EP1763504A1 - Concentrated aqueous methacrylamide solution comprising methacrylic acid - Google Patents

Concentrated aqueous methacrylamide solution comprising methacrylic acid

Info

Publication number
EP1763504A1
EP1763504A1 EP05745488A EP05745488A EP1763504A1 EP 1763504 A1 EP1763504 A1 EP 1763504A1 EP 05745488 A EP05745488 A EP 05745488A EP 05745488 A EP05745488 A EP 05745488A EP 1763504 A1 EP1763504 A1 EP 1763504A1
Authority
EP
European Patent Office
Prior art keywords
methacrylamide
methacrylic acid
acrylic acid
meth
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05745488A
Other languages
German (de)
French (fr)
Inventor
Joachim Knebel
Wolfgang Klesse
Bardo Schmitt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1763504A1 publication Critical patent/EP1763504A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • 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
    • 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

Definitions

  • the invention relates to a new and improved form of delivery of
  • Methacrylic acid and the respective derivatives understood.
  • Methacrylamide as a polymerizable derivative of methacrylic acid is known per se and is commercially available (CAS No. 79-39-0).
  • a problem in the commercial use of methacrylamide is its tendency to clump and cake in solid form and to develop fine dust. This requires the user consuming devices for handling and dosing of the material, such as tuber breaker and suction with the associated filters.
  • Acrylamide has a neurotoxic and carcinogenic potential and is therefore used predominantly as an aqueous solution. This avoids contamination by dust formation and significantly reduces handling hazards. Since methacrylamide also has a certain neurotoxic potential, it is also desirable for this reason to provide a liquid commercial and transport form for methacrylamide as well.
  • methacrylamide While acrylamide has a high water solubility, and as for example, 40 - 50% solution commercially available, methacrylamide is soluble at 2O 0 C only about 20 wt .-% in water. So far, methacrylamide was to avoid the dust problem and the problem of agglomeration in the solid formulation, brought strength in the form of a 15 wt .-% aqueous solution in the trade, since only approximately 25 g of monomer per 100 g water at 2O 0 Release C. The concentration of methacrylamide in H 2 O is quite low, so that a relatively large amount of water must be transported as a solvent. Furthermore, such a large proportion of water may be undesirable in certain polymerizations.
  • the values in the table show that the replacement of part of the water by (meth) acrylic acid leads to a significant increase in the amount of methacrylamide which is soluble in the solvent mixture of water and (meth) acrylic acid.
  • the solution of the invention can be used directly as a raw material mixture for the preparation of polymers and / or copolymers, if these polymers simultaneously contain (meth) acrylic acid as a comonomer. Possible polymerization processes are emulsion polymerization, suspension polymerization or polymerization in solution.
  • methacrylamide in particular in the emulsion polymerization, the most important application for methacrylamide, is usually used in combination with (meth) acrylic acid, the concentrated methacrylamide in water / (meth) acrylic acid for a large part of existing applications. This is especially true when the (meth) acrylic acid content in the concentrated aqueous delivery form is smaller than the methacrylamide.
  • the weight ratio of methacrylamide: (meth) acrylic acid is preferably at least 2: 1, more preferably at least 3: 1.
  • the selected methacrylamide concentration of the delivery form depends on the requirements placed on the cold stability of the solution. If crystallization at lower temperatures than room temperature is to be avoided, then a lower concentration than the maximum possible room temperature of 44 g in 100 ml of water / methacrylic acid mixture will be set.
  • the methacrylamide content of the solution is preferably at least 25% by weight, more preferably at least 30% by weight and in particular at least 35% by weight.
  • the solution is generally mixed with conventional stabilizers.
  • stabilizers include phenols such as hydroquinone and hydroquinone monomethyl ether but also Cu ++ ions. Preference is given to hydroquinone monomethyl ether and Cu ++ ions.

Abstract

The invention relates to a liquid, concentrated formulation containing methacrylamide.

