TW201242957A - Synergistic polymerization inhibitor composition and method - Google Patents

Abstract

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

201242957 VI. Description of the invention: [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to Provisional Application No. 61/450,734, filed on March 29, 2011, which is hereby incorporated by reference in its entirety. TECHNICAL FIELD The present invention relates to a vinyl monomer polymerization inhibitor composition and a method for inhibiting polymerization of a vinyl monomer. [Prior Art] Ethylene monomers include ethylene glycol and g and acrylic monomers. Ethylene monomers are widely used in the chemical industry. For example, acrylic monomers can be used to prepare polyacrylate type polymers (eg, poly(acrylic acid) and poly(methacrylic acid)), which are especially useful as additives (eg, in rubbers, coatings, and adhesives). ) and the ingredients in fibers and other items. The presence of a vinyl monomer is a premature aggregation. In the absence of sufficient polymerization inhibitors, the ethylene monomer will undesirably polymerize during the manufacturing, purification, handling, and storage operations. The only solution to this problem is mentioned in W〇201_12ai. The I patent is about containing trapping polymerization inhibitors and short-acting. Monomer polymerization inhibitor group of inhibitors ^ ^ ^ ^ product. The synergistic effect of the polymerization inhibitor is that the oyster sauce and the steamable monomer are twisted from the first position (for example, the distillation pot) and the distillable monomer, and the position (for example, in the distillation) In the tower) condensation. The problems solved by the present invention include a composition in which an I6 a rib is supplied to a vinyl monomer polymerization inhibitor, which contains a suppressing ethylene-based single-handed person #1 , ^ ^ . The inhibition is unexpectedly superior to the inhibition of the polymerization of the thiophene, and wherein 201242957 the composition lacks a short-acting polymerization inhibitor of the ethyl group monomer. SUMMARY OF THE INVENTION In the first specific example, the present invention provides a vinyl monomer polymerization inhibitor composition comprising a liquid mixture containing an inhibitor of an effective amount of an inhibitor of an effective amount of a polymerization inhibitor. The composition lacks a ethylene single-effect polymerization inhibitor' and capture-type polymerization: independently a synergistic effective inhibitor of ethylene monomer polymerization, and the polymerization of the ethylene-based precursor is synergistically inhibited by the capture polymerization inhibitor And the t-type polymerization inhibitor is a compound of formula (I):

(I), or its first acid addition salt, of which (CVC3) is based. Ί R is 虱 or in some aspects of the first specific example, the monomer of the formula (M), the acrylic acid type single system is an acrylic acid

