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EP4298146A1 - Composition ignifuge réactive - Google Patents

Composition ignifuge réactive

Info

Publication number
EP4298146A1
EP4298146A1 EP22710344.7A EP22710344A EP4298146A1 EP 4298146 A1 EP4298146 A1 EP 4298146A1 EP 22710344 A EP22710344 A EP 22710344A EP 4298146 A1 EP4298146 A1 EP 4298146A1
Authority
EP
European Patent Office
Prior art keywords
flame retardant
substituted
unsubstituted
reactive flame
polymer
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
EP22710344.7A
Other languages
German (de)
English (en)
Inventor
Andreas Moser
Gernot Peer
Christian Buchinger
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.)
Sunpor Kunststoff GmbH
Original Assignee
Sunpor Kunststoff 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 Sunpor Kunststoff GmbH filed Critical Sunpor Kunststoff GmbH
Publication of EP4298146A1 publication Critical patent/EP4298146A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties

Definitions

  • the present invention relates to a reactive flame retardant composition for vinyl polymers, a reactive flame retardant polymer, a use of the flame retardant composition and the flame retardant polymer, methods for producing flame retardant vinyl polymers, and flame retardant vinyl polymers.
  • Vinyl polymers are polymers made from vinyl monomers, which are mostly obtained by free-radical polymerization of the vinyl groups. Vinyl polymers find applications in numerous industrial sectors. Of particular relevance is the vinyl polymer polystyrene, which is used in particular as an insulating material.
  • Polystyrene is a thermoplastic polymer made from styrene monomers, which is usually available as granules with a density of approx. 1050 kg/m 3 . Polystyrene granulate is often further processed in a known manner for various applications. Depending on the type of processing, a distinction is made between expanded polystyrene (EPS) and extruded polystyrene (XPS).
  • EPS expanded polystyrene
  • XPS extruded polystyrene
  • XPS is produced in a known manner with an extruder by melting the raw granules and pressing the melt, in particular with a blowing agent, through a nozzle.
  • the homogeneous material foams up and can be removed from the process as a continuous part.
  • EPS is obtained in a known manner by expanding raw granules loaded with a blowing agent (for example with pentane) at temperatures above 90.degree.
  • the granules are usually pre-expanded in a first step.
  • the pre-expanded granules are further expanded in a hollow mold.
  • the expanded granulate particles fuse to form a cohesive molded body and form a particle of foam.
  • XPS and EPS moldings are often used for thermal insulation or impact sound insulation or as precisely fitting transport packaging for sensitive objects. Furthermore, moldings made of EPS are used for special applications, for example for helmets. In addition, such moldings can be used as a positive model in metal casting processes.
  • the invention proposes a reactive flame retardant composition for vinyl polymers.
  • the reactive flame retardant composition consists of at least a first monomer and a second monomer polymerizable with the first monomer, the first monomer having at least one aliphatic double bond and being polymerizable with the second monomer to form a reactive flame retardant polymer having an aliphatic double bond.
  • a vinyl polymer is understood to mean a polymer made from monomers which have a vinyl group, ie an ethene radical.
  • an aliphatic double bond is understood as meaning a carbon-carbon double bond of an aliphatic hydrocarbon.
  • an aromatic hydrocarbon can also have an aliphatic double bond if the carbon-carbon double bond is not part of the aromatic system.
  • an aliphatic double bond is also understood to mean a carbon-carbon double bond of a cycloaliphatic hydrocarbon, it being possible for the aliphatic double bond to also be provided within the ring structure of the cycloaliphatic hydrocarbon.
  • polymerizable is to be understood as meaning that the first and the second monomer each have reactive groups which can react with one another to form a bond between the first and second monomer, it being possible overall for a step-growth reaction to take place with the formation of an optionally branched polymer chain or A polymer network of interconnected first and second monomers.
  • the term reactive means that the flame retardant composition or the flame retardant polymer improves the flame retardancy and/or the dripping behavior of a polymer in the event of a fire by chemical reaction.
  • the reactive flame retardant composition described above can advantageously result in vinyl polymers having such a reactive flame retardant composition having improved fire retardant properties. Furthermore, can be achieved by the above-described reactive flame retardant composition that vinyl polymers having such a reactive flame retardant composition harden in a fire and flow less accordingly. As a result, it can advantageously be achieved that the vinyl polymer drips less in the event of a fire, as a result of which the spread of fire can be greatly reduced.