Description

Konzentrierte wässrige Methacrylamidlösung unter Zugabe von MethacrylsäureConcentrated aqueous methacrylamide solution with the addition of methacrylic acid
Gebiet der ErfindungField of the invention
Die Erfindung betrifft eine neue und verbesserte Lieferform vonThe invention relates to a new and improved form of delivery of
Methacrylsäureamid.Methacrylamide.
Im folgenden werden unter (Meth)acrylsäure die Verbindungen Acrylsäure undIn the following, under (meth) acrylic acid, the compounds acrylic acid and
Methacrylsäure und die jeweiligen Derivate verstanden.Methacrylic acid and the respective derivatives understood.
Stand der TechnikState of the art
Methacrylamid als polymerisierbares Derivat der Methacrylsäure ist an sich bekannt und im Handel erhältlich (CAS-Nr. 79-39-0). Ein Problem beim gewerblichen Umgang mit Methacrylamid ist seine Neigung, in fester Form zu verklumpen und zu verbacken sowie Feinstaub zu entwickeln. Dies erfordert beim Anwender aufwendige Vorrichtungen zur Handhabung und Dosierung des Materials, beispielsweise Knollenbrecher und Absaugvorrichtungen mit den zugehörigen Filtern. Acrylamid weist ein neurotoxisches und cancerogenes Potential auf und wird deshalb überwiegend als wässrige Lösung eingesetzt. Damit werden Kontaminationen durch Staubbildung vermieden und Gefahren bei der Handhabung deutlich verringert. Da auch Methacrylamid ein gewisses neurotoxisches Potential aufweist, ist es auch aus diesem Grunde erstrebenswert, eine flüssige Handels- und Transportform auch für Methacrylamid zur Verfügung zu stellen. Während Acrylamid eine hohe Wasserlöslichkeit aufweist und als z.B. 40 - 50 %ige Lösung im Handel ist, ist Methacrylamid bei 2O0C nur zu ca. 20 Gew.-% in Wasser löslich. Bisher wurde Methacrylamid, um das Staubproblem und das Problem der Verklumpung bei der festen Formulierung zu vermeiden, in Form einer 15 Gew.-%igen wässrigen Lösung in den Handel gebracht, da sich nur ca. 25 g Monomer pro 100 g Wasser bei 2O0C lösen. Die Konzentration an Methacrylamid in H2O ist recht gering, so dass eine verhältnismäßig große Menge Wasser als Lösemittel transportiert werden muss. Ferner kann ein derart großer Wasseranteil bei bestimmten Polymerisationen unerwünscht sein.Methacrylamide as a polymerizable derivative of methacrylic acid is known per se and is commercially available (CAS No. 79-39-0). A problem in the commercial use of methacrylamide is its tendency to clump and cake in solid form and to develop fine dust. This requires the user consuming devices for handling and dosing of the material, such as tuber breaker and suction with the associated filters. Acrylamide has a neurotoxic and carcinogenic potential and is therefore used predominantly as an aqueous solution. This avoids contamination by dust formation and significantly reduces handling hazards. Since methacrylamide also has a certain neurotoxic potential, it is also desirable for this reason to provide a liquid commercial and transport form for methacrylamide as well. While acrylamide has a high water solubility, and as for example, 40 - 50% solution commercially available, methacrylamide is soluble at 2O 0 C only about 20 wt .-% in water. So far, methacrylamide was to avoid the dust problem and the problem of agglomeration in the solid formulation, brought strength in the form of a 15 wt .-% aqueous solution in the trade, since only approximately 25 g of monomer per 100 g water at 2O 0 Release C. The concentration of methacrylamide in H 2 O is quite low, so that a relatively large amount of water must be transported as a solvent. Furthermore, such a large proportion of water may be undesirable in certain polymerizations.
Aufgabetask
Es bestand also die Aufgabe, eine Transport- und Handelsform für Methacrylamid zu entwickeln, dieIt was therefore the task of developing a transport and commercial form of methacrylamide, the
die Handhabungsnachteile des kristallinen Methacrylamids vermeidet, für den Kunden leicht einsetzbar ist und wenig oder möglichst keinen Umstellungsaufwand erfordert und einen höheren Gehalt an Methacrylamid als polymerisierbare Verbindung aufweist.avoids the handling disadvantages of the crystalline methacrylamide, is easy for the customer to use and requires little or no conversion effort and has a higher content of methacrylamide as a polymerizable compound.
