EP4301594A1 - Composition polymérisable pour la production d'un hydrogel de polyacrylamide pour vitrage ignifuge, processus de production et utilisations correspondants - Google Patents

Composition polymérisable pour la production d'un hydrogel de polyacrylamide pour vitrage ignifuge, processus de production et utilisations correspondants

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Publication number
EP4301594A1
EP4301594A1 EP22708155.1A EP22708155A EP4301594A1 EP 4301594 A1 EP4301594 A1 EP 4301594A1 EP 22708155 A EP22708155 A EP 22708155A EP 4301594 A1 EP4301594 A1 EP 4301594A1
Authority
EP
European Patent Office
Prior art keywords
mass
polymerizable composition
fire
component
polyacrylamide hydrogel
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.)
Pending
Application number
EP22708155.1A
Other languages
German (de)
English (en)
Inventor
Hermann Wegmann
Heinz-Hermann ROSS
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.)
Skanbel Ug
Original Assignee
Skanbel Ug
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 Skanbel Ug filed Critical Skanbel Ug
Publication of EP4301594A1 publication Critical patent/EP4301594A1/fr
Pending legal-status Critical Current

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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
    • B32B17/069—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 of intumescent material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • B32B17/10—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 of synthetic resin
    • B32B17/10005—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 of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
    • B32B17/10917—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form between two pre-positioned glass layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant

Definitions

  • the present invention relates to a polymerizable composition for producing a polyacrylamide hydrogel, a corresponding polyacrylamide hydrogel and fire-resistant glazing comprising an aforementioned polymerizable composition or an aforementioned polyacrylamide hydrogel.
  • the present invention also relates to a method for producing fire-resistant glazing and the use of an aforementioned polymerizable composition and/or an aforementioned polyacrylamide hydrogel, each as a fire retardant for fire-resistant glazing and/or in the manufacture of fire-resistant glazing.
  • the present invention also relates to the use of one or more polyhydroxy compounds, in particular glycerol, to improve the adhesion of a polyacrylamide hydrogel to fire-resistant glazing.
  • Fire protection glazing usually consists of two glass panes which are arranged essentially parallel to one another and are separated from one another by an intermediate space (or a gap), between which a fire protection agent is arranged.
  • the fire retardant is usually foamed up when exposed to fire, loses its transparency for thermal radiation and releases water vapor, so that the side of the fire-resistant glazing facing away from the fire is cooled and protected against the protected from the effects of thermal radiation from the fire.
  • Such fire-resistant glazing is described, for example, in document DE 102 37 395 A1.
  • Fire protection glazings are also already known from the prior art, which are relatively light and at most contain only slightly corrosive fire retardants, ie little or no attack on metal parts present in the fire protection glazing. Likewise, fire-resistant glazing is known which—in everyday use—permanently retains its transparency.
  • the document DE 102005018842 A1 describes fire-resistant glazing which comprises a polyacrylamide hydrogel as a fire retardant.
  • the document DE 102006035262 A1 deals with UV-impermeable fire protection glazing.
  • the document EP 0 705 685 A1 relates to a fire protection glass unit with two panes and in the space between the panes an intermediate layer that foams up in the event of a fire.
  • the intermediate layer consists mainly of soda water glass and water.
  • a fireproof glass is specified in the document WO 01/70495 A1.
  • EP 0542 022 A1 describes a modified, transparent aqueous alkali metal silicate solution, processes for its production and its use for the production of transparent hydrogels.
  • Document DE 3530 968 A1 relates to fire-resistant glazing.
  • a primary object of the present invention to provide a fireproofing agent which should allow the production of light fireproof glazing and at most should be slightly corrosive to metal parts of a fireproof glazing.
  • the fire retardant in a fire-resistant glazing should ensure the most permanent and high transparency possible with the least possible impairment, for example through the formation of bubbles or unwanted discoloration of the fire-resistant glazing, and above all also have good or improved adhesion to the glass panes of the fire-resistant glazing.
  • further objects of the present invention consisted in specifying a composition for producing an improved fireproofing agent and providing improved fireproof glass and a method for its production.
  • a polymerizable composition according to the invention described above is excellently suited for the production of a polyacrylamide hydrogel according to the invention, which is suitable as a fire retardant for relatively light fire-resistant glazing and which at most has low corrosive properties towards metal parts of fire-resistant glazing.