  • the reactive flame retardant composition which is present in a vinyl polymer at least partially as a reactive flame retardant polymer, can react in a fire with nascent vinyl radicals, which arise from a reaction of the vinyl polymer and vinyl polymers, vinyl oligomers or vinyl monomers of the vinyl polymer.
  • This binds the vinyl radicals to form a duromer, which greatly increases the viscosity of the melt produced during firing. The dripping of the melt during the fire can thus be greatly reduced and improved fire protection can result.
  • the vinyl polymer is a particle foam.
  • a particle foam is to be understood as meaning a polymer which can be expanded or has been expanded from granules to form a foam body.
  • the vinyl polymer is polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl acetate or polyacrylonitrile, as well as a copolymer and/or a mixture thereof.
  • the vinyl polymer is a polystyrene, particularly preferably expandable polystyrene (EPS).
  • polystyrene is also understood to mean copolymers of polystyrene, such as, for example, styrene-butadiene graft copolymers, styrene-butadiene block copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers and mixtures thereof.
  • the polystyrene is selected from the group consisting of crystal-clear polystyrene (GPPS), high-impact polystyrene (HIPS), anionically polymerized polystyrene or high-impact polystyrene (A-IPS), styrene-alpha-methylstyrene copolymer, acrylonitrile-butadiene-styrene polymer (ABS), styrene-acrylonitrile polymer (SAN), acrylonitrile-styrene-acrylic ester polymer (ASA), methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS) or mixtures thereof, and optionally blended with polyphenylene ether (PPE) or polyphenylene sulfide (PPS).
  • GPPS crystal-clear polystyrene
  • HIPS high-impact
  • the polystyrene mentioned may contain thermoplastic polymers such as polyamides (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT),
  • thermoplastic polymers such as polyamides (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate ( PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT),
  • Polyether sulfones PES
  • polyether ketones PES
  • polyether sulfides PES
  • mixtures thereof usually in proportions totaling up to less than or equal to 30% by weight, preferably in the range from greater than or equal to 1 to less than or equal to 10% by weight, based on the polystyrene.
  • the first monomer is a monomer of the general formula (I):
  • a 1 and A 2 each separately or linked together being a polymerizable group is meant that A 1 and A 2 are each a polymerized group or A 1 and A 2 are linked together to form a group which can be split into two Groups can be split, which in turn are each polymerizable.
  • a 1 and A 2 can together form a carboxylic acid anhydride which can react with cleavage with two monomers.
  • the reactive flame retardant composition described above can be achieved in that the reactive flame retardant composition can be converted particularly easily in a vinyl polymer to form a corresponding reactive flame retardant polymer.
  • this can advantageously result in the aliphatic double bond of the reactive flame retardant polymer corresponding to the aliphatic double bond of the first monomer.
  • the chemical properties of the aliphatic double bond of the reactive flame retardant polymer can advantageously be adjusted in a particularly simple manner.
  • a 1 and A 2 are each a carboxylic acid, an alcohol or an amine, or A 1 and A 2 together form a carboxylic acid anhydride.
  • the *-X-* is selected from the general formula (Ia), (Ib), (Ic) or (Id):
  • R 3 is selected from a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 heteroalkyl, a substituted or unsubstituted C6-C24 aryl, and a substituted or unsubstituted C6-C24 heteroaryl
  • R 4 is selected from H, halogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 heteroalkyl, a substituted or unsubstituted C6-C24 aryl, and a substituted or unsubstituted C6-C24 heteroaryl.
  • the aliphatic double bond of a corresponding reactive flame retardant polymer has a particularly positive influence on the drip properties of the vinyl polymer in the event of a fire.
  • B 1 and B 2 are each an epoxide, an alcohol, an amine, a carboxylic acid or an isocyanate. It was surprisingly possible to show that such second monomers can be incorporated particularly well into vinyl polymers and polymerized therein with the first monomers to form the reactive flame retardant polymer.
  • a 1 and A 2 are a carboxylic acid and B 1 and B 2 are each an epoxide, an alcohol or an amine; that A 1 and A 2 together form a carboxylic acid anhydride and B 1 and B 2 are each an epoxide, an alcohol, or an amine; that A 1 and A 2 are an alcohol and B 1 and B 2 are each a carboxylic acid; or that A 1 and A 2 are an amine and B 1 and B 2 are each an epoxide or a carboxylic acid.
  • the aforementioned combinations of first and second monomers can advantageously be achieved in that the reactive flame retardant composition can also be polymerized in a vinyl polymer to form the reactive flame retardant polymer using particularly simple means and under mild conditions.
  • a 1 and A 2 together form a carboxylic acid anhydride and B 1 and B 2 are each an epoxide.