Lösungsolution
Es wurde nun gefunden, dass durch Verwendung wässriger (Meth)acrylsäure es gelingt, bis zu 67 g Methacrylamid in 100 g Lösungsmittelgemisch zu lösen. It has now been found that by using aqueous (meth) acrylic acid it is possible to dissolve up to 67 g of methacrylamide in 100 g of solvent mixture.
(Gewichtsteile, bei 20° C)(Parts by weight, at 20 ° C)
Die Werte in der Tabelle zeigen, dass der Ersatz eines Teils des Wassers durch (Meth)acrylsäure zu einer deutlichen Erhöhung der im Lösungsmittelgemisch aus Wasser und (Meth)acrylsäure löslichen Menge an Methacrylsäureamid führt. Die erfindungsgemäße Lösung kann direkt als Rohstoffmischung zur Herstellung von Polymeren und/oder Copolymeren eingesetzt werden, wenn diese Polymeren gleichzeitig (Meth)acrylsäure als Comonomer enthalten. Mögliche Polymerisationsverfahren sind Emulsionspolymerisation, Suspensionspolymerisation oder die Polymerisation in Lösung. Da Methacrylamid, insbesondere bei der Emulsionspolymerisation, dem wichtigsten Einsatzgebiet für Methacrylamid, meist in Kombination mit (Meth)acrylsäure eingesetzt wird, eignen sich die konzentrierten Methacrylamidlösungen in Wasser/(Meth)acrylsäure für einen großen Teil der bestehenden Anwendungen. Das gilt insbesondere dann, wenn der (Meth)acrylsäureanteil in der konzentrierten wässrigen Lieferform kleiner als der Methacrylamidanteil ist. Vorzugsweise beträgt das Gewichtsverhältnis Methacrylamid : (Meth)acrylsäure mindestens 2:1 , besonders bevorzugt mindestens 3:1.The values in the table show that the replacement of part of the water by (meth) acrylic acid leads to a significant increase in the amount of methacrylamide which is soluble in the solvent mixture of water and (meth) acrylic acid. The solution of the invention can be used directly as a raw material mixture for the preparation of polymers and / or copolymers, if these polymers simultaneously contain (meth) acrylic acid as a comonomer. Possible polymerization processes are emulsion polymerization, suspension polymerization or polymerization in solution. Since methacrylamide, in particular in the emulsion polymerization, the most important application for methacrylamide, is usually used in combination with (meth) acrylic acid, the concentrated methacrylamide in water / (meth) acrylic acid for a large part of existing applications. This is especially true when the (meth) acrylic acid content in the concentrated aqueous delivery form is smaller than the methacrylamide. The weight ratio of methacrylamide: (meth) acrylic acid is preferably at least 2: 1, more preferably at least 3: 1.
Die gewählte Methacrylamidkonzentration der Lieferform richtet sich nach den Anforderungen, die an die Kältestabilität der Lösung gestellt wird. Soll ein Auskristallisieren bei niedrigeren Temperaturen als Raumtemperatur vermieden werden, so wird man eine niedrigere Konzentration als die bei Raumtemperatur maximal möglichen 44 g in 100 ml Wasser/Methacrylsäuregemisch einstellen. Vorzugsweise beträgt der Methacrylamidgehalt der Lösung mindestens 25 Gew-%, besonders bevorzugt mindestens 30 Gew.-% und insbesondere mindestens 35 Gew.-%.The selected methacrylamide concentration of the delivery form depends on the requirements placed on the cold stability of the solution. If crystallization at lower temperatures than room temperature is to be avoided, then a lower concentration than the maximum possible room temperature of 44 g in 100 ml of water / methacrylic acid mixture will be set. The methacrylamide content of the solution is preferably at least 25% by weight, more preferably at least 30% by weight and in particular at least 35% by weight.
Um unerwünschte vorzeitige Polymerisation zu unterbinden, wird die Lösung im allgemeinen mit üblichen Stabilisatoren versetzt. Dazu zählen Phenole wie Hydrochinon und Hydrochinonmonomethylether aber auch Cu++-Ionen. Bevorzugt werden Hydrochinonmonomethylether und Cu++-Ionen. In order to prevent unwanted premature polymerization, the solution is generally mixed with conventional stabilizers. These include phenols such as hydroquinone and hydroquinone monomethyl ether but also Cu ++ ions. Preference is given to hydroquinone monomethyl ether and Cu ++ ions.