  • a polyacrylamide hydrogel according to the invention used as a fire retardant ensures permanent and high transparency of fire-resistant glazing, with at most very little impairment of the transparency of the fire-resistant glazing, for example through blistering or unwanted discoloration.
  • an above-mentioned polyacrylamide hydrogel according to the invention has excellent adhesion properties on or on the surface of a pane of fire-resistant glazing.
  • a polyacrylamide hydrogel is understood to mean a polyacrylamide-containing, hydrous gel known per se in the art.
  • a gel is understood to mean a disperse system which consists of at least two components, as is customary in general usage (but without specifying a specific structure of a gel).
  • a solid component (solid phase) forms a spongy, three-dimensional network whose pores are filled with a liquid component (liquid phase).
  • a polymerizable composition according to the invention described above or a polymerizable composition according to the invention described as preferred in this text
  • the substituted acrylamides of component (A) comprise N-methylolacrylamide or consist of N-methylolacrylamide, or component (A) consists of N -Methylolacrylamide
  • the one or more polymerizable monomers of component (A) are selected from the group consisting of substituted acrylamides and mixtures thereof, with preferably one or at least one of the more polymerizable
  • Monomers of component (A) is N-methylolacrylamide and/or component (A) is present in a total amount in the range from 3 to 12% by mass, preferably from 4 to 10% by mass, based on the total mass of the polymerizable Composition.
  • a polymerizable composition according to the invention described in more detail in this text which comprises N-methylolacrylamide as polymerizable monomers (in particular in a proportion of >80 mole percent of the polymerizable monomers of component (A) present in the polymerizable composition) ), Especially in the total amount given above, or in the preferred total amounts given above, is particularly suitable for the production of a polyacrylamide hydrogel for fire-resistant glazing, since in this way a transparent, at most slightly corrosive polyacrylamide hydrogel is very good for the filling of fire-resistant glazing can be produced with a suitable viscosity.
  • a polymerizable composition according to the invention described above or a polymerizable composition according to the invention described as preferred in this text
  • the one or more salts of component (B) comprise or are salts of monovalent and/or divalent metal ions
  • the one or more salts of component (B) comprise or are salts of the alkali metals and/or alkaline earth metals, preferably halogen salts, particularly preferably chlorides, of the alkali metals and/or alkaline earth metals, with preferably one, several, or all salts of the component (B) are selected from the group consisting of NaCl, KCl, MgC, CaCh and mixtures thereof, with all salts of component (B) preferably being selected from the group consisting of NaCl, MgCh and mixtures thereof; and/or component (B) is present in a total amount in the range from 8 to 35% by mass, preferably from 10 to 30% by mass, particularly preferably from 15 to 25% by mass,
  • a polymerizable composition according to the invention described above (or a polymerizable composition according to the invention described as preferred in this text), wherein one, several, or all crosslinking aids of component (C) are selected from the group consisting of N,N'-methylenebisacrylamide, formaldehyde and mixtures thereof, with preferably one or at least one of the several crosslinking aids of component (C) N, is N'-methylenebisacrylamide; with particular preference the crosslinking aid of component (C) is N,N'-methylenebisacrylamide; and/or component (C), preferably N,N'-methylenebisacrylamide, in a total amount in the range from 0.001 to 1.0% by mass, preferably from 0.005 to 0.5% by mass, particularly preferably from 0.01 to 0.35% by mass, based on the total mass of the polymerizable composition.
  • the mass fractions of the N,N'-methylenebisacrylamide present in the polymerizable composition are only used as or for the (calculation of the mass fractions of) component (C) as a crosslinking aid of the polymerizable composition according to the invention, but not (also) as or for another component (such as component (A)) of the polymerizable composition according to the invention.
  • N,N'-methylene-bisacrylamide as a crosslinking agent of component (C) of the polymerizable composition according to the invention in the total amount specified above, or in the preferred total amounts specified above, a polyacrylamide hydrogel with a degree of crosslinking that is particularly suitable for use as a fire retardant.
  • component (D) is selected from the group consisting of ethylene glycol; diethanolamine; triethanolamine; N,N,N',N'-tetramethylethylenediamine and mixtures thereof, component (D) preferably comprising or being a mixture of ethylene glycol and triethanolamine, with the mass ratio of ethylene glycol to triethanolamine particularly preferably being in the range of 0.5: from 1 to 1:0.5, more preferably from 0.75:1 to 1:0.75 and most preferably 1:1; and/or component (D) is present in a total amount in the range from 0.009 to 1.5% by mass, preferably from 0.01 to 1% by mass, particularly preferably from 0.015 to 0.5% by mass, based on the total mass of the polymerizable composition.
