EP3740516A1 - Phosphorhaltige thermoplastische polymere - Google Patents
Phosphorhaltige thermoplastische polymereInfo
- Publication number
- EP3740516A1 EP3740516A1 EP19700367.6A EP19700367A EP3740516A1 EP 3740516 A1 EP3740516 A1 EP 3740516A1 EP 19700367 A EP19700367 A EP 19700367A EP 3740516 A1 EP3740516 A1 EP 3740516A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- flame retardant
- compounds
- weight
- melamine
- 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- Withdrawn
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the invention relates to a phosphorus-containing polymer based on an acrylate, a process for the preparation of the polymer, the use of the polymer and the polymer-containing flame retardants and plastic compositions.
- the polymer according to the invention is uncrosslinked or only slightly crosslinked.
- the polymer is useful as a flame retardant and for use in flame retardants for plastics.
- halogen-free substances are used to prevent the formation and release of HX gases and other toxic compounds.
- the known halogen-free flame retardants include those based on metal hydroxides, organic or inorganic phosphates, phosphonates or phosphinates and derivatives of 1, 3,5-triazine compounds and mixtures thereof.
- some monomeric, low molecular flame retardant additives are known, but due to their strong plasticizer effect lead to significant deterioration of the material properties of the plastic matrix to be protected both in processing and in use.
- low molecular flame retardant additives due to their tendency to migrate in the plastic material, which can lead to aggregation (less good distribution of the flame retardant additive) or leaching (migration to the surface and possibly escape from the plastic), their flame retardancy decreases after a certain period of time. Leaching may also result in contact of the plastic flame retardant additives with the environment.
- polymers containing high molecular weight flameproofing additives generally have only minor plasticizer effects and low migration capacity.
- low-molecular flame retardant additives they are often less compatible with the plastic to be protected during industrial processing, especially if the melting point is low.
- a polyester is known which is obtained by Michael addition of 6H-dibenz [c, e] [1,2-oxaphosphorine 6-oxide (DOPO) to an itaconic acid and subsequent polycondensation with ethylene glycol becomes.
- this polymer When using this polymer in a plastic matrix, such as a polyester or a polyamide, this has übli Chen extrusion conditions (250 to 270 ° C) on a sticky and strongly adhering consistency, which increased clogging and sticking (clogging) especially in the metering area of parts of the extrusion apparatus is observed.
- this polymer decomposes already from temperatures of about 300 ° C, so that the use in Kunststoffmatrizes that are processed at very ho hen temperatures, such as polyamide 6.6 (PA 6.6) and very special high-temperature polyamides such as polyamide 4.6, not possible is.
- the polymer contains only one phosphorus-containing group per repeat unit. The maximum phosphorus content is 8.5% by weight.
- thermosetting phosphorus-containing flame retardants which are obtained by radikali cal polymerization of polyfunctional acrylates.
- the synthesis of these flame retardants involves a two-step process involving the addition of an organophosphorus compound to a portion of the acrylate groups and the subsequent radical polymerization of the remaining acrylate groups.
- these thermoset phosphorus flame retardants have a high decomposition temperature of at least 300 ° C, but they are not meltable due to their thermoset structure and therefore not miscible with the plastic matrix, which is to be flame retardant. Therefore, they can only be incorporated as solid particles in the plastic matrix.
- the object of the present invention was therefore to provide a comparison with the prior Tech nik improved phosphorus-containing polymer, which has similar or even better flame retardancy than the compounds of the prior art and a very good Miscibility with the plastic to be protected in order to overcome the above problems.
- R 1 is hydrogen, a C 1 -C 6 -alkyl, a C 6 -C 12 -aryl or a C 6 -C 12 -alkylaryl,
- R 4 is hydrogen, -CH 2 OH, -OH, a C 1 -C 6 -alkyl, a C 6 -C 12 -aryl, a C 6 -C 12 -alkylaryl or
- R 6 and R 7 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 6 -C 12 -aryl or C 6 -C 12 -alkylaryl and n in the compounds according to the formulas I and III or the mixtures of compounds according to the formulas I and III, an average chain length in the range of 1 to 100, preferably 1 to 10, particularly preferably 1 to 3, represented, characterized in that the average number of R 3 radicals of the formula
- the polymer is a thermoplastic.
