EP3414301A1 - Gel ignifuge - Google Patents

Gel ignifuge

Info

Publication number
EP3414301A1
EP3414301A1 EP17705010.1A EP17705010A EP3414301A1 EP 3414301 A1 EP3414301 A1 EP 3414301A1 EP 17705010 A EP17705010 A EP 17705010A EP 3414301 A1 EP3414301 A1 EP 3414301A1
Authority
EP
European Patent Office
Prior art keywords
fire protection
protection gel
carboxylic acids
unsaturated carboxylic
gel according
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Withdrawn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
EP17705010.1A
Other languages
German (de)
English (en)
Inventor
Robert SCHERF
Meinhard Langenbahn
Horst Eckard
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.)
Raschig GmbH
Original Assignee
Raschig GmbH
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 Raschig GmbH filed Critical Raschig GmbH
Publication of EP3414301A1 publication Critical patent/EP3414301A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material

Definitions

  • the present invention relates to a fire protection gel, its preparation and its use in fire-resistant glass.
  • a disadvantage of the known acrylic acid derivative-based gels is the toxicity of the monomers which are classified as mutagenic, carcinogenic and / or reprotoxic. It was therefore the object to provide a fire protection gel which is just as effective but less toxic.
  • dialdehyde-crosslinked polyvinyl alcohols in DE 38 38 806 C2 and organically modified alkali water glass DE 10 2006 035 262 A1.
  • dialdehydes are also toxicologically problematic and organically modified
  • Alkali water glass requires special UV protection.
  • WO 00/65143 A1 and WO 2007/007115 A2 disclose hydrogels for medical applications which describe sulfonated carboxylic acid derivatives as monomers of hydrogels.
  • a fire protection gel based on a polymer containing sulfonated derivatives of unsaturated aliphatic
  • Carboxylic acids as monomers solves the task. These monomers and the polymers thereof are readily water soluble and the monomers become
  • the invention therefore relates to fire protection gels comprising a polymer of one or more sulfonated derivatives of unsaturated aliphatic
  • the invention further relates to a method for producing a fire protection gel, comprising the steps
  • the monomers are esters or amides of aliphatic, unsaturated carboxylic acids substituted with an alkylsulfonic acid group.
  • the carboxylic acid is in particular acrylic acid, methacrylic acid or itaconic acid.
  • R 1 is H, methyl, ethyl, iso-propyl, n-propyl or 2-hydroxy-propyl, most preferably H and methyl.
  • R 2 are methylene, ethylene or -CH 2 -CH 2 -CH 2 -, -CH (CH 3 ) -CH 2 -,
  • the sulphonic acid group is present, except for betaines, as salt or ester, preferably as salt.
  • Preferred salts are the alkali metal salts, especially the sodium salts and the potassium salts.
  • the esters are short chain esters, i. Methyl, ethyl, propyl or butyl ester, preferably methyl or ethyl ester, to ensure the water solubility of the polymers. In principle, longer-chain esters would also be useful if the polymers are water-soluble.
  • Particularly preferred monomers are acrylic acid (3-sulfopropyl) esters,
  • Potassium salt available under the name Ralumer SPA from Raschig GmbH, DE
  • 2-acrylamido-2-methylpropanesulfonic acid, sodium salt are methacrylic acid (3-sulfopropyl) ester, potassium salt (available under the name Ralumer SPM from Raschig GmbH, DE) and N, N-dimethyl-N- (2-methacryloxyethyl) -N- (3-sulfopropyl ) ammonium betaine (available under the name Ralumer SPE from Raschig GmbH, DE) advantageous.
  • sulfonated ethers or polyethers based on allyl alcohol for example sodium 3- (allyloxy) -2-hydroxypropanesulfonate (available under the name Ralumer SPAE from Raschig GmbH, DE) and Polyethylene glycol allyl (3-sulfopropyl) diether, potassium salt (available under the name Ralumer SPPE from Raschig GmbH, DE).
  • Useful gels contain from 5 to 30% by weight, preferably from 7.5 to 20% by weight and in particular from 10 to 15% by weight of polymerized monomers, based on the total weight of the fire protection gel.
  • crosslinking agents for example poly (ethylene glycol) diacrylate (PEGDA), to the reaction solution.
  • PEGDA poly (ethylene glycol) diacrylate
  • the amount of crosslinker is preferably in the range of 0.1 to 1 wt .-%.
  • the fire protection gels according to the invention preferably contain, like the known fire protection gels, one or more salts. These are usually chlorides, especially sodium chloride and magnesium chloride. These can be introduced according to the invention up to a total salt concentration of about 20% by weight, calculated as anhydrous salts. The optimal concentration depends on the ratio of the amounts of salt to each other. Other chlorides such as potassium chloride, calcium chloride or zinc chloride can also be used.
  • the fire protection gel can also contain water-miscible alcohols, for example ethylene glycol, glycerol and / or isopropyl alcohol, which are known as typical antifreeze additives. A concentration of at most 10% by weight of alcohol is expedient. It is also the use of optical brighteners, UV protectants and / or dyes conceivable. As an optical brightener is about Tinopal CBS-X (BASF SE, DE) in question. UV protectants can be selected from known groups such as, for example, the salicylates, the hydroxybenzophenones, the
  • Hydroxyphenylbenzotriazolen or hydroxyphenyltriazines are selected, provided that sufficient water solubility and no staining or turbidity of the gel occurs.
  • the use of multiple UV protection agents is conceivable.
  • the fire-retardant gel may have adhesion promoter, e.g. Silane coupling agent, contained in the usual amounts.
  • adhesion promoter e.g. Silane coupling agent
  • a preferred fire protection gel contains:
  • a particularly preferred fire protection gel contains:
  • the preparation according to the invention typically comprises, as a first step, the admixture of an aqueous solution containing from 20 to 60% by weight, preferably from 30 to 55% by weight and in particular about 50% by weight, of sulphonated derivatives of unsaturated carboxylic acids. If desired, the further components crosslinker and / or salt (s) are then added to the solution.