A# r12 t , wherein R" is hydrogen or (18), and R to R are each independently argon or (C^c, 8). In a second embodiment, the present invention provides a method for synergistically inhibiting polymerization of a monomer. The method comprises contacting an ethylenic monomer with a polymerization inhibiting effective amount of a capture polymerization inhibitor to obtain a 丄 & To the composition of the present invention. The composition of the present invention is a composition which can be in the second embodiment of * ιτι. The compositions of the present invention are useful, for example, in containers (such as steamed steel, storage containers, and shipping containers) in the manufacture, purification, processing, and storage of vinyl precursors (e.g., 201242957 vinyl alcohol and vinegar and acrylic monomers). A polymerization inhibitor of a vinyl monomer. Other specific examples are described in the remainder of the description. [Embodiment] Specific examples of the invention as outlined in the foregoing and in the Abstract are incorporated herein by reference. The term "vinyl monomer" as used herein means a molecule containing the structural fragment h2C=C(h)- and having a molecular weight of less than 1'〇〇〇g/mole (g/mol). The term "acrylic monomer (acryHc 'Τι /? c C=C - C - m〇nomer)" means a vinyl monomer having a structural fragment %, wherein '^ represents a moiety having a covalent bond. The term "captive p〇lymerization inhibh〇r" means a substance which does not evaporate from the distillation pot during the distillation of an ethylene monomer (e.g., an acrylic monomer) from a distillation pot. The term "fugitive p〇lymed zati〇n inhibitor" means a substance which is capable of evaporating and condensing with acrylic acid in a polymerization inhibiting amount. The term "inhibit" means delaying the initiation, reducing the extent of the suppressed event or preferably preventing the suppressed event. The phrase "synergistica Uy effeetive inhibit 〇 r polymerization" means preventing the appearance of solid poly (vinyl monomer) (eg poly (acrylic monomer)) at least, 7 〇, average The time value of the substance 'which is about twice the average time value available for the well D itself. The first room is determined by the following procedure: sealing a liquid mixture containing a vinyl monomer (for example, a propionic acid monomer) and 100 ppm of the substance or 100, which is only a long time ζυ ppm 6 6 201242957 formulation regulator (as a liquid mixture) Total weight) glass vial. The vial was placed in a mineral oil bath at 113 t. Record the time at which the solid poly(ethylene monomer > (eg poly(acrylic acid)) is visually present at any position of the vial (ie, in the liquid mixture or above the liquid mixture). 4 times. On average, five times, the average time value is obtained. The term "inhibit 〇rm〇difier j" means a substance (such as a manganese salt) in which a derivative of a compound is produced or regenerated. "Lack" and its similar forms (such as lack of (丨"匕%)) means that it does not exist at all. The term "effectiveness of polymerization inhibition ((4)") means that the substance is sufficient to delay the polymerization. Initiating, reducing the extent or preferably preventing the absolute weight of the polymerization (for example, in grams of juice) or relative weight (for example, expressed in parts per million (ppm) or weight percent (wt%). ___(10)k synefgistically inhibited ) and its like means that if the polymerizable monomer is violent in the polymerization conditions (the chemistry of bonding two or more polymerizable monomer molecules to produce its organic S-polymer or polymer) Process) The contact of the S彳 polymer monomer with the capture polymerization inhibitor is then the rate of the chemical process is significantly lower than the rate of the chemical process in the presence of the control inhibitor, the thiophene D well. Contradictory solution: incorporated by reference In the event of any conflict between the written content of the patent, the patent application or the patent application disclosure or its part and the written content in this manual, the written content in this manual shall prevail. Any conflict between the name and structure of the object In the case of any conflict between the unit value of the international system (SI) and the unit value of the non-international system, 'in any non-international system unit value. In the written description of the pattern 201242957 In the event of any conflict, the following is a preferred embodiment or a specific example of any defined lower limit of any lower limit or range of values, which may be combined with any upper limit or any preferred upper limit of the range. Unless otherwise stated, '''''''''''''''''''''' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' T0 5 )" includes, for example, !, 1, 5, 2, 2.75, 3, 3.81, 4, and 5). "(Ci-C|8)alkyl" ((Ci-Ci8)alkyl)" An example of an unsubstituted saturated linear or branched hydrocarbon "Cl_Cl8" alkyl group of 18 carbon atoms is ((VCi8)alkyl (eg (Cu)alkyl, such as CH3(CH2)I7_) and (kC8)) The base 'includes (CiA) alkyl, including methyl, ethyl, phenyl and 2-propyl, and (c4_c8), including ! butyl (also known as n-butyl), 2-butyl, 2 Methyl propyl, methyl ethyl, i. pentyl, hexyl 1 heptyl and 1-octyl. The term "(CVC3) yard base-0_" means a (Cl_c3) alkyl group bonded to an oxygen atom group. The trapping polymerization inhibitor is particularly useful for inhibiting the polymerization of a vinylic mono H (e.g., acrylic acid monomer) in a distillation vessel (pot), storage vessel, or piping (e.g., piping and piping). The polymerization inhibiting effective amount of the trapping polymerization inhibitor can be, for example, the presence or absence of a specific ethylenic monomer (for example, an acrylic monomer) and its inhibition amount, 14 (such as temperature and pressure), and other trapping polymerization inhibitors. And change. The process of the present invention can be initiated using A in an amount effective to inhibit polymerization which is considered to be a necessary amount. Thereafter, 1 reduces the effective amount of polymerization inhibition (eg, during polymerization inhibitor reaction) i to obtain a suitable steady state amount of polymerization inhibitor 8 201242957 (eg, by achieving the desired technique between container cleaning) Can be in a specific situation:: 2. Confirmation). - Generally inhibit the effective amount. Formula (n=eight catches), over-tested to determine proper poly(). The preferred _ is about - to about 500 ppm, the first is effective. - 4 is about 10 ppm to about A. 250 ppm, more preferably from about 20 ppm to about 2 〇〇m, even more preferably from about 40 ppm to about (10) ppm, based on the total weight of the liquid mixture. The capture polymerization inhibitor does not include a derivative of the body. Ethylene steroids (eg, acrylic acid in some specific examples, the capture polymerization inhibitor is a compound of formula (1) wherein R1 is hydrogen. In some specific examples t, RU (Ci_C. In some embodiments, ' Ri It is an ethyl group, a propyl group or a 2-propyl group, and more preferably a fluorenyl group. In some embodiments, the compound is a benzoquinone-morphothionium well, in other embodiments, a ^(1) _Phenylethyl) thiophene, and in other specific examples 'as its first acid addition salt. The synthesis of the compound of formula (I) is not critical to the invention and covers all successful synthesis methods. In some specific examples In the above, the compound of the formula (1) is synthesized by alkylating the corresponding intermediate amino compound of the formula (IA) as shown in Scheme 1 below.