- the polymers according to the invention are linear or branched thermoplastics with a low degree of crosslinking, which in the case of amorphous thermoplastics in a temperature range above the glass transition temperature (T g ), in the case of crystalline or semicrystalline thermoplastics above the melting temperature (T m ) are in principle viscous flowable and to be deformed.
- This deformation process is reversible, that is, it can be repeated as many times as required by cooling and rewarming in the molten state, as long as not through overheating the thermal decomposition of the material begins.
- thermoplastics can be easily processed, for example by pressing, extruding, injection molding or other molding process.
- the polymers according to the invention can very easily be homogeneously mixed and processed under suitable conditions with meltable plastic matrices in the molten, flowable state. In this way, a uniform flame retardancy even in plastic matrices can be achieved with very thin dimensions and avoided the above problems in the processing of Kunststoffmatrizes who the.
- plastic matrix in the sense of this invention encompasses any plastic or any mixture of plastics into which the polymer according to the invention can be incorporated.
- the polymers according to the invention have both a high thermal stability and a very good flameproofing effect. It would have been expected that an inventive Po lymer decomposes compared to the thermosets from the prior art at significantly lower temperatures and thus in the range of processing temperatures of common plastic matrices. The flame retardant effect would have been significantly reduced or even vollkom missed men.
- the thermoplastic according to the invention is obtainable by the above-described sequence of reac tion steps, in which in the first step, an organophosphorus compound of formula II in a phospha-Michael addition to a polyfunctional acrylate compound of the formula I is added.
- the reaction of a compound of the formula I leads the 4 CC double bonds in structural elements of the form having three equivalents of a compound of the formula II to give a compound of the formula III having an average number of carbon atoms
- the substances which are suitable as compounds of the formula II according to the invention are 6H-dibenzo [c, e] [1,2] -oxaphosphorine 6-oxide (DOPO, CAS No. 35948-25-5), diphenylphosphine oxide (DPhPO, CAS No. 4559-70-0), 5,5-dimethyl-1,2,3-dioxophosphorinane-2-oxide (DDPO, CAS No. 4090-60-2), preferably DOPO.
- the phospha-Michael addition in the first step and the free-radical polymerization in the second step take place under reaction conditions which are known to those skilled in the Einzelreaktio NEN.
- the two steps are carried out in organic solvents such as example toluene.
- the reaction is preferably carried out by adding the compound of formula II to the compound of formula I with stirring. Furthermore, the addition of the compounds of the formula II is preferably carried out in portions in several steps, more preferably continuously in within several minutes, most preferably within several hours. By means of one of these or a combination of these addition conditions, it is ensured that no larger amounts of unreacted compound of the formula II are accumulated in the reaction mixture, so that the individual CC double bonds in structural elements of the formula rL " in the compound of the formula I react stepwise with the compound of formula II, ie that first the first carbon i /
- Control of the completeness of the phospha-Michael addition process and formation of a substantially uniform product is accomplished by techniques known to those skilled in the art, preferably by NMR spectroscopy, more preferably by 1 H NMR spectroscopy and / or 31 P NMR spectroscopy.
- the polymerization reaction of the second step is initiated by means of free-radical or ionic initiators.
- free-radical initiators such as azobis (isobutyronitrile) (AIBN), dibenzoyl peroxide or peroxodisulfate.
- the polymerization reaction can be initiated by the action of radiation, heat and / or a catalyst.
- the polymer according to the invention is produced in pure form after the second reaction step and requires no further purification.
- Solvents can be contained in particular only by incorporation, which, however, can be removed by a subsequent drying step.
- Such a drying step is preferably carried out at temperatures in the range of about 200 ° C to 270 ° C, preferably under vacuum or reduced pressure in the range of about 1 mbar to 10 mbar.
- the polymer according to the invention has a similar high, sometimes even higher, thermal stability than the thermosets known from the prior art.
- the thermoplastic has a higher residual mass after decomposition. This is advantageous in the event of a fire because it results in less development of flue gases.
- the polymer according to the invention preferably has a decomposition temperature of at least 320 ° C on. More preferably, the decomposition temperature is at least 340 ° C, most preferably at least 370 ° C.
- the polymer is particularly suitable for incorporation into a plastic matrix which is to be processed by extrusion, since it does not decompose at the usual processing temperatures for the extrusion, but unfolds only at the higher temperatures occurring during fires and then its flame retardant effect.