  • the time required for the polymerization of the polymerizable composition according to the invention to form a polyacrylamide hydrogel according to the invention depends, inter alia, on the type and concentration of the polymerization catalyst(s) used. It has been shown in our own tests that when using the polymerization catalysts specified here above, in particular when using the preferred polymerization catalysts specified here above, in the total amount specified above, in particular in the preferred total amounts specified above, rapid and complete polymerization of the polymerizable composition according to the invention to form a polyacrylamide hydrogel according to the invention, the latter being outstandingly suitable as a fire retardant for fire-resistant glazing.
  • the one or more polyhydroxy compounds of component (E) comprise or are one or more polyhydroxy compounds, each of which independently has a total number of carbon atoms ranging from 3 to 6, and/or each independently having a total number of hydroxy groups ranging from 2 to 6, preferably from 3 to 6, preferably one, several, or all of the polyhydroxy compounds of component (E) are selected from the group consisting of propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, mannitol, sorbitol, xylitol, glucose, glycerol and mixtures thereof, with more preferably one, several , or all polyhydroxy compounds of
  • Component (E) are selected from the group consisting of propylene glycol, diethylene glycol, triethylene glycol, mannitol, sorbitol, xylitol, glucose, glycerol and mixtures thereof, with the or at least one of the one or more polyhydroxy compounds of component (E) glycerol being particularly preferred is and most preferably the
  • component (E) is glycerin; and/or component (E), preferably glycerol, in a total amount in the range from >1 to ⁇ 12% by mass, preferably from >1.5 to ⁇ 11% by mass, particularly preferably from >2 to ⁇ 7 .5% by mass, very particularly preferably from >3 to ⁇ 7.5% by mass
  • % is present, based on the total mass of the polymerizable composition or component (E), preferably glycerol, in a total amount in the range from> 1 to ⁇ 15% by mass, preferably from> 2 to ⁇ 15% by mass, particularly preferably from >3 to ⁇ 15% by mass, very particularly preferably from >3.5 to ⁇ 12% by mass, based on the total mass of the polymerizable composition.
  • the compounds ethylene glycol, diethanolamine and/or triethanolamine which can be used as polymerization catalysts of component (D) in the polymerizable composition according to the invention can also be used or be present in the polymerizable composition according to the invention as polyhydroxy compounds of component (E).
  • ethylene glycol, diethanolamine and/or triethanolamine are present or used in the polymerizable composition according to the invention, for the purposes of the present invention (only) the 1% by mass (based on the total mass of the polymerizable composition) will exceed- the mass fractions of ethylene glycol, diethanolamine, triethanolamine, or mixtures thereof present in total in the polymerizable composition, are taken into account when calculating the mass fractions of component (E) in the polymerizable composition according to the invention.
  • the improved adhesion of the polyacrylamide hydrogel according to the invention to the surface of the pane of fire-resistant glazing increases road safety even without the occurrence of a fire, since, for example, in the event of a breakage due to traffic load, glass particles or broken glass of the fire-resistant glazing according to the invention are already held back by the fire retardant and move away from the breaking point only to a significantly lesser extent, for example being thrown through the adjacent room. In this way, among other things, the risk of injury to people is reduced.
  • An additional advantage associated with the use of the polyhydroxy compounds specified here above, in particular with the use of the preferred or particularly preferred polyhydroxy compounds specified here above, is in the total amount specified above, in particular in the preferred total amounts specified above in that a fire-resistant glazing according to the invention, which was produced with the aid of a polymerizable composition according to the invention or a polyacrylamide hydrogel according to the invention, has improved frost protection compared to comparable fire-resistant glazing, which, however, does not contain any of the polyhydroxy compounds specified here above or which polyhydroxy compounds specified here above only contained in small amounts.
  • the fire-resistant glazing according to the invention described in this text is therefore also particularly suitable for use outdoors.
  • a polymerizable composition according to the invention as described above is furthermore also preferred, where component (F), water, is present in the polymerizable composition in a concentration to achieve 100% by mass the total amount required of the polymerizable composition; and/or the polymerizable composition has a pH in the range from 5 to 9, preferably in the range from 5.5 to 8.5, particularly preferably in the range from 6 to 8.
