Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters

Definitions

• the present invention relates to a vinyl monomer polymerization inhibitor composition and method of inhibiting polymerization of a vinyl monomer therein.
• Vinyl monomers include vinyl alcohols and esters and acrylic monomers. Vinyl monomers are widely used in chemical industry. For example, acrylic monomers are used to prepare polyacrylate-type polymers (e.g., poly( acrylic acids) and poly(methacrylic acids)), which are useful as, among other things, additives (e.g., for use in rubbers, coatings and adhesives) and ingredients in fibers and other articles.
• polyacrylate-type polymers e.g., poly( acrylic acids) and poly(methacrylic acids)
• additives e.g., for use in rubbers, coatings and adhesives
• ingredients in fibers and other articles e.g., for use in rubbers, coatings and adhesives
• a major problem with the vinyl monomers is premature polymerization. In the absence of sufficient amounts of polymerization inhibitors, vinyl monomers undesirably polymerize during manufacture, purification, handling, and storage operations.
• WO 2010/096512 Al relates to a monomer polymerization inhibitor composition comprising a captive polymerization inhibitor and a fugitive polymerization inhibitor.
• the fugitive polymerization inhibitor is characterizable as being capable of evaporating with a distillable monomer from a first location (e.g., distillation pot) and condensing with the distillable monomer at a second location (e.g., in a distillation tower).
• a problem addressed by the present invention includes providing a vinyl monomer polymerization inhibitor composition comprising a captive polymerization inhibitor that inhibits polymerization of a vinyl monomer unexpectedly better than phenothiazine inhibits such polymerization, and wherein the composition lacks a fugitive polymerization inhibitor of the vinyl monomer.
• composition lacks a fugitive polymerization inhibitor of polymerization of the vinyl monomer and the captive polymerization inhibitor independently is characterizable as being a synergistically effective inhibitor of polymerization of the vinyl monomer and polymerization of the vinyl monomer is synergistically inhibited by the captive polymerization inhibitor, and wherein the
• the vinyl monomer is an acrylic monomer, preferably an acrylic acid- type monomer of formula (M):
• R is hydrogen or (C j -C ⁇ alkyl and each of R to
• R 1 ⁇ independently is hydrogen or (C j -Cg)aikyl.
• the present invention provides a method of synergistically inhibiting polymerization of a vinyl monomer, the method comprising contacting together a vinyl monomer with a polymerization inhibiting effective amount of a captive polymerization inhibitor so as to give the invention composition.
• the invention composition is one that is capable of functioning in the method of the second embodiment.
• the invention composition is useful in manufacture, purification, handling, and storage of vinyl monomers (e.g., vinyl alcohols and esters and acrylic monomers) as an inhibitor of polymerization of the vinyl monomers in, for example, vessels such as distillation pots, storage vessels, and transportation vessels.
• vinyl monomers e.g., vinyl alcohols and esters and acrylic monomers
• acrylic monomer means a vinyl monomer with the structural fragment, , wherein represent portions of covalent bonds.
• captive polymerization inhibitor means a substance that does not evaporate from a distillation pot during distillation of the vinyl monomer (e.g., acrylic monomer) therefrom.
• fugitive polymerization inhibitor means a substance that does not evaporate from a distillation pot during distillation of the vinyl monomer (e.g., acrylic monomer) therefrom.
• fugitive polymerization inhibitor means a substance that does not evaporate from a distillation pot during distillation of the vinyl monomer (e.g., acrylic monomer) therefrom.
• fugitive polymerization inhibitor means a substance that does not evaporate from a distillation pot during distillation of the vinyl monomer (e.g., acrylic monomer) there
• polymerization inhibitor means a substance that is capable of evaporating and condensing in a polymerization inhibiting amount with the acrylic.
• inhibitor means to delay onset of, reduce degree of, or, preferably, prevent that which is being inhibited.