  • the reactive flame retardant composition can be mixed particularly well with the vinyl polymer and can be polymerized particularly easily to give the reactive flame retardant polymer. Furthermore, it can be achieved that the mechanical properties of the vinyl polymer are changed as little as possible. In addition, the above-described flame retardant composition can achieve a particularly good increase in the viscosity of the melt of the vinyl polymer in the event of a fire, resulting in particularly improved flame retardant properties.
  • B 1 and B 2 are an epoxide and *-Y-* is a novolak.
  • novolaks are low molecular weight phenolic resins which have been obtained from phenols or phenol derivatives, such as cresols, and formaldehyde, and have a formaldehyde/phenol (derivative) ratio of less than 1:1.
  • the second monomer is an epoxidized novolak, ie for example an epoxy phenol novolak (EPN). It can thereby be achieved that the reactive flame retardant composition is particularly thermally stable.
  • EPN epoxy phenol novolak
  • B 1 and B 2 are an epoxide
  • *-Y-* has the general formula (Ha): [Formula Ha] wherein Z is selected from a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 heteroalkyl, a substituted or unsubstituted C6-C24 aryl, and a substituted or unsubstituted C6-C24 heteroaryl, where n is an integer greater than or equal to is equal to 0 to less than or equal to 60.
  • the viscosity of the reactive flame retardant composition can be adjusted.
  • small n can result in a low viscosity and thus possibly a high reactivity of the second monomer be reached.
  • Large n can result in the second monomer being a solid and the polymerization to form the reactive flame retardant polymer first having to be activated. This allows better control of the polymerization to be achieved.
  • *-B' and *-B 2 have the general formula (Ile): [Formula (Ile)]
  • the second monomer can be polymerized particularly easily with the first monomer.
  • the second monomer is an epoxy resin, for example a brominated epoxy resin, the second monomer being a brominated epoxy resin with the following formula in one embodiment
  • the second monomer is particularly easy to polymerize with the first monomer and, in addition to increasing the viscosity of the melt of the vinyl polymer provided with the corresponding reactive flame retardant polymer, additional flame retardancy can also be achieved through the formation of bromine-containing gases during combustion .
  • first monomers are particularly suitable for increasing the viscosity of the melt of a corresponding vinyl polymer particularly strongly in the event of a fire. Without being bound to a theory, it is assumed that the aliphatic double bond of such monomers allows the aliphatic double bond to remain particularly reactive for vinyl radicals in the corresponding reactive flame retardant polymer as well.
  • the first monomer is a diene, preferably selected from butadiene, isoprene and mixtures thereof
  • the second monomer has a vinyl group, the second monomer preferably being selected from styrene, ethylene, propylene and mixtures of them.
  • a reactive flame retardant polymer can also be obtained by the first and second monomers described above, which can increase the viscosity of the melt in the event of a fire in a vinyl polymer containing the reactive flame retardant polymer and can thus positively influence the drip and fire properties.
  • Flame retardant composition for reactive flame retardant polymer can also be mixed well in a vinyl polymer.
  • the reactive flame retardant composition has the polymerization catalyst in an amount of greater than or equal to 0.1% by weight to less than or equal to 20% by weight, based on the reactive flame retardant composition, preferably greater than or equal to 1% by weight. -% to less than or equal to 5% by weight, particularly preferably 2% by weight.
  • Flame retardant composition can be well controlled and at the same time the resulting flame retardant polymer is not too contaminated by remaining catalyst.
  • a 1 and A 2 together form a carboxylic acid anhydride
  • B 1 and B 2 are each an epoxide and the polymerization catalyst is an N-based catalyst, preferably an imidazole, particularly preferably isopropylimidazole.
  • Such catalysts are particularly suitable for the polymerization of such monomers, especially when the reactive flame retardant composition has already been introduced into a vinyl polymer and is to be polymerized to form the reactive flame retardant polymer.
  • the molar ratio of the reactive groups of the first monomer to the second monomer is greater than or equal to 1:5 to less than or equal to 5:1, preferably greater than or equal to 1:2 to less than or equal to 2:1, more preferably greater than or equal to 1:1.1 to less than or equal to 1.1:1, most preferably 1:1. What can thereby be achieved is that the degree of polymerization of the reactive flame-retardant polymer obtained from the reactive flame-retardant composition can be adjusted.
  • a reactive flame retardant polymer is also proposed with the invention.