  • the present invention also relates to a polyacrylamide hydrogel produced or producible by polymerization of the polymerizable portions of a polymerizable composition according to the invention described above (or a polymerizable composition according to the invention described as preferred in this text).
  • a polyacrylamide hydrogel according to the invention is excellently suitable as a fire retardant for fire-resistant glazing, since it remains stable over long periods of time and has little or no tendency to form bubbles and, especially if the preferred ones specified above or particularly preferred polyhydroxy compounds in the total amount specified above, in particular in the preferred total amounts specified above, used for the production thereof, is largely or completely UV-stable.
  • a fire-resistant glazing according to the invention containing the polyacrylamide hydrogel according to the invention as a fire retardant is therefore characterized by only extremely slight or non-existent, age-related, undesirable discoloration or impairment of the transparency and/or the design aesthetics.
  • the present invention also relates to fire-resistant glazing, comprising an arrangement of at least two panes which are at least partially transparent to visible light and which are spaced apart from one another, preferably in one
  • the array having at least one space between any two panes, preferably the space being defined by the spacing of the two panes from each other and by the surfaces of the two panes; and in the at least one interspace a polymerizable composition according to the invention (or a polymerizable composition according to the invention described as preferred in this text) or a polyacrylamide hydrogel according to the invention (or a polymerizable polyacrylamide hydrogel according to the invention described as preferred in this text).
  • the panes that are at least partially transparent to visible light being glass panes and preferably comprising or consisting of silicate-containing glass (in the present text and as is customary in the art also referred to as “mineral glass”), which is preferably uncoated is, particularly preferably silicate-containing glass which is selected from the group consisting of soda-lime silicate glass, flat glass, sun protection glass, toughened safety glass (ESG), laminated safety glass (LSG), borosilicate glass and combinations thereof.
  • silicate-containing glass in the present text and as is customary in the art also referred to as “mineral glass”
  • silicate-containing glass which is selected from the group consisting of soda-lime silicate glass, flat glass, sun protection glass, toughened safety glass (ESG), laminated safety glass (LSG), borosilicate glass and combinations thereof.
  • the distance at which the (at least two) aforementioned panes are arranged from one another preferably defines the intermediate space of the above-specified fire-resistant glazing according to the invention.
  • the distance at which the at least two aforementioned panes are arranged from one another and/or the space between the fire-resistant glazing according to the invention specified above preferably defines the gel strength (i.e. the layer thickness) of the polyacrylamide hydrogel according to the invention used in the fire-resistant glazing according to the invention.
  • the aforementioned glass panes which are suitable for use in fire-resistant glazing according to the invention as specified above, can be colorless or tinted.
  • a fire-resistant glazing according to the invention also has excellent soundproofing properties, which were even better than the soundproofing properties of a fire-resistant glazing similar to the fire-resistant glazing according to the invention, but whose polyacrylamide hydrogel was not in a total amount of >1% by mass, preferably > 2% by mass, particularly preferably >3.5% by mass, based on the total mass of the polymerizable composition, of one or more polyhydroxy compounds each independently having a total number of carbon atoms in the range from 2 to 6 (and which polyacrylamide hydrogel in particular contained no glycerol).
  • the present invention also relates to a method for producing fire-resistant glazing, comprising the steps
  • V1 Providing or producing an arrangement of at least two panes, at least partially transparent to visible light, which are arranged at a distance from one another, preferably at a distance from one another and parallel to one another, with the arrangement at least one between two panes in each case lying, has space,
  • step V3) at least partially, preferably completely, filling at least one space between two panes of the arrangement provided or manufactured in step V1) with the polymerizable composition provided or manufactured in step V2) and
  • step V4) Polymerize or allow to polymerize the polymerizable portions of the polymerizable composition specified in step V3) in the at least one space between two panes of the arrangement, preferably in contact with the surfaces of the two panes facing the at least one space or in contact with the adhesive-coated (see below) surfaces of the two discs facing the at least one gap, preferably so that a polyacrylamide hydrogel according to the invention results.
  • the polymerizable composition according to the invention provided or produced in step V2) of the method according to the invention given above can be used in a first variant as a ready-mixed composition comprising all components (A) to (F).
  • the quality of a fire-resistant glass produced by the method according to the invention could also ultimately be adversely affected by a polymerizable composition that is not used in a homogeneous state. It is also preferred in this variant if the completely mixed polymerizable composition is at least partially degassed before carrying out step V3).