Claims

Patentansprüche claims
1. Wässrige Lösung von Methacrylamid,1. Aqueous solution of methacrylamide,
dadurch gekennzeichnet,characterized,
dass diese zur Erhöhung der Löslichkeit des Methacrylamidsthat these increase the solubility of the methacrylamide
5 - 65 Gew.-%, bezogen auf die Lösungsmittelmenge, (Meth)acrylsäure enthält.5-65% by weight, based on the amount of solvent, of (meth) acrylic acid.
2. Wässrige Lösung nach Anspruch 1 ,2. Aqueous solution according to claim 1,
dadurch gekennzeichnet,characterized,
dass der Methacrylamidgehalt der Lösung mindest 25 Gew.-% beträgt.the methacrylamide content of the solution is at least 25% by weight.
3. Wässrige Lösung nach Anspruch 1 ,3. Aqueous solution according to claim 1,
dadurch gekennzeichnet,characterized,
dass der Methacrylamidgehalt der Lösung mindest 30 Gew.-% beträgt.the methacrylamide content of the solution is at least 30% by weight.
4. Wässrige Lösung nach Anspruch 1 ,4. Aqueous solution according to claim 1,
dadurch gekennzeichnet,characterized,
dass der Methacrylamidgehalt der Lösung mindest 35 Gew.-% beträgt. the methacrylamide content of the solution is at least 35% by weight.
5. Wässrige Lösung nach einem der Ansprüche 1 - 4,5. An aqueous solution according to any one of claims 1 - 4,
dadurch gekennzeichnet,characterized,
dass das Gewichtsverhältnis Methacrylamid zu (Meth)acrylsäure mindestens 2:1 beträgt.the weight ratio of methacrylamide to (meth) acrylic acid is at least 2: 1.
6. Wässrige Lösung nach einem der Ansprüche 1 - 4,6. An aqueous solution according to any one of claims 1 - 4,
dadurch gekennzeichnet,characterized,
dass das Gewichtsverhältnis Methacrylamid zu (Meth)acrylsäure mindestens 3:1 beträgt.the weight ratio of methacrylamide to (meth) acrylic acid is at least 3: 1.
7. Verwendung der Lösung nach den Ansprüchen 1 - 6 zur Herstellung von Polymeren.7. Use of the solution according to claims 1-6 for the preparation of polymers.
8. Polymer, erhältlich durch Polymerisation oder Copolymerisation der Lösung nach Anspruch 1. 8. Polymer obtainable by polymerization or copolymerization of the solution according to claim 1.
EP05745488A 2004-07-06 2005-05-20 Concentrated aqueous methacrylamide solution comprising methacrylic acid Withdrawn EP1763504A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004032766A DE102004032766A1 (en) 2004-07-06 2004-07-06 Concentrated aqueous methacrylamide solution with the addition of methacrylic acid
PCT/EP2005/005466 WO2006002717A1 (en) 2004-07-06 2005-05-20 Concentrated aqueous methacrylamide solution comprising methacrylic acid

Publications (1)

Publication Number Publication Date
EP1763504A1 true EP1763504A1 (en) 2007-03-21

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Country Status (10)