9 201242957 wherein R is as described for formula (1) and LG is a leaving group. In the process of: in the presence of a non-nucleophilic strong base and an aprotic solvent at a nucleophilic displacement temperature, preferably about 1:1 to about, the amine compound of formula (IA) and a formula having a leaving group (IB) contacting the compound to give a compound of formula (1). Examples of aprotic solvents are tetrahydrofuran, 1,2-dimethoxyethane and dioxane. Examples of non-nucleophilic bases are sodium hydride, potassium hydride, potassium hexamethyldioxane (KHMDS) and lithium diisopropylamide (LDA). Examples of leaving groups are iodine, bromine, gas, activated hydroxyl groups, trifluoromethanesulfonate, trifluoroacetate and toluenesulfonate. In some embodiments, the activated hydroxyl groups are from a compound of formula (IB) wherein LG is HO- and a coupling agent such as triphenylphosphine in diisopropyl azodicarboxylate (DIAD), 1- (3-Didecylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC, EDCI or EDAC), N,N'-carbonyldiimidazole (CDI) or hydrazine, Ν'-bicyclic In the presence of hexylcarbodiimide (DCC) and optionally in 1-meridyl and tris(HOBt); and hexampampic acid (benzotriazol-1-yloxy)tripyrrolidinyl-indole Prepared under. Other synthetic methods for compounds of formula (I) are contemplated. For example, when r 1 is hydrogen, the compound of formula (I) can be obtained by reacting a compound of formula (IA) with a halo-C(= 〇)-phenyl acid halide or a phenyl-C (= 0)-0-C(=0)-Phenyl acid liver coupling synthesis 'Get the end of formula (1C) (penultimate) Rebellion 201242957

(1C) Domain. The carboxamide of the formula (IC) can then be reduced (e.g., a solution of the tetrahydrofuran) to give a compound of the formula (I) wherein R1 is hydrazine. The invention further encompasses the use of acid addition salts of the compounds of formula (1). The term "acidadditionsal" means an ionic substance f comprising an organic cation and an organic or preferably inorganic anion. The organic cation comprises a protein or a protonated form of a compound of the formula (1). The anion comprises an organic or a preferred machine. a compound having at least one proton having a characteristic A pKa of less than 7 (ie, a residue of Bronsted acid preferably having an acidity of iLa 0.9 to 1.1 molar equivalents of a single proton Browns Polyacid, 〇45 to 〇·55 molar equivalent of the double proton Bronsted acid or 0 3 纟m molar equivalent of the three proton Bronsted acid, all of which are thiophene or formula (1) = Preferably, the Bronsted acid comprises hydrochloric acid, nitric acid, phosphoric acid, sulphuric acid, hydrobromic acid, hydrostatic acid, phosphoric acid, formic acid and acetic acid. In some embodiments, the composition of the present invention further comprises an ethylene monomer. At least one other capture-type polymerization inhibitor of a body (eg, an acrylic monomer). In some embodiments, other capture-type polymerization inhibitors are aggressive, =Mn(Hc〇2-)2, Mn((Ci.C8) Burning base c〇2.) 2 or high clock acid / in some specific examples The manganese salt is combined with the trapping polymerization inhibitor for use in the method of the second specific example as an inhibitor. In the specific example: in the 'manganese salt 4 Mn(HC02-)2» in some specific examples, the manganese salt For] 201242957