• sinergistically effective inhibitor of polymerization means a substance that prevents visual appearance of solid poly( vinyl monomer) (e.g., poly( acrylic monomer)) for an average time value of at least 70 hours, which is about two times the average time value obtainable with phenothiazine per se.
• the time is determined using the following procedure: seal a glass vial containing a liquid mixture of the vinyl monomer (e.g., acrylic monomer) and 100 ppm of the substance or 100 ppm of the substance and 20 ppm of an inhibitor modifier, based on total weight of the liquid mixture. Place the vial in a mineral oil bath thermostated at 113 °C. Record time to the visual appearance of the solid poly( vinyl monomer) (e.g., poly( acrylic monomer)) anywhere in the vial (i.e., in the liquid mixture or on wall of vial above the liquid mixture). Repeat 4 times. Average the five times to give the average time value.
• the vinyl monomer e.g., acrylic monomer
• inhibitor modifier means a substance (e.g., a manganese salt) that generates or regenerates the compound from a derivative thereof.
• lacts and the like (e.g., lacking) means entirely absent.
• polymerization inhibiting effective amount means an absolute weight (e.g., in grams) or relative weight (e.g., expressed in parts per million (ppm) or weight percent (wt )) of a substance that is sufficient to delay onset of, reduce degree of, or, preferably, prevent polymerization.
• polymerization is synergistically inhibited and the like means where a polymerizable monomer is exposed to polymerization conditions (a chemical process resulting in bonding between two or more molecules of the polymerizable monomer to produce an organic oligomer or polymer thereof) and the polymerizable monomer is in contact with the captive polymerization inhibitor, rate of the chemical process is significantly lowered compared to a rate of the chemical process in presence of the comparator inhibitor, phenothiazine.
• Numerical ranges any lower limit of a range of numbers, or any preferred lower limit of the range, may be combined with any upper limit of the range, or any preferred upper limit of the range, to define a preferred aspect or embodiment of the range.
• each range of numbers includes all numbers, both rational and irrational numbers, subsumed in that range (e.g., "from 1 to 5" includes, for example, 1, 1.5, 2, 2.75, 3, 3.81, 4, and 5).
• (C j -C ⁇ alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 18 carbon atoms that is unsubstituted.
• Examples of (C j -C ⁇ alkyl are (CQ-C j g)alkyl (e.g., a (C j g)aikyl such as CH ⁇ Ct ⁇ ) ⁇ -) and (C j -Cg)aikyl, which includes (C j -C3)aikyl, including methyl, ethyl, 1 -propyl, and 2-propyl; and (C4-Cg)alkyl, including 1 -butyl (also known as normal- butyl or «-butyl), 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, and 1- octyl.
• the term "(C j -C ⁇ alkyl-O-" means the (C j -C ⁇ alkyl bonded to an oxygen atom radical.
• the captive polymerization inhibitor is especially useful for inhibiting polymerization of the vinyl monomer (e.g., acrylic monomer) in a distillation vessel (pot), storage vessel, or conduit (e.g., piping and tubing).
• the vinyl monomer e.g., acrylic monomer
• a distillation vessel pot
• storage vessel or conduit (e.g., piping and tubing).
• a polymerization inhibiting effective amount of the captive polymerization inhibitor can be varied depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, and presence or absence of other captive polymerization inhibitors.
• An invention process may be initiated with a larger polymerization inhibiting effective amount than is believed required. Thereafter the polymerization inhibiting effective amount can be allowed to decrease (e.g., as polymerization inhibitor is reacted) until a desirable steady-state amount of polymerization inhibitor is obtained under the conditions (e.g., as evidenced by achieving a desired time interval between vessel cleanings).
• a preferred first polymerization inhibiting effective amount of the compound of formula (I) is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
• the captive polymerization inhibitors do not include derivatives of the vinyl monomer (e.g., acrylic monomer).
• the captive polymerization inhibitor is the compound of formula (I) wherein is hydrogen. In some embodiments is (C j -C3)aikyl. In some embodiments is ethyl, 1 -propyl, or 2-propyl, and more preferably, is methyl. In some embodiments the compound of formula (I) is N-benzyl-phenothiazine, in other embodiments N-(l- phenylethyl)phenothiazine, and in still other embodiments the first acid addition salt thereof.