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US (1) US20070225398A1 (en)
EP (1) EP1763504A1 (en)
JP (1) JP2008505135A (en)
KR (2) KR20080102325A (en)
CN (1) CN1934070A (en)
CA (1) CA2566027A1 (en)
DE (1) DE102004032766A1 (en)
MX (1) MXPA06014048A (en)
RU (1) RU2007104233A (en)
WO (1) WO2006002717A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006006200B4 (en) * 2006-02-09 2008-01-10 Röhm Gmbh Aqueous N-methylol-methacrylamide-methacrylamide mixture
DE102008037207A1 (en) 2008-08-11 2010-02-18 Evonik Röhm Gmbh Process and solid container for the preparation of an aqueous methacrylamide solution

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL252972A (en) * 1959-06-24
DE1469616A1 (en) * 1965-01-08 1969-10-30 Basf Ag Printing pastes
US4236545A (en) * 1977-12-30 1980-12-02 Hercules Incorporated Use of radiation-induced polymers as friction reducing agents
US4314044A (en) * 1979-01-22 1982-02-02 Rohm And Haas Company Process for preparing low molecular weight water-soluble polymers
JPS5747309A (en) * 1980-09-04 1982-03-18 Mitsui Toatsu Chem Inc Preparation of acrylamide cationic high polymeric coagulant
EP0100493B1 (en) * 1982-07-28 1985-12-18 BASF Aktiengesellschaft Process for finishing leather or leather substitutes
DE3228128A1 (en) * 1982-07-28 1984-02-02 Basf Ag, 6700 Ludwigshafen Method for dressing leather or synthetic leather replacement material
DE3246904A1 (en) * 1982-12-18 1984-06-20 Röhm GmbH, 6100 Darmstadt Polymers containing imide groups, and process for their preparation
DE3317396A1 (en) * 1983-05-13 1984-11-15 Henkel KGaA, 4000 Düsseldorf USE OF COLOYERS FROM ESTERS AND AMIDES OF ACRYLIC AND / OR METHACRYLIC ACIDS AS STOCK POINTS LOW FOR PARAFFIN SOLUTIONS
US4536539A (en) * 1983-12-12 1985-08-20 Exxon Research And Engineering Co. Dilatant behavior of interpolymer complexes in aqueous solution
JPH0672397B2 (en) * 1985-03-08 1994-09-14 日本合成化学工業株式会社 How to give gloss to the surface of paper
DE3513550C1 (en) * 1985-04-16 1986-11-06 Th. Goldschmidt Ag, 4300 Essen Use of copolymers of polyoxyalkylene ethers of allyl and / or methallyl alcohol and acrylic or methacrylic esters as demulsifiers for petroleum containing water
US5216098A (en) * 1990-10-31 1993-06-01 Phillips Petroleum Company Superabsorbent crosslinked ampholytic ion pair copolymers
US5360710A (en) * 1992-05-06 1994-11-01 Eastman Kodak Company Color photographic materials containing polymeric couplers
KR960000850A (en) * 1994-06-06 1996-01-25 사토 아키오 Continuous production method of methyl methacrylate
RU2104292C1 (en) * 1995-01-13 1998-02-10 Акционерное общество закрытого типа научно-производственное предприятие "Хемекс Дор" Heat-salt resistant drilling mud
EP1167061B1 (en) * 2000-01-19 2006-06-14 Mitsui Chemicals, Inc. Emulsion for thermal recording material and thermal recording materials made by using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006002717A1 *

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KR20070031333A (en) 2007-03-19
MXPA06014048A (en) 2007-01-31
RU2007104233A (en) 2008-08-27
DE102004032766A1 (en) 2006-02-09
CN1934070A (en) 2007-03-21
KR20080102325A (en) 2008-11-24
KR100908024B1 (en) 2009-07-15
CA2566027A1 (en) 2006-01-12
JP2008505135A (en) 2008-02-21
WO2006002717A1 (en) 2006-01-12
US20070225398A1 (en) 2007-09-27

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