  • the polymerizable composition according to the invention provided or produced in step V2) of the method according to the invention specified above can only be fully mixed shortly before carrying out step V3), with components (A) to (D) and (F) (or Components (A) to (C) and (E) to (F), or components (A) to (C) and (F)) can be used as a ready-mixed premix, while component (E) (and/or optionally Component (D)) is combined and mixed with the aforementioned ready-mixed premix only shortly before carrying out step V3).
  • step V3 it is preferred if local concentration gradients of individual components of the polymerizable composition are avoided as far as possible by adequate mixing of all components before or during the implementation of step V3) and/or if the ready-mixed polymerizable composition is removed before the implementation of step V3) is at least partially degassed.
  • polyacrylamide hydrogel according to the invention is produced in situ in an intermediate space between two adjacent panes of the aforementioned arrangement.
  • step V3) preferably at least one interstice lying between each two panes of the arrangement provided or produced in step V1) is created at least partially and preferably almost completely filled with the polymerizable composition provided or produced in step V2).
  • the (preferably homogenized and/or at least partially degassed, see above) polymerizable composition according to the invention is used as a ready-mixed composition comprising all components (A) to (F).
  • components (A) to (D) and (F) of the polymerizable composition according to the invention are used as a ready-mixed premix and are combined with component (E) and with this only shortly before step V3) is carried out mixed.
  • the composition comprising all components (A) to (F) present before carrying out step V3) is preferably homogenized and/or at least partially degassed.
  • the components (A) to (C) and (F) of the polymerizable composition according to the invention are used as a ready-mixed premix and only shortly before carrying out step V3) with the components (D) and ( E) combined and mixed with these.
  • the composition comprising all components (A) to (F) present before carrying out step V3) is preferably homogenized and/or at least partially degassed.
  • the space between two adjacent panes of the fire-resistant glazing is essentially completely filled by the polymerizable composition according to the invention or by the polyacrylamide hydrogel according to the invention.
  • cavities in particular air bubbles, are avoided between the panes. Such cavities could cloud the transparency of the panes (under non-fire conditions), which is generally undesirable.
  • essentially complete filling of the gap with the polymerizable composition according to the invention or the polyacrylamide hydrogel according to the invention ensures that in the event of a fire under the influence of heat, the aforementioned advantages of fire-resistant glazing are achieved to the greatest possible extent.
  • the intermediate space and essentially any end faces of the panes that are present are preferably surrounded by an outer casing.
  • the outer casing serves the purpose of preventing the fire retardant from leaking out during the filling process of the fire-resistant glazing.
  • the sheath is a flexible body. Alternatively, however, a rigid frame can also be provided.
  • panes of fire-resistant glazing heat up more in the event of a fire
  • the pane facing the source of the fire expands as a result of the heating.
  • the pressure in the space increases due to the gases released, such as water vapour. Both causes mean that the pane of the fire-resistant glazing facing the source of the fire expands more than the pane facing away from the source of the fire.
  • the intermediate space should preferably be released completely, so that the degassing of the fire protection agent can take place at least in the vicinity of the end faces of the gap. In this way, a good cooling effect is ensured by the polyacrylamide hydrogel according to the invention even if the pane facing the seat of the fire has not yet broken.
  • step V3) it is also possible to carry out step V3) such that the polymerizable composition according to the invention or the polyacrylamide hydrogel according to the invention is applied to at least one of the two panes before the panes are bonded.
  • the procedure here is expediently and preferably such that no gas bubbles are enclosed between the polymerizable composition according to the invention or the polyacrylamide hydrogel and the associated pane.
  • step V4) the polymerizable components of the polymerizable composition specified in step V3) are polymerized (or allowed to polymerize).
  • a free-radical initiator is preferably added to the polymerizable composition specified in step V3) in order to accelerate the polymerization.
  • a free-radical initiator preferably a free-radical initiator
  • a free-radical initiator is additionally added to the polymerizable composition, preferably after step V3) and/or before or during step V4).
  • a peroxide-containing compound preferably selected from the group consisting of dibenzoyl peroxide, a salt of peroxodisulfuric acid (preferably disodium peroxodisulfate and ammonium peroxodisulfate) and mixtures thereof; an azo group-containing compound, preferably azobisisobutyronitrile and - riboflavin.
  • Peroxide-containing compounds are particularly preferred as radical initiators for addition to the polymerizable composition according to the invention, salts of peroxodisulfuric acid and mixtures thereof are very particularly preferred, particularly preferably disodium peroxodisulfate, ammonium peroxodisulfate and mixtures thereof.