• non-nucleophilic base examples include sodium hydride, potassium hydride, potassium hexamethyldisilazide (KHMDS), and lithium diisopropylamide (LDA).
• leaving groups are iodo, bromo, chloro, an activated hydroxyl, trifluoromethanesulfonate, trifluoroacetate, and tosylate.
• activated hydroxyls are prepared from a compound of formula (IB) wherein LG is HO- and a coupling agent such as, for example, triphenylphosphine with either
• the carboxamide of formula (IC) can then be reduced (e.g., lithium aluminum hydride in tetrahydrofuran) to give the compound of formula (I) wherein is H.
• the invention further contemplates employing acid addition salts of the compound of formula (I).
• acid addition salt means an ionic substance comprising an organic cation and an organic, or preferably inorganic anion.
• the organic cation comprises a protonated form of phenothiazine or the compound of formula (I).
• the anion comprises a residual of an organic or, preferably, inorganic compound having at least one proton characterized by a pKa value of less than 7 (i.e., a residual of a Br0nsted acid).
• Preferred acid addition salts comprise from 0.9 to 1.1 mole equivalents of a monoprotic Br0nsted acid, from 0.45 to 0.55 mole equivalents of a diprotic Br0nsted acid, or from 0.3 to 0.37 mole equivalents of a triprotic Br0nsted acid, all per mole of phenothiazine or the compound of formula (I).
• Preferred Br0nsted acids include hydrochloric, nitric, phosphoric, sulfuric, hydrobromic, hydroiodic, phosphorus, formic, and acetic acids.
• the invention composition further comprises at least one additional captive polymerization inhibitor of the vinyl monomer (e.g., acrylic monomer).
• the vinyl monomer e.g., acrylic monomer
• the additional captive polymerization inhibitor is a manganese salt that is Mn(HC02 ⁇
• the manganese salt is employed in a method of the second embodiment as the inhibitor modifier in combination with the captive polymerization inhibitor.
• the manganese salt is Mn(HC02 ⁇ )2- I n
• the manganese salt is Mn((C j -Cg)aikylC02 ⁇ )2 > ar >d more preferably manganese(II) acetate, including manganese(II) acetate (M ⁇ C ⁇ CCH ⁇ ) and manganese(II) acetate tetrahydrate
• the manganese salt is potassium permanganate.
• the additional captive polymerization inhibitor is hydroquinone.
• the additional captive polymerization inhibitor is phenothiazine or a second mixture of molecular oxygen and phenothiazine, or a second acid addition salt thereof.
• nothiazine per se each mean the compound of the following formula:
• the additional captive polymerization inhibitor when used, is employed in its own independent polymerization inhibiting effective amount.
• a polymerization inhibiting effective amount of the manganese salt, hydroquinone, or phenothiazine can vary depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, presence or absence of other captive polymerization inhibitors, and amount of inhibitor modifier, if any, that is present.
• the person of ordinary skill in the art would be able to determine appropriate polymerization inhibiting effective amounts under particular circumstances without undue experimentation.
• a preferred polymerization inhibiting effective amount of the manganese salt, hydroquinone, or phenothiazine independently is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
• the invention composition further comprises a first mixture of an N- oxyl compound and the manganese salt that is Mn(HC02 ⁇ )2> Mn((Cj-Cg)aikylC02 ⁇ )2> or potassium permanganate.
• N-oxyl compound means a chemical substance having a
• the N-oxyl compound is 2,2,5 ,5-tetramethyl-3-oxopyrrolidine-l-oxyl; 2,2,6,6-tetramethylpiperidine-l-oxyl; tris(2,2,6,6-tetramethylpiperidine-l-oxyl-4-yl)-phosphite; and, more preferably, 4-hydroxy-2,2,6,6- tetramethylpiperidine-l-oxyl.