  • the initiation of the polymerization is possible by typical free-radical initiators such as sodium persulfate.
  • typical free-radical initiators such as sodium persulfate.
  • the amount of radical generator is e.g. in case of
  • a polymerization accelerator such as triethanolamine (TEA) can be used. Amounts of 0.01 to 0.5% by weight, especially 0.02 to 0.2% by weight, are useful. If no polymerization accelerator is used, temperatures of 50-70 ° C., preferably 55-65 ° C., are required. In the presence of a polymerization accelerator, the reaction can also be carried out at room temperature.
  • TAA triethanolamine
  • the polymerization is started by addition of the radical generator, if appropriate in admixture with the polymerization accelerator or after its addition, wherein the required temperature is to be observed.
  • the polymerization usually takes a few minutes to a few hours, often from 15 to 60 minutes. To prevent premature polymerization during the preparation, transport or storage of the still containing no initiator
  • Monomer solution is preferably added an inhibitor.
  • a particularly preferred inhibitor is 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, but also some aromatic compounds such as derivatives of phenol or hydroquinone have a stabilizing effect.
  • several inhibitors can be used. The amounts are usually from 1 to 100 ppm, preferably 10 to 30 ppm per inhibitor. It should be noted that the
  • the fire protection gel according to the invention comes as the known
  • Fire protection gels usually as a filling between at least two
  • the glass sheets may also be known per se, special, high-temperature resistant discs.
  • the thickness of the panes and the fire protection gel layer corresponds to the usual dimensions of the respective fire resistance class. In case of fire, the gel cools the side of the pane facing away from the fire by evaporating water and also forms an insulating crust, at the latest when the pane facing the fire is no longer intact.
  • Gelation must be sufficient here and can be adjusted by varying the amount of initiator and accelerator if necessary, taking into account the inhibitor used.
  • the invention also relates to all combinations of preferred embodiments, as far as these are not mutually exclusive.
  • the information "about” or “approx.” in conjunction with a numerical indication, means that at least 10% higher or lower values or 5% higher or lower values and in any case 1% higher or lower values are included.
  • AMPS 2-acrylamido-2-methylpropanesulphonic acid
  • demineralized water demineralized water
  • 12.84 g of sodium hydroxide were added gradually and the pH was adjusted to 9.7 with another 2.41 g of 1 M sodium hydroxide solution.
  • the yellowish-colored solution was then decolorized with 1.75 g of activated carbon ("1 wt .-% based on the solution) and stirred vigorously for one hour. The subsequent filtration caused a mass loss of 8.63 g, but the solution had only a slight yellowish hue.
  • composition of the solution according to the weighings and taking into account the filtration loss was: 11, 6 wt .-% SPA, 1, 56 wt .-% PEGDA and 36.1 wt .-% Na-AMPS.
  • Hydroquinone monomethyl ether in the range of 10 to 15 ppm.
  • composition of the solution according to the weights and taking into account the filtration loss and the samples taken were: 11, 6 wt .-% SPA, 1, 55 wt .-% PEGDA, 36.7 wt .-% Na-AMPS.
  • As a result of the raw materials used there was also a content of 13 ppm of the inhibitor hydroquinone monomethyl ether.
  • Example 2 containing 11, 6 wt .-% SPA, 1, 55 wt .-% PEGDA, 36.7 wt .-% Na AMPS, examined and confirmed the effectiveness.
  • Example 4 containing 11, 6 wt .-% SPA, 1, 55 wt .-% PEGDA, 36.7 wt .-% Na AMPS, examined and confirmed the effectiveness.
  • Example 4 containing 11, 6 wt .-% SPA, 1, 55 wt .-% PEGDA, 36.7 wt .-% Na AMPS, examined and confirmed the effectiveness.
  • Example 4 Example 4
  • DI demineralised
  • Polymerization inhibitor added to the solution.
  • 2740 g of a 49.2% sodium hydroxide solution were metered in slowly via the dropping funnel, the temperature of the solution not exceeding 30 ° C.
  • a pH of 9.6 was set.
  • 2440 g of SPA were added with stirring.
  • the solution thus obtained was stirred with 103 g of activated carbon for two hours at a temperature of 20 to 25 ° C.
  • 20420 g of the solution were present. This still 319.6 PEGDA were added and adjusted with 14.0 g of a 25% sodium hydroxide solution to a pH of 7.5.
  • composition of the solution according to the HPLC analysis was 37.8% Na-AMPS, 12.1% SPA and 1.42% PEGDA.
  • the content of 4-hydroxy TEMPO corresponding to the initial weight was 25 ppm.
  • hydrogels were prepared from a monomer solution prepared only in 2 L scale according to Example 4. To this was dissolved in 25.84 g of this solution, 30.00 g of magnesium chloride hexahydrate and 2.50 g of sodium chloride and diluted with 35.00 g of water. The solution was then degassed for one hour at room temperature and a pressure of about 50 mbar in a vacuum oven. The resulting loss of water of 380 mg was compensated by adding new demineralised water. The solution was then overlaid with argon and then the initiator solution of 0.035 g of sodium persulfate, 0.1 g of triethanolamine and 6.53 g of water was added.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des gels ignifuges contenant un polymère fait d'un ou plusieurs dérivés sulfonés d'acides carboxyliques aliphatiques insaturés en tant que monomères et de l'eau. L'invention concerne par ailleurs un procédé pour produire un gel ignifuge comprenant les étapes consistant à fournir un ou plusieurs dérivés sulfonés d'acides carboxyliques aliphatiques insaturés en tant que monomères, à mélanger avec de l'eau et à polymériser le(s) monomère(s). L'invention a également pour objet l'utilisation des gels ignifuges pour produire un vert ignifuge, le gel ignifuge étant produit par polymérisation des monomères entre deux vitres.
EP17705010.1A 2016-02-08 2017-01-30 Gel ignifuge Withdrawn EP3414301A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016201857 2016-02-08
PCT/EP2017/000108 WO2017137148A1 (fr) 2016-02-08 2017-01-30 Gel ignifuge