MnGCVCd is based on (:02·)2, and p 4 u is more preferably manganese (II) acetate, including manganese (II) acetate (Mn(02CCH3)2) and ethane group, ττ, 酉夂 chain (II) Tetrahydrate (Mn(〇2CCH3)2.4H2〇). In some specific examples, the sulphate is unloaded with high acid. In some specific examples, "his capture polymerization inhibitor is (4) 4 - & (4) (d)", the other capture polymerization inhibitor is a second mixture of thiophene or molecular oxygen and morphine or its second acid addition salt. . The proverb "Ph_hiazine" and "Ping 嗔 井 井 ” ( ( 〇 _ 自身 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各 各

Other capture polymerization inhibitors are used in their own independent polymerization inhibiting effective amounts. The polymerization inhibiting effective amount of the manganese salt, hydroquinone or thiophene well can be, for example, a specific ethylenic monomer (for example, an acrylic monomer) and its inhibiting amount, conditions (such as temperature and pressure), and other trapping polymerization inhibitors. The presence or absence and the amount of inhibitor modulator, if any, will vary. Persons of ordinary skill should be able to determine the appropriate effective amount of inhibition in a particular situation without undue experimentation. The preferred polymerization inhibiting effective amount of manganese salt, hydroquinone or morphine is independently from about 5 ppm to about 5 GG P (four), more preferably from about 1 G PPm to about 250 PPm', more preferably from about 20 ppm to about 2 ppm. 'And even more preferably from about ppm to about 1 〇〇 ppm, all based on the total weight of the liquid mixture. In some embodiments, the composition of the present invention further comprises a Mnoxy compound and a manganese salt which is Mn(HC〇2-)2, Mn((Ci_C8)alkyl C(V)2 or high short acid 12 201242957 potassium. The first mixture. The term "r__xyl compound" means a chemical substance having a % structural fragment, wherein · represents a radical (electron) and each $ represents a bond to a quaternary carbon a part of a covalent bond of an atom. The N-oxyl compound is preferably 2,2,5,5-tetramethyl_3_sideoxypyrrolidin-1-yl; 2,2,6,6-tetra Methylpiperidine-1-oxyl; ginseng (2 2 6 6 tetramethylpiperidin-1-yloxy-4-yl)-phosphite; and more preferably 4-hydroxy-2,2,6, 6_ Tetramethylpiperidin-1-yloxy. The term "4. hydroxy-2,2,6,6-tetramethylpiperidine-oxyl (4-hydroxy-2,2,6,6-tetramethylpiperidine- L-〇xyi)" and 4-hydroxy-TEMPO (4-hydroxy-TEMPO) are synonymous and each means a compound of the formula:

The step contains any two or more of the above, wherein • represents a radical (electron). The invention further encompasses compositions further comprising a combination of any two or other capture-type polymerization inhibitors.