• the terms "4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl" and "4- hydroxy are synonymous and each mean a compound of the following formula:
• compositions further comprising a combination of any two or more of the aforementioned additional captive polymerization inhibitors.
• a polymerization inhibiting effective amount of 4-hydroxy-TEMPO can vary depending on, for example, the particular vinyl monomer (e.g., acrylic monomer) and amount thereof being inhibited, conditions such as temperature and pressure, presence or absence of other captive polymerization inhibitors, and amount of the manganese salt present.
• the person of ordinary skill in the art would be able to determine appropriate polymerization inhibiting effective amounts under particular circumstances without undue experimentation.
• a preferred polymerization effective inhibiting amount of the N-oxyl compound such as 4-hydroxy-TEMPO is from about 5 ppm to about 500 ppm, more preferably from about 10 ppm to about 250 ppm, still more preferably from about 20 ppm to about 200 ppm, and even more preferably from about 40 ppm to about 100 ppm, all based on a total weight of the liquid mixture.
• the present invention further contemplates compositions further comprising the inhibitor modifier.
• the inhibitor modifier are molecular oxygen and the manganese salt (e.g., when no additional captive polymerization inhibitor is employed or when the invention composition further comprises the N-oxyl compound (e.g., the 4-hydroxy-2,2,6,6-tetramethylpiperidine-l-oxyl).
• the acrylic monomer is the acrylic acid-type monomers of formula (M).
• Preferred is the acrylic acid- type monomer of formula (M) wherein one of R 1 1 to R 14 is (C j -Cg)aikyl and the remainder of R ⁇ to R ⁇ 4 is hydrogen.
• R ⁇ is (C j -
• R ⁇ is (C Q -C j g)alkyl. In some embodiments, R ⁇ is (C j -
• R ⁇ is (C j -Cg)aikyl and each of R ⁇ to R ⁇ 4 is hydrogen. In some embodiments, R ⁇ is (C j -Cg)aikyl and each of R ⁇ , R ⁇ , and R ⁇ 4 is hydrogen. In some embodiments, R ⁇ is (C j -Cg)aikyl and each of R ⁇ , R ⁇ , and R ⁇ 4 is hydrogen. In some embodiments, R ⁇ 4 is (C j -Cg)aikyl and each of R ⁇ to R ⁇ is hydrogen. In some embodiments, each of R 1 1 to R 14 is hydro gen, i.e., the acrylic acid-type monomer of formula (M) is acrylic acid itself. Also preferred is the acrylic acid-type monomer of formula (M) wherein two of R ⁇ to R ⁇ 4 is (C j -
• R ⁇ ⁇ is one of the two of
• R11 to R ⁇ 4 that is (C j -Cg)aikyl.
• the acrylic acid-type monomer of formula (M) wherein three of R ⁇ to R ⁇ 4 is (C j -Cg)aikyl and the remainder of R ⁇ ⁇ to R ⁇ 4 is hydrogen.
• each (C j -Cg)aikyl is (C j -C3)aikyl and, more preferably, methyl.
• the fugitive polymerization inhibitor that is lacking in the invention composition is a nitroso compound of formula (II): , wherein m is an integer of from 1 to 3 and each R A
• the vinyl monomer e.g., acrylic monomer
• polymerizing conditions are exposure to a polymerizing agent (e.g., oxygen gas, water, or a free radical or initiator) or condition (e.g., free radical generation conditions such as ultraviolet light or a high temperature zone).
• a polymerizing agent e.g., oxygen gas, water, or a free radical or initiator
• condition e.g., free radical generation conditions such as ultraviolet light or a high temperature zone
• a preferred method of the second embodiment employs any one of the preferred acrylic acid-type monomer polymerization inhibitor compositions described herein and any one of the preferred acrylic acid-type monomers of formula (M) described herein.
• Another preferred of the second embodiment employs a mixture of any two or more of the preferred acrylic acid-type monomers of formula (M) described herein such as, for example, a mixture of acrylic acid and either ethyl acrylate or «-butyl acrylate.