  • the reactive flame retardant polymer is produced by polymerizing the reactive flame retardant composition described above, the reactive flame retardant polymer having an aliphatic double bond.
  • the reactive flame retardant polymer introduced into a vinyl polymer can react in the event of a fire with vinyl radicals that are produced. This binds the vinyl radicals to form a duromer, which greatly increases the viscosity of the melt produced during firing. The dripping of the melt during the fire can thus be greatly reduced and improved fire protection can result.
  • the reactive flame retardant polymer is an epoxy resin crosslinked with tetrahydrophthalic anhydride, for example a brominated epoxy resin crosslinked with tetrahydrophthalic anhydride.
  • the dripping behavior of the vinyl polymer in the event of a fire can be improved particularly well and the flameproofing polymer can be introduced into the vinyl polymer particularly easily.
  • the reactive flame retardant polymer is a styrene-butadiene-styrene (SBS) block copolymer, a styrene-isoprene-styrene (SIS) block copolymer, a rubber-modified polystyrene (high-impact polystyrene; HIPS ) or an ethylene-propylene-diene rubber.
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • HIPS high-impact polystyrene
  • ethylene-propylene-diene rubber ethylene-propylene-diene rubber
  • the above reactive flame retardant composition for vinyl polymers and the above reactive flame retardant polymer each serve to improve flame retardancy for vinyl polymers.
  • the invention thus also proposes the use of a reactive flame retardant composition as described above as flame retardant for vinyl polymers and products made from them, and the use of a reactive flame retardant polymer as described above as flame retardant for vinyl polymers and products made from them.
  • the invention also proposes a method for producing a flame retardant vinyl polymer.
  • a vinyl polymer is mixed with the reactive flame retardant composition described above with the input of energy, the reactive flame retardant composition polymerizing at least partially to form the reactive flame retardant polymer having an aliphatic double bond.
  • the reactive flame retardant polymer is thus only obtained in the vinyl polymer from the reactive flame retardant composition.
  • reactive flame retardant polymer in particular in comparison to commercially available unsaturated polymers homogeneously distributed in the vinyl polymer.
  • reactive flame retardant polymers with mechanical properties that differ significantly from those of the vinyl polymer can also be introduced homogeneously into the vinyl polymer.
  • reactive flame retardant polymers with significantly higher hardness or higher melting point can be well incorporated into the vinyl polymer because the blending is realized with the reactive flame retardant composition, which may have different mechanical properties than the reactive flame retardant polymer.
  • a vinyl polymer is mixed with the reactive flame retardant polymer described above.
  • the reactive flame retardant polymer is thus incorporated directly into the vinyl polymer.
  • the vinyl polymer with reactive flame retardant composition or reactive flame retardant polymer in an amount based on the vinyl polymer of greater than or equal to 1 wt .-% to less than or equal to 20 wt .-%, preferably greater than or equal to 3 wt .-% to less than or equal to 7% by weight, particularly preferably 5% by weight.
  • an extruder in particular with a twin-screw extruder
  • a polymer melt that is produced in the process preferably being conveyed through a nozzle plate and being granulated with a pressurized underwater granulator.
  • the reactive flame retardant composition can be polymerized in a simple manner and/or the reactive flame retardant polymer can be distributed homogeneously in the vinyl polymer.
  • the proposed extruder makes it possible to control the process in a particularly simple manner. Furthermore, it can optionally be achieved that a homogeneous granulate is obtained.
  • the method described above can be used to obtain polystyrene granules if the vinyl polymer is polystyrene, in particular expandable polystyrene granules if a blowing agent is added to the vinyl polymer or polystyrene.
  • the blowing agent is particularly preferably metered in in an amount of greater than or equal to 2% by weight to less than or equal to 10% by weight, based on the sum of the masses of the vinyl polymer, the reactive flame retardant composition or the reactive flame retardant polymer and the blowing agent.
  • the blowing agent can preferably be an aliphatic hydrocarbon having 2 to 7 carbon atoms, an alcohol, a ketone, an ether or a halogenated hydrocarbon.
  • the propellant can particularly preferably be isobutane, n-butane, isopentane or n-pentane.
  • the blowing agent can very particularly preferably be n-pentane.
  • additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and/or organic dyes and pigments can be added to the vinyl polymer in the extruder together or separately, e.g. via mixers or side extruders. be admitted.
  • the dyes and pigments are added in amounts ranging from 0.01 to 30% by weight, based on the vinyl polymer, preferably in the range from 1 to 10% by weight.
  • a dispersing agent e.g.