Publications (1)

Publication Number Publication Date
EP3414301A1 true EP3414301A1 (fr) 2018-12-19

Family

ID=58044003

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17705010.1A Withdrawn EP3414301A1 (fr) 2016-02-08 2017-01-30 Gel ignifuge

Country Status (2)

Country Link
EP (1) EP3414301A1 (fr)
WO (1) WO2017137148A1 (fr)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2346548A1 (fr) 1976-03-30 1977-10-28 Saint Gobain Vitrage multiple anti-feu, comportant une couche intercalaire de gel
DE3530968A1 (de) 1985-08-30 1987-03-12 Ver Glaswerke Gmbh Feuerwiderstandsfaehige verglasung
FR2624546B1 (fr) 1987-12-15 1993-11-26 Saint Gobain Vitrage Vitrage antifeu et procede de fabrication
GB9909349D0 (en) 1999-04-23 1999-06-16 First Water Ltd Process
US20040057986A1 (en) * 2001-03-30 2004-03-25 The Procter & Gamble Company Polymerized hydrogel adhesives comprising low amounts of residual monomers
DE10237395B4 (de) 2002-01-24 2012-12-20 C. G. I. International Limited Verfahren zur Herstellung einer Brandschutzverglasung und Brandschutzverglasung
GB0403510D0 (en) * 2004-02-18 2004-03-24 Mantra Internat Ltd Bioadhesive compositions and their use in medical electrodes
DE102005018842B4 (de) 2005-04-22 2017-05-11 Hero-Glas Veredelungs Gmbh Polymerisierbare Zusammensetzung zum Herstellen eines Hydrogels, Hydrogel sowie Verwendung des Hydrogels
EP1917047B1 (fr) 2005-07-14 2019-09-04 First Water Limited Traitement de lesions cutanees ulcereuses chroniques
DE102006035262A1 (de) 2006-07-29 2008-01-31 Schott Ag UV-undurchlässige Brandschutzverglasung
EP2234653B1 (fr) * 2008-01-17 2014-07-30 First Water Limited Composition copolymère d'hydrogel et ses utilisations, par exemple en tant que pansement

Also Published As

Publication number Publication date
WO2017137148A1 (fr) 2017-08-17

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