• the step comprises evaporating at least some of the vinyl monomer (e.g., acrylic monomer) and under a reduced pressure that is less than 90 kPa and an elevated temperature of the liquid mixture (e.g., distillation pot temperature) that is greater than 50 °C, and more preferably greater than 90 °C.
• a reduced pressure that is less than 90 kPa
• an elevated temperature of the liquid mixture e.g., distillation pot temperature
• a vessel e.g., distillation pot or reactor
• a vessel containing the invention composition is in fluid communication with a distillation column.
• a preferred distillation column is one that contains dual-flow plates or trays. An example of such a dual-flow tray column is described in U.S. Patent Number US 7,306,204 B2.
• distillation columns comprise, and the liquid mixture is in sequential fluid communication with, bottom, middle and upper zones, wherein the middle zone optionally defines a feed inlet.
• temperature in the bottom zone is within about 5 °C of the elevated temperature of the liquid mixture and reduced pressure in the top zone is within about 30 kPa of reduced pressure in the bottom zone.
• a manufacturing scale dual- flow 40-tray column during steady state operation is characterized by a temperature of about 111 °C and reduced pressure of about 35 kPa in its bottom zone, a temperature of about 46 °C and reduced pressure of about 21 kPa in its top zone, and a temperature of about 56 °C in its middle zone.
• the present invention contemplates batch (single addition of vinyl monomer (e.g., acrylic monomer)) and continuous (continuous addition or multiple separate additions of vinyl monomer (e.g., acrylic monomer)) to the vessel containing the invention composition.
• vinyl monomer e.g., acrylic monomer
• continuous processes especially continuous processes, preferably one or more additional polymerization inhibiting effective amounts of the captive polymerization inhibitor are added to the vinyl monomer (e.g., acrylic monomer) in the vessel.
• such one or more additional polymerization inhibiting effective amounts can be added to the distillation vessel containing vinyl monomer (e.g., acrylic monomer) so as to replace portions of the captive polymerization inhibitor lost to reaction thereof in the distillation vessel.
• the additions of the captive polymerization inhibitor independently comprise continuous or multiple separate additions and can be made by conventional means such as, for example, an addition funnel or valved feed line.
• Acrylic acid, phenothiazine, 4-hydroxy-TEMPO and a number of manganese salts are commercially available from various suppliers including Sigma- Aldrich Company, St. Louis, Missouri, USA.
• Examples 1 and 2 compositions of acrylic acid and compound (1) or (2).
• Examples 3 and 4 inhibition of polymerization of acrylic acid with compound (1) or (2).
• Example 3 seal vials and heat the compositions of Example 1 and for Example 4 seal vials and heat the compositions of Example 2, all at 113 degrees Celsius (°C) and record time of first appearance of change in density (gel formation) in compositions.
• a comparative, non-invention composition comprising 5 mL acrylic acid and 100 ppm of
• phenothiazine per se and likewise record time to gel formation.
• PTZ phenothiazine per se
• vinyl monomer e.g., acrylic monomer
• acrylic monomers especially acrylic acid-type monomers, as an inhibitor of polymerization of the acrylic monomers in, e.g., vessels and piping.

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• Organic Chemistry (AREA)
• Polymerisation Methods In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Citations (6)

• 2012
  • 2012-02-14 WO PCT/US2012/024936 patent/WO2012121836A1/en active Application Filing
  • 2012-02-14 JP JP2013557726A patent/JP2014507547A/ja 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/zh active Pending
  • 2012-02-14 KR KR1020137026379A patent/KR20140012122A/ko not_active Application Discontinuation
  • 2012-02-14 BR BR112013022992A patent/BR112013022992A2/pt not_active IP Right Cessation
  • 2012-02-14 MX MX2013010259A patent/MX2013010259A/es unknown
  • 2012-03-08 TW TW101107832A patent/TW201242957A/zh unknown

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