The polymerization inhibiting effective amount of 4-hydroxy-TEMPO can be, for example, a specific monomer) and its inhibitory amount, a barley monomer (for example, an acrylic monomer) and its inhibition amount, and pressure), and other trap polymerization inhibitors. Existence or stress), conditions (such as temperature • or non-existence and the presence of X salt in a given situation). _. General technology should be able to be in a specific situation

The total weight of the π-V μ bottle. 5 13 201242957 Another example of further inclusion of inhibitor inhibitors in this month is molecular oxygen and fibrin. He captures polymerization inhibition _ or when the present invention is silk-in, /;

., ^ base,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Soap body. Preferably, the acrylic type 勹艽(Μ) acrylic type monomer of the formula f _ ( Μ ), wherein one of the four is (C|-C8) burns a BD 1丨 to R " sinking base and R丨丨In the example of Rl4, R丨丨 is (, 'for the wind. In some specific two (q-cu) alkyl groups. In a peptide and the voice is a gentleman's clan (c9-ca base. In _-/, In the examples, R11 is a two specific example, Rn is (Ci. in some specific examples, RnA 8) alkyl. In the case of (C,-C8)alkyl and R丨2 to rI4 In some specific examples, rI2 Each is hydrogen. It is (Ci-C8)alkyl and RU, 丨3 and |4 are hydrogen. In some specific sound positions R each rI4, , , R *(C|_C8) alkyl and R1!, R12 And in each specific example, rm is (c , , r r13 4 .. horse (l|-C8) alkyl and Rii is WW. In a specific example, Rn to R14 are each hydrogen, that is, The acrylic type i._ of the formula (Μ) is acrylic itself. It is also preferably a formula (Μ)

Acrylic monomer, wherein rU

Two of Rn 5 dI4 to R are (Κ8)alkyl and the remainder to Ru is hydrogen. R, · is more preferably as the (Cl_c8) alkyl group R11. Also preferred is an acrylic monomer of the formula (M), wherein R 丨丨 to r 丨 4 Φ 夕 土 土 又 又 又 二者 二者 二者 二者 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且In the acrylic acid-type monomer of M), a preferred (Ci-Cs) alkyl group is (Ci-C: 3) alkyl group, and more preferably a methyl group. In two specific examples, the short-acting polymerization inhibitor lacking in the composition of the present invention is an anthracene compound of the formula (Π): 201242957

(RA) mt J (Π) 'where m is i to 3 棼 helmet is nitrogen, (CVC3) yard base, (Cl_C3) yard base · 〇 = each C is independently applicable to the formula (1) and formula (M) of the present invention Chemicals: TM-, "acid addition salts, inhibition::, base inhibitors include solvates (including hydrates). and lack of short-acting in the method of the second specific example, monomer) exposure Under polymerization conditions and thus become easy; (:; such as acrylic acid into oligomers or homopolymers), and the present invention: (for example, easy shape polymerization is inhibited by a trapping polymerization inhibitor. Any of the polymonomers a polymerization agent (for example, oxygen, water or a radical free radical generating condition such as ultraviolet light or a high temperature region). For example, a preferred method of the specific example uses the olefinic type monomer polymerization inhibitor composition described herein and the article Any of the (M) acrylic acid type monomers. The second embodiment of the preferred embodiment uses: any of the preferred formula (M) of the acrylic acid type monomers described above. a mixture such as a mixture of acrylic acid and acetoacetate or propylene glycol. t using ethylene monomer (such as acrylic acid monomer) and trapping In the method of the second embodiment of the type polymerization inhibitor, the step preferably comprises a pressure reduction of less than 卯 kPa and a liquid mixture (for example, a distillation pot temperature) of more than it and more preferably more than 90. (: at least some of the evaporation at high temperatures A monomer (e.g., an acrylic monomer). In a test plant or manufacturing environment, a container 15 201242957 (e.g., a distillation pot or reactor) containing the composition of the present invention is in fluid communication with a distillation column. Preferably, the distillation column contains a double stream. A distillation column of a plate or a double-flow plate. An example of the two-flow tray is described in U.S. Patent No. 7,3,6,2,4, B2. The steaming tower preferably comprises: a section, a middle zone and a top zone. And the liquid mixture is in fluid communication with the I region, the intermediate region and the top region in sequence, wherein the intermediate region defines the feed inlet as appropriate. In the method of the second embodiment, preferably the temperature in the bottom region during the steady operation In the vicinity of the high temperature of the liquid mixture, and the top region is depressurized in the bottom region for about 3 Torr. For purposes of illustration, during steady state operation, the manufacturing grade double (d) The characteristics of a are: in the bottom region, the temperature is about (1) t and the pressure is about ^ a' in the top region, the temperature is about 46 t and the decompression is about m in the middle region, the temperature is about 56. The invention covers batchwise addition to a container containing the composition of the invention (early-human addition of a vinyl monomer (for example, acrylic monomer)) continued addition or multi-female 2, 丨法* y bite only hard (Lianyi Duo-People's Knife is added with vinyl monomer (for example, in batch or continuous m, continuous μ/monomer)). The ethylenic monofluorene is added to the acrylic acid in the container. In the process of adding or containing a polymerization efficiency to a trapping polymerization inhibitor. For example, in a continuous process such as a distillation pot and a column, "', and the arsenal (the effective amount of the sample can be suspected to contain A la toe/or a long-term addition of a polymerization inhibitor is added by a monomer (for example, an acrylic monomer) to replace the loss of the distillation vessel in the distillation vessel. ^. Adding capture-type polymerization is added several times separately and can be carried out by a conventional "3 continuous gate feed line." 4 such as Jiake funnel or valve-containing 201242957 Material: Acrylic acid, thiophene d well, 4-hydroxy- TEMPO and a variety of salt can be purchased from a variety of suppliers, including Sigma-Aldrich, st. Louis.