  • organosilanes polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
  • Preferred plasticizers are mineral oils, phthalates, which can be used in amounts of 0.05 to 10% by weight, based on the vinyl polymer.
  • the invention also proposes a flame retardant vinyl polymer.
  • the flame-retardant vinyl polymer was produced according to the process described above, with the vinyl polymer having the reactive flame retardant polymer described above and optionally having an additional flame retardant.
  • the flame-retardant vinyl polymer described above can advantageously have better dripping behavior in the event of a fire than known flame-retardant vinyl polymers.
  • An additional flame retardant can further improve the flame retardant properties of the flame-retardant vinyl polymer in a known manner.
  • the additional flame retardant can be brominated styrene-butadiene copolymer.
  • a flame-retardant polystyrene granulate is also proposed with the invention. The flame-retardant polystyrene granulate was produced as described above, with the vinyl polymer being polystyrene, and has the reactive flame-retardant polymer described above and optionally an additional flame-retardant.
  • the above-described flame-retardant polystyrene granules can advantageously have improved dripping behavior in the event of a fire compared to known flame-retardant polystyrene granules.
  • the invention also proposes a molded body made of expanded, flame-retardant polystyrene granules, the molded body having been produced with the flame-retardant polystyrene granules described above, in particular with the flame-retardant, expandable polystyrene granules.
  • the mixture was melted in the extruder at 170.degree.
  • the polymer melt obtained in this way was conveyed through a nozzle plate at a throughput of 15 kg/h and granulated using a pressurized underwater granulator to give compact EPS granules.
  • the EPS granules obtained in this way had improved flame retardancy and drainage properties compared to EPS granules produced without a reactive flame retardant composition.
  • Example 2 Analogously to Example 1, additives were added in the intake area of a twin-screw extruder which, in contrast to the subject invention, cannot be polymerized to form a reactive flame-retardant polymer having an aliphatic double bond and do not form a flame-retardant composition for the purposes of the present invention.
  • 1% by weight of phthalic anhydride (PA) was used as the first polymer instead of THPA, which, in contrast to tetrahydrophthalic anhydride (THPA), contains no aliphatic double bond.
  • the second monomer used was again 4% by weight of F2200HM and the polymerization catalyst was also 0.1% by weight of isopropylimidazole, based on the total amount of the EPS granules obtained.
  • the EPS granules produced from example 1, reference example 1 and a commercially available EPS granulate were used at 2 melted directly on a hot plate at different temperatures.
  • the temperatures selected were 240° C. and 280° C., and 2 g of the EPS granules were melted for 5 minutes (measured after a homogeneous melt was obtained). The samples treated in this way were subsequently examined further.
  • a TA Instruments HR 20 rheometer was used for this, which was used with a 25 mm plate-plate system with a 1 mm gap spacing at 180°C. The deflection during the measurement was 1% and the shear rate range from 0.01 Hz to 100 Hz was measured.
  • Table 1 shows the dynamic viscosity (h) at 1 Hz and the frequency intercept (Fs) of the storage modulus and loss modulus.
  • Table 1 shows a clear influence of the subject according to the invention both on the dynamic viscosity and on the frequency intersection point. While the viscosity of example 1 is already -40% higher at a melting temperature of 240° C., the difference at a melting temperature of 280° C. is particularly evident compared to the reference example without a polymerizable double bond. Here the increase in Example 1 is already 240%, while an increase in viscosity of 24% can also be determined for the commercial product.
  • the frequency intercept of the storage modulus and loss modulus is a measure of the molecular mobility at a given temperature. While a completely continuous network, e.g. with duromers, means that the storage modulus is above the loss modulus even at the lowest frequencies and all temperatures, with thermoplastics the temperature, the molecular weight and any gel fractions are very important. Thus, the crossover point is a good measure of the effectiveness of the subject invention.
  • Table 1 shows that example 1 has a significantly lower frequency crossing point than the commercial product and the reference example at both 240 °C and 280 °C melting temperature. This clearly shows that the molecular mobility is significantly restricted and a reaction has taken place in the simulated fire.
  • the flame retardant compositions according to the invention accordingly show improved run-off properties in the event of fire for vinyl polymers, in particular also compared to compositions which differ from the compositions according to the invention only in that the first monomer has no aliphatic double bond.

