinylformic acid and a certain amount of compound (1) or mixing (2) (preparing 1 or 2), described compound amount is enough to produce the mixture with 100ppm trap-type polymerization retarder, and described mixture is respectively the composition of embodiment 1 or 2.Embodiment 1 and 2 composition especially can be used for suppressing acrylic acid polymerization.Repeat again embodiment 1 and 2 four times, to obtain 5 bottles of embodiment 1 and 2.
Embodiment 3 and 4: suppress acrylic acid polymerization with compound (1) or (2)
In embodiment 3, sealed vial also heats the composition of embodiment 1, and in embodiment 4, and sealed vial also heats the composition of embodiment 2, all 113 degrees Celsius (℃) under, and record the time that occurs first variable density (gel formation) in composition.At five, independently in bottle, heat non-comparative composition of the present invention, it comprises 5mL vinylformic acid and 100ppm thiodiphenylamine itself (PTZ), and the time of recording equally gel formation.Embodiment 3 and 4 and comparative example move altogether separately 5 times.The gel formation time scope of embodiment 3 was from 81 hours to 97 hours; Embodiment 4 from 94 to 99 hours; Comparative example PTZ was from 31 hours to 34 hours.Average result report in the following Table 1.
Table 1: gel formation time
| No. embodiment | No. embodiment, composition | Average gel formation time (hour) |
| 3 | 1 | 85 |
| 4 | 2 | 97 |
| Comparative example | PTZ | 33 |
As above-mentioned data presentation, the collaborative polymerization that has suppressed vinyl monomer (for example Acrylic Acid Monomer) of the present composition, and especially can manufacture in for example container and pipeline, purifying, processing and storage Acrylic Acid Monomer, especially during acrylic type monomer as the polymerization retarder of described Acrylic Acid Monomer.
Claims (8)
1. polymerization of vinyl monomer inhibitor combination, the liquid mixture that it comprises the trap-type polymerization retarder that contains vinyl monomer and polymerization retardation significant quantity, wherein said composition lacks the loss type polymerization retarder of polymerization of vinyl monomer, and described trap-type polymerization retarder be characterised in that can be independently as the collaborative effective inhibitor of polymerization of vinyl monomer, and the polymerization of described vinyl monomer is by the collaborative inhibition of described trap-type polymerization retarder, and wherein said trap-type polymerization retarder is the compound of formula (I), or its first acid salt:
2. the composition of claim 1, wherein said vinyl monomer is the acrylic type monomer of formula (M):
r wherein
11hydrogen or (C
1-C
18) alkyl and R
12to R
14hydrogen or (C independently of one another
1-C
8) alkyl.
3. claim 1 or 2 composition, wherein R
1hydrogen.
4. claim 1 or 2 composition, wherein R
1(C
1-C
3) alkyl.
5. claim 1 or 2 composition, wherein said trap-type polymerization retarder is N-benzyl-thiodiphenylamine, N-(1-styroyl) thiodiphenylamine or its first acid salt.
6. the composition of claim 5, wherein said trap-type polymerization retarder is N-benzyl-thiodiphenylamine or N-(1-styroyl) thiodiphenylamine.
7. the composition of aforementioned claim any one, wherein said composition also comprises: (a) manganese salt, described manganese salt is Mn (HCO
2 -)
2, Mn ((C
1-C
8) alkyl CO
2 -)
2, or potassium permanganate; (b) the first mixture of N-oxycompound and manganese salt, described manganese salt is Mn (HCO
2 -)
2, Mn ((C
1-C
8) alkyl CO
2 -)
2, or potassium permanganate; (c) quinhydrones; (d) the second mixture of molecular oxygen and thiodiphenylamine or its second acid salt, or the combination of any two or more trap-type polymerization retarders of (a) to (d) (e) above.