  • salts of peroxodisulfuric acid and mixtures thereof are very particularly preferred, particularly preferably disodium peroxodisulfate, ammonium peroxodisulfate and mixtures thereof.
  • the person skilled in the art is familiar with the usual amounts or concentrations of free-radical initiators that are also suitable in the present case, or the person skilled in the art can easily determine appropriate amounts or concentrations of free-radical initiators for the purpose described above using routine measures.
  • the time required for the polymerization in step V4) depends, among other things, on the concentration of a free-radical initiator used.
  • the free-radical reaction can be started in a manner known per se by the targeted irradiation of blue be started with violet light.
  • the point in time at which the radical reaction begins can be selected in a targeted manner, which can be advantageous in particular in the industrial production of fire-resistant glazing.
  • the person skilled in the art will of course only use riboflavin as a free-radical initiator in those cases in which the other properties of riboflavin (eg color, UV activity) do not interfere or are even desired under the conditions of the method according to the invention or in fire-resistant glazing according to the invention.
  • step V3 A method according to the invention as described above (or a method according to the invention described as preferred in this text) is also preferred, with an additional step V2a) being carried out before step V3):
  • V2a Application to at least a portion of the surfaces of the at least two panes facing the intermediate space, of a composition containing a silane-containing adhesive, preferably an adhesive containing one or more silanes containing trimethoxysilyl groups.
  • a composition containing a silane-containing adhesive preferably an adhesive containing one or more silanes containing trimethoxysilyl groups.
  • N-[3-(trimethoxysilyl)propyl]ethylenediamine and/or derivatives thereof are preferably used as silane-containing adhesives, preferably 1,2-ethanediamine, N-(3-trimethoxysilyl)propyl-N-(ethenylphenyl)methyl ⁇ derivatives, each (in all cases) including their salts with mineral acids, preferably their hydrochlorides.
  • step V2a is carried out in the method according to the invention, this results in at least partially coated (see above) surfaces of the aforementioned (at least) two panes facing the intermediate space, which form such an intermediate space.
  • the surfaces of the at least two panes facing an intermediate space are partially or completely coated with a silane-containing adhesive.
  • a method according to the invention in which the polymerization (or polycondensation) of the polymerizable composition according to the invention to give the polyacrylamide hydrogel according to the invention in step V4) (see below) takes place directly in the or in a space between two adjacent panes of fire-resistant glazing. If, on the other hand, the polyacrylamide hydrogel according to the invention is sufficiently free-flowing, the said gap can also be filled after the polyacrylamide hydrogel has been produced (then with this polyacrylamide hydrogel).
  • panes are connected to one another essentially over their entire surface by the polyacrylamide hydrogel according to the invention, the panes being connected to one another in particular due to the high adhesive forces of the fire protection agent. If the adhesion forces of the polyacrylamide hydrogel according to the invention are sufficiently high, ideally the use of other fastening means, e.g. metal clamps, can be completely dispensed with.
  • panes of the fire-resistant glazing according to the invention are expediently connected to one another in such a way that a position shift of the pane in the direction of the seat of the fire relative to the pane facing away from the seat of the fire is possible, preferably both in the direction of the end faces of the pane and transversely thereto.
  • the width of the gap between two adjacent panes of a fire-resistant glazing according to the invention results after the gap has been completely filled with the fire retardant (i.e. the polyacrylamide hydrogel according to the invention) essentially by the layer thickness of the fire retardant or by appropriate spacers that are used between the adjacent panes are.
  • the fire retardant i.e. the polyacrylamide hydrogel according to the invention
  • the layer thickness of the fire protection agent By choosing the layer thickness of the fire protection agent, the fire protection time and the intensity of the radiation reduction through the fire protection glazing can be adjusted, among other things.
  • a constant thickness of the fire-resistant glazing is also desirable with regard to later installation, e.g. in a window frame.
  • the present invention also relates to the use of a polymerizable composition according to the invention as described above (or a described as preferred polymerizable composition according to the invention), or a polyacrylamide hydrogel according to the invention described above (or a polyacrylamide hydrogel according to the invention described as preferred in this text) as a fire retardant for fire-resistant glazing and/or in the production of fire-resistant glazing.