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une composition ignifuge réactive pour des polymères vinyliques, composée d'au moins un premier monomère et d'un deuxième monomère polymérisable avec le premier monomère, le premier monomère présentant au moins une double liaison aliphatique et pouvant être polymérisé avec le deuxième monomère en un polymère ignifuge réactif présentant au moins une double liaison aliphatique. L'invention concerne en outre un polymère ignifuge réactif obtenu par polymérisation de la composition ignifuge réactive, une utilisation de la composition ignifuge et du polymère ignifuge, un polymère vinylique ignifuge qui présente le polymère ignifuge réactif, et un procédé pour sa préparation. Les objets de l'invention permettent en particulier de diminuer avantageusement la formation de gouttes de polymères vinyliques en cas d'incendies et ainsi d'améliorer l'ignifugation de tels polymères.
EP22710344.7A 2021-02-26 2022-02-24 Composition ignifuge réactive Pending EP4298146A1 (fr)

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DE102021104714.5A DE102021104714A1 (de) 2021-02-26 2021-02-26 Reaktive Flammschutzzusammensetzung
PCT/EP2022/054634 WO2022180156A1 (fr) 2021-02-26 2022-02-24 Composition ignifuge réactive

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CN (1) CN116670230A (fr)
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WO (1) WO2022180156A1 (fr)

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JPS5220513B2 (fr) * 1975-03-05 1977-06-03
JPH08248630A (ja) * 1995-03-07 1996-09-27 Hitachi Chem Co Ltd フォトビア形成用感光性エレメント
ES2142606T3 (es) 1995-09-07 2000-04-16 Bromine Compounds Ltd Materiales ignifugos de hexabromociclododecano con estabilidad termica.
US6583205B2 (en) * 2001-05-07 2003-06-24 General Electric Company Flame retardant expandable poly(arylene ether)/polystyrene compositions and preparation thereof
EP1405879A4 (fr) * 2001-09-10 2006-06-21 Win Tech Polymer Ltd Composition ignifugeante de resine de polyethylene terephthalate
RU2528677C2 (ru) 2008-12-18 2014-09-20 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи Стабилизаторы для полимеров, содержащих бром алифатического присоединения
DE102009059781A1 (de) * 2009-12-18 2011-06-22 Basf Se, 67063 Flammgeschützte Polymerschaumstoffe
ITMI20121973A1 (it) 2012-11-20 2014-05-21 Versalis Spa Composizione polimerica autoestinguente
TWI557177B (zh) 2015-12-16 2016-11-11 財團法人工業技術研究院 低介電無溶劑型樹脂組成物及基板結構
KR102524392B1 (ko) * 2018-10-19 2023-04-20 재팬 콤퍼짓 가부시키가이샤 불포화 폴리에스터 수지 조성물, 성형 재료, 성형품, 및 전동 차량의 배터리 팩 하우징

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DE102021104714A1 (de) 2022-09-01
CN116670230A (zh) 2023-08-29

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