Add a solution of g gram (g; 0·01 mol (m〇l)) morphine p-α well to 1 〇ml (paw [) anhydrous tetrahydrofuran (THF) to j 〇g sodium hydride (NaH; 〇〇42 mol) In a suspension in 20 mL of anhydrous THF (NaH was previously obtained by washing NaH in EtOAc EtOAc EtOAc EtOAc). The mixture was stirred for 4 hours or until hydrogen gas was released and the color of the mixture turned orange. Then 2 mL (〇 〇 17 m〇i) phenylhydrazine bromide was slowly added to the orange mixture at room temperature and the resulting mixture was stirred overnight. The mixture was heated to 6 Torr and maintained for a few hours. The color of the board faded. The reaction mixture which was acidified to pH 用 with concentrated hydrochloric acid was poured into ice water. The resulting aqueous mixture was extracted with ethyl acetate, dehydrated over anhydrous sulphuric acid and solvent was removed in vacuo. The resulting extract residue was purified by neutral alumina column chromatography eluting with a solvent mixture of n-hexane: acetonitrile (50:1). The solvent was evaporated and the residue was recrystallized from ethanol to give 2 g (yield: 6% yield) of N. benzylmorpholine D. The 1H NMR spectrum is compared with the pure N-benzyl group 0 ° ° plug B well β 1 ττ '

H NMR (CDC13) (ppm): 7.25-7.40 (m 5HV 7.11 (d, 2H /=7 cr ’ '

.Hz); 7.00 (t, 2H, J~ 8.0 Hz); 6.88 ft 2H ^7-5HZ); 6.67 (dj 2H5,= s.0HZ); 5.12(s52H)〇' Preparation 2: Synthesis of N-(i -Phenylethyl)·Synthesis (2) (2) 201242957