  • the present invention also relates to the use of one or more polyhydroxy compounds defined above (or of one or more polyhydroxy compounds described as preferred in this text) as an additive to a polymerizable composition for the production of a polyacrylamide hydrogel and/or to a polyacrylamide hydrogel, preferably to form a polyacrylamide hydrogel produced or producible from the polymerizable composition, preferably to improve the adhesion of the polyacrylamide hydrogel to a pane, preferably a pane comprising or consisting of mineral glass, fire-resistant glazing; and/or to improve the adhesion of a polyacrylamide hydrogel to or on fire-resistant glazing, preferably on or on the surface of a pane, preferably a pane comprising or consisting of silicate glass, fire-resistant glazing.
  • a polymerizable composition according to the invention or a polyacrylamide hydrogel according to the invention to the method according to the invention, to the fire-resistant glazing according to the invention, to the polyacrylamide hydrogel according to the invention and/or to the according to the invention polymerizable composition according to the explanations given above, in particular with regard to possible preferred embodiments and possible or preferred combinations (if appropriate analogously), and vice versa.
  • polyhydroxy compounds or of one or more polyhydroxy compounds described as preferred in this text
  • a polymerizable composition for the production of a polyacrylamide hydrogel and/or to a polyacrylamide hydrogel in a total amount of> 1% by mass, preferably of> 2% by mass, particularly preferably of> 3% by mass and particularly preferably of> 3.5% by mass, based on the total mass of the polymerizable composition, or in a total amount of> 1 to ⁇ 15% by mass, preferably from> 2 to ⁇ 15% by mass, particularly preferably from> 3 to ⁇ 15% by mass, very particularly preferably from> 3.5 to ⁇ 12% by mass, based on the total mass of polymerizable composition.
  • a polymerizable composition according to the invention was prepared from the components given below in Table 1 and homogenized by intensive mechanical mixing of the components with one another: Table 1: Components of a polymerizable composition according to the invention
  • An arrangement was provided of two transparent panes made of 5 mm thick toughened safety glass (ESG), which were arranged parallel to each other at a distance of 12 mm, so that there was a 12 mm wide, fillable space between the two panes (gap ) found.
  • ESG toughened safety glass
  • fire-resistant glazing according to the invention resulted.
  • the production process indicated above was repeated several times, the amount of glycerol used in the polymerizable composition being varied in the range from 6 to 10% by mass, based on the total mass of the polymerizable composition.
  • Example 2b Production with ready-mixed premix An arrangement of two transparent panes was provided, as described above in Example 2a.
  • This partially degassed premix was then intensively mechanically mixed with glycerol in the amount specified in Example 1, Table 1 (cf. component (E)) and with disodium peroxodisulfate as a radical initiator in the amount customary for this purpose using a filling pump system, and the composition thus obtained was also filled with the aid of the filling pump system into the gap of the arrangement described above until the gap was almost completely filled.
  • samples of further fire-resistant glazing BSV-1 to BSV-4 were produced, with the following parameters being varied: (i) the content of glycerol in the polymerizable composition used in each case and (ii) the gel strength, i.e. the width of the gap in the assembly of two transparent sheets into which the polymerizable composition has been filled.
  • the fire-resistant glazings obtained in each case in this way are given in Table 2 below.
  • Example 5 Adhesion test under non-fire conditions on a fire-resistant glazing according to the invention Another adhesion test of glass or glass splinters on a polyacrylamide hydrogel was carried out under non-fire conditions, with fire-resistant glazing of the type BSV-4 according to the invention (for the production see above in Example 3) was tested in a pendulum impact test according to DIN EN 12600: 2003-04. This test was carried out on five types of BSV-4 fire-resistant glazing at fall heights of 190 mm, 450 mm and 1200 mm. In no case was a breakage of the fire-resistant glazing found.
  • the glass of one of the fire-resistant glazings according to the invention tested as above was then broken by a stop mandrel in a vertical position in order to test the adhesion of the glass or the glass splinters to the polyacrylamide hydrogel. It was found that the resulting small glass splinters from the partially (mechanically) destroyed ESG glazing adhered very well to the polyacrylamide hydrogel.
  • Fire tests were carried out in order to check the quality of the fire protection effect of fire protection glazing according to the invention and also the quality of the adhesion of glass or glass splinters to polyacrylamide hydrogels according to the invention under fire conditions.
  • fire-resistant glazing of the types BSV-1, BSV-2, BSV-3 and BSV-4 were each based on the standards DIN EN 1363-1:2020-05 and DIN EN 1364-1:2015- 09 tested with the standard temperature curve (ETK).