8. the method for collaborative ethene suppressing base monomer polymerization, described method comprises the trap-type polymerization retarder of vinyl monomer and polymerization retardation significant quantity is contacted, thus generation is as the polymerization retarder composition in claim 1 to 7 any one.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161450734P | 2011-03-09 | 2011-03-09 | |
| US61/450,734 | 2011-03-09 | ||
| PCT/US2012/024936 WO2012121836A1 (en) | 2011-03-09 | 2012-02-14 | Synergistic polymerization inhibitor composition and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103582655A true CN103582655A (en) | 2014-02-12 |
Family
ID=45757217
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280012225.8A Pending CN103582655A (en) | 2011-03-09 | 2012-02-14 | Synergistic polymerization inhibitor composition and method |
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| Country | Link |
|---|---|
| EP (1) | EP2683748A1 (en) |
| JP (1) | JP2014507547A (en) |
| KR (1) | KR20140012122A (en) |
| CN (1) | CN103582655A (en) |
| BR (1) | BR112013022992A2 (en) |
| MX (1) | MX2013010259A (en) |
| SG (1) | SG192979A1 (en) |
| TW (1) | TW201242957A (en) |
| WO (1) | WO2012121836A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020037656A1 (en) * | 2018-08-24 | 2020-02-27 | Bl Technologies, Inc. | Synergistic combination for inhibiting polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016007306A1 (en) | 2014-07-07 | 2016-01-14 | Dow Global Technologies Llc | Extractive dehydration process |
| CN104864266B (en) * | 2015-05-07 | 2017-11-17 | 中国海洋石油总公司 | A kind of unimolecule hydrate inhibitor |
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| CN1762965A (en) * | 2004-10-01 | 2006-04-26 | 罗门哈斯公司 | A method for inhibiting polymerization of (meth) acrylic acid and its esters using an inhibitor and a process for making a compound useful as such an inhibitor |
| CN101273049A (en) * | 2005-08-19 | 2008-09-24 | 陶氏康宁东丽株式会社 | A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group |
| CN101351449A (en) * | 2005-12-27 | 2009-01-21 | 株式会社Adeka | Nitroxyl compound, and polymerization inhibitor and polymerization inhibitor composition using same |
| WO2010096512A1 (en) * | 2009-02-18 | 2010-08-26 | Dow Global Technologies Inc. | Polymerization inhibitor composition and method of inhibiting polymerization of distillable monomers |
| CN101878190A (en) * | 2007-08-31 | 2010-11-03 | 阿科玛股份有限公司 | The method that in vinylformic acid and acrylate processes, suppresses polymerization and fouling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10156988A1 (en) | 2001-11-21 | 2003-05-28 | Basf Ag | Column for the thermal treatment of polymerizable mixture, e.g. (meth)acrolein, has dual-flow stages characterized in that stages at an increasing distance from the addition point of the gases have openings of decreasing diameter |
-
2012
- 2012-02-14 WO PCT/US2012/024936 patent/WO2012121836A1/en active Application Filing
- 2012-02-14 JP JP2013557726A patent/JP2014507547A/en active Pending
- 2012-02-14 SG SG2013064969A patent/SG192979A1/en unknown
- 2012-02-14 EP EP12705754.5A patent/EP2683748A1/en not_active Withdrawn
- 2012-02-14 CN CN201280012225.8A patent/CN103582655A/en active Pending
- 2012-02-14 KR KR1020137026379A patent/KR20140012122A/en not_active Application Discontinuation
- 2012-02-14 BR BR112013022992A patent/BR112013022992A2/en not_active IP Right Cessation
- 2012-02-14 MX MX2013010259A patent/MX2013010259A/en unknown
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762965A (en) * | 2004-10-01 | 2006-04-26 | 罗门哈斯公司 | A method for inhibiting polymerization of (meth) acrylic acid and its esters using an inhibitor and a process for making a compound useful as such an inhibitor |
| CN101273049A (en) * | 2005-08-19 | 2008-09-24 | 陶氏康宁东丽株式会社 | A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group |
| CN101351449A (en) * | 2005-12-27 | 2009-01-21 | 株式会社Adeka | Nitroxyl compound, and polymerization inhibitor and polymerization inhibitor composition using same |
| CN101878190A (en) * | 2007-08-31 | 2010-11-03 | 阿科玛股份有限公司 | The method that in vinylformic acid and acrylate processes, suppresses polymerization and fouling |
| WO2010096512A1 (en) * | 2009-02-18 | 2010-08-26 | Dow Global Technologies Inc. | Polymerization inhibitor composition and method of inhibiting polymerization of distillable monomers |
Cited By (1)
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| WO2020037656A1 (en) * | 2018-08-24 | 2020-02-27 | Bl Technologies, Inc. | Synergistic combination for inhibiting polymerization |
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| Publication number | Publication date |
|---|---|
| KR20140012122A (en) | 2014-01-29 |
| WO2012121836A1 (en) | 2012-09-13 |
| SG192979A1 (en) | 2013-09-30 |
| EP2683748A1 (en) | 2014-01-15 |
| BR112013022992A2 (en) | 2016-12-06 |
| JP2014507547A (en) | 2014-03-27 |
| MX2013010259A (en) | 2014-12-04 |
| TW201242957A (en) | 2012-11-01 |
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