. The Ν-(ι_phenylethyl)-morphothionium well was prepared in a procedure similar to that of Preparation 1, but using (1-bromoethyl)benzene instead of benzyl bromide. The product was purified by neutral alumina column chromatography using a solvent mixture of n-hexane: ethyl acetate (5 〇: 丨) as an eluent. Evaporation of the solvent gave N-(l-phenylethyl)- phenoxythiophene as a white solid. The iH NMR spectrum was consistent with N-(l-phenylethyl)-morphothiophene. iHNMR (CDC13) (ppm): 7.30-7.45 (m, 5H, Ar-CH-); 7.14 (d, 2H, J = 7.5 Hz, Ar-PTZ); 6.85-7.05 (m, 4H, Ar-PTZ) ; 6.74 (d, 2H, J = 7.0 Hz, Ar-PTZ); 5.42 (q, 1H, Ar-CH-CH3); 1.98 (d, 3H, J = 7.0 Hz, CH-CHO. More in the following examples) DETAILED DESCRIPTION OF THE INVENTION Some specific examples of the invention e Example 1 and Example 2: Acrylic acid and the composition of compound (1) or compound (2). In two separate vials, 5 ml (mL) of acrylic acid was mixed with Compound (1) or compound (2) (Preparation 1 or 2) in an amount sufficient to produce a mixture of 100 ppm of a capture polymerization inhibitor, the mixture being the composition of Example 1 or 2, respectively. Example 1 and Example 2 The composition is particularly suitable for inhibiting the polymerization of acrylic acid. The first embodiment and the second embodiment were repeated four times to obtain five vials of Example 1 and Example 2. Example 3 and Example 4: inhibition of acrylic acid and compound (丨) Or the polymerization of compound (2). For Example 3 'sealing the vial and heating the composition of Example 1, and for Example 4, sealing the vial and heating the composition of Example 2, both at 18 201242957 113 (°C), and record the time of the first density change (gel formation) in the composition. In 5 separate vials, heat contains 5 mL of acrylic acid and 100 ppm of morphine D well itself (PTZ It is not the comparative composition of the present invention and the time of gel formation is also recorded. For each of Example 3 and Example 4 and the comparative example, a total of 5 operations were performed. The gel formation time of Example 3 was 81 hours. Within the range of 97 hours; Example 4 is in the range of 94 to 99 hours; and the control PTZ is in the range of 31 hours to 34 hours. The average results are reported in Table 1. Table 1: Time of gel formation

As shown by the above data, the composition of the present invention synergistically inhibits the polymerization of vinylic monomers (e.g., acrylic acid monomers), and in particular, the manufacture, purification, processing, and storage of acrylic acid monomers, especially C-type monomers. It is suitable, for example, as a polymerization inhibitor for acrylic monomers in containers and pipes. . [Simple diagram description] None [Main component symbol description] None 19

Claims (1)

201242957 VII. Patent application scope: 1_ A vinyl monomer polymerization inhibitor composition comprising a liquid mixture containing a vinyl monomer and a polymerization inhibiting effective amount of a trap polymerization inhibitor, wherein the composition lacks the vinyl series a short-acting polymerization inhibitor of bulk polymerization, and the property of the S-capture-type polymerization inhibitor is independently a synergistic effective inhibitor of the polymerization of the ethylene-based monomer and the polymerization of the vinyl-based monomer is inhibited by the capture-type polymerization Agent synergistic inhibition, and wherein the capture polymerization inhibitor is a compound of formula (I): Or a first acid addition salt thereof, wherein R1 hydrogen or (Ci-CO alkyl group. 2. The composition of claim 1 wherein the ethylenic monomer is an acrylic monomer of formula (M) R13 0 (Μ) wherein R11 is hydrogen or alkyl, and R12 to R14 are each independently hydrogen or (Ci_C8)alkyl. 3. The composition of claim 1 or 2, 4. For the composition of claim 1 or 2, where ri is (CVC3) alkyl. 5. If the composition of claim 1 or 2, the catch 20 201242957 • The polymerization inhibitor is N-benzoinyl, morphine, N-(l-phenylethyl) thiophene or its first acid addition salt. 6. The composition of claim 5 The composition in which the trapping polymerization inhibitor is N. phenylmethyl non-tanning or N-(l-phenylethyl) thiophene. 7. The composition of any one of the claims. The composition further comprises: (a) a manganese salt of Mn(HC02.)2, Mn((C丨-C8)alkyl C〇2-)2 or potassium permanganate; (b) an N-oxyl compound And Mn(HC〇2-)2, ((Ci Cs) burnt c〇2)2 a first mixture of shovel salt: (C) hydroquinone; (d) a second mixture of molecular oxygen and morphine or its second acid addition salt, or (e) (a) i(4) above a combination of any two or more types of trapping polymerization inhibitors. 8. A method for inhibiting the polymerization of an acetamidine monomer, which comprises trapping polymerization of an effective amount of an oxime monomer and a polymerization inhibition The inhibitors are contacted together to obtain a polymerization inhibitor composition according to any one of claims 1 to 7 of the patent application.