  • thermocouples were attached to the surface of the pane on the side of the fire-resistant glazing to be tested, which was averted from the fire, in accordance with the standards mentioned.
  • the determined temperature data was recorded and then evaluated in accordance with the information in the standards referred to above.
  • the service lives given in Table 4 below were determined in accordance with or based on the standards specified above.
  • the average temperature from five measuring points was used as a basis.
  • the "standing time” was recorded as the length of time, beginning with the time when the temperature of 50 °C was reached inside the furnace until a temperature increase of 180 K compared to the temperature measured on the side facing away from the fire was reached on the side facing away from the fire at the beginning of the fire test.
  • Table 4 Results of fire tests
  • Example 2b three further samples of fire-resistant glazing, referred to as BSV-5 to BSV-7, were produced, the partially degassed premix each containing ethylene glycol (instead of glycerol) as the polyhydroxy compound in the amount given below in Table 5 (cf. component (E)) and with disodium peroxodisulfate as a free-radical initiator in the amount customary for this purpose using a filling pump system.
  • the composition obtained in this way was filled with the aid of the filling pump system into the intermediate space of an arrangement as described above under Example 2a until the intermediate space was almost completely filled.
  • Table 7 Results of fire tests with fire-resistant glazing BSV-6 and BSV-7 The results given above in Table 7 show that good or improved service lives and good or improved results with regard to the adhesion of glass or glass splinters are achieved with ethylene glycol as the polyhydroxy compound for fire-resistant glazing under fire conditions.

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne une composition polymérisable pour la production d'un hydrogel de polyacrylamide, un hydrogel de polyacrylamide correspondant, et un vitrage ignifuge comprenant une composition polymérisable mentionnée précédemment ou un hydrogel de polyacrylamide mentionné précédemment. L'invention concerne également un procédé de production d'un vitrage ignifuge ainsi que l'utilisation d'une composition polymérisable mentionnée précédemment et/ou d'un hydrogel de polyacrylamide mentionné précédemment, dans chaque cas comme agent ignifuge pour un vitrage ignifuge et/ou dans la production d'un vitrage ignifuge. L'invention concerne également l'utilisation d'un ou de plusieurs composés polyhydroxy, en particulier le glycérol, pour améliorer l'adhérence d'un hydrogel de polyacrylamide à un vitrage ignifuge.
EP22708155.1A 2021-03-01 2022-02-28 Composition polymérisable pour la production d'un hydrogel de polyacrylamide pour vitrage ignifuge, processus de production et utilisations correspondants Pending EP4301594A1 (fr)

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EP21159826.3A EP4052900A1 (fr) 2021-03-01 2021-03-01 Composition polymérisable destinée à la production d'un hydrogel de polyacrylamide pour un vitrage de protection contre l'incendie, procédés de fabrication et utilisations correspondants
PCT/EP2022/054938 WO2022184619A1 (fr) 2021-03-01 2022-02-28 Composition polymérisable pour la production d'un hydrogel de polyacrylamide pour vitrage ignifuge, processus de production et utilisations correspondants

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DE3530968A1 (de) * 1985-08-30 1987-03-12 Ver Glaswerke Gmbh Feuerwiderstandsfaehige verglasung
DE4137593C2 (de) * 1991-11-15 1994-01-20 Fraunhofer Ges Forschung Modifizierte, transparente, wässrige Alkalisilicat-Lösung, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von transparenten Hydrogelen
DE4435841A1 (de) 1994-10-07 1996-04-11 Flachglas Ag Brandschutz-Glaseinheit
GB0006443D0 (en) 2000-03-18 2000-05-10 Pilkington Plc Fire resistant glazings
DE10237395B4 (de) 2002-01-24 2012-12-20 C. G. I. International Limited Verfahren zur Herstellung einer Brandschutzverglasung und Brandschutzverglasung
DE102005018842B4 (de) 2005-04-22 2017-05-11 Hero-Glas Veredelungs Gmbh Polymerisierbare Zusammensetzung zum Herstellen eines Hydrogels, Hydrogel sowie Verwendung des Hydrogels
DE102006035262A1 (de) 2006-07-29 2008-01-31 Schott Ag UV-undurchlässige Brandschutzverglasung
CN105295742B (zh) 2015-11-18 2017-11-03 中国建筑材料科学研究总院 防火玻璃的防火胶及其制备方法以及复合防火玻璃

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