- the decomposition temperature of the polymer is determined using the thermogravimetric analysis method described in the section Measuring Methods.
- the decomposition temperature is the temperature at which, at a heating rate of 10 K / min, a dry matter mass loss of 2% is achieved.
- the polymer of the invention is soluble in a variety of common solvents such as DMSO, DMF, CHCl 3 or THF and can therefore be processed very easily, but also analyze. For example, a chromatographic purification of the polymer obtained can be carried out so that it can be used in applications which require a particularly high purity, for example in medical technology.
- the decomposition temperature of the polymer is higher than the processing temperature of the plastic matrix in the thermal processing process by which the polymer is to be incorporated into the plastic matrix. This ensures that no decomposition processes of the polymer take place when the processing temperature of the plastic matrix is reached.
- the decomposition temperature of the polymer is above 10 ° C above the processing temperature of the plastic matrix, more preferably above 20 ° C above the processing temperature of the plastic matrix, most preferably above 50 ° C above the processing temperature of the plastic matrix.
- the difference between the decomposition temperatures of the polymer and the plastic matrix is less than 100 ° C, more preferably less than 50 ° C, most preferably less than 20 ° C.
- the meltability and flowability of the polymer according to the invention and the consequent good miscibility with the plastic matrix, in which the polymer is incorporated, ensure that in Thermal processing method, the melt viscosity of the plastic matrix is hardly affected, so that unlike the flame retardants of the prior art, no problems occur in thermal processing.
- a strong pressure drop at the spinneret during melt spinning which can lead to capillary breakage of the fibers among other things, upon addition of the polymer according to the invention or at least to a lesser extent than with the flame retardants according to the prior art observed.
- bonds and Verstopfun conditions that can lead to pressure fluctuations during thermal processing, do not occur or at least to a lesser extent than with the flame retardants according to the prior art.
- the homogeneous mixing of the plastic matrix to be provided with flame retardant with the polymer according to the invention achieves a uniform distribution of the flame retardant. This makes it possible to effectively protect even plastic matrices with thin dimensions such as films, fibers or foams. Due to the homogeneous mixing can continue to avoid a Ver blockage of the melt filter in plastic processing machines.
- a copolymer By adding one or more methacrylates and / or acrylates of the general structure IV before the second step, a copolymer can be obtained and thereby the thermal and mechanical properties such as the glass transition point (T g ), the melting point (T m ) or the modulus of elasticity to be influenced. Furthermore, the compatibility with the plastic matrix can be improved.
- the polydispersity index (PDI) of the polymer is at most 10, more preferably at most 5, most preferably at most 2.5.
- a low PDI enables a uniform melting and flow behavior of the polymer, so that it can be processed better.
- the PDI can be determined according to methods which are familiar to the person skilled in the art, such as, for example, size exclusion chromatography (GPC) in conjunction with customary analytical methods such as light scattering, viscometry, NMR spectroscopy, IR spectroscopy or the like.
- GPC size exclusion chromatography
- the polymer preferably contains two phosphorus-containing groups per repeat unit. unit, more preferably three, more preferably four.
- the phosphorus content of the polymer is preferably at least 8.5% by weight, more preferably at least 8.75% by weight, and most preferably at least 9% by weight, based on the total weight of the polymer.
- the compound of the formula I is selected from pentaerythritol tetraacrylate (PETA), dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate and tris (2-acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate (PETA, CAS No. 4986-89-4), dipentaerythritol pentaacrylate (DPPA, CAS No. 60506-81-2), dipentaerythritol hexaacrylate (DPEHA, CAS No.
- PETA pentaerythritol tetraacrylate
- DPPA dipentaerythritol pentaacrylate
- DPEHA dipentaerythritol hexaacrylate
- TMPTA trimethylolpropane triacrylate
- TMP-TMA trimethylolpropane trimethacrylate
- TEICTA 2, 3-acyloxyethyl isocyanurate
- PETA pentaerythritol tetraacrylate
- DPEHA dipentaerythritol hexaacrylate
- TEEICTA tris (2-acryloxyethyl) isocyanurate
- mixtures of the compounds of the formula I can also be used.
- a molar amount of compound of formula II is used, so that the average number of C-C double bonds in structural elements of the
- Form of the compound of formula III after the first step is 0.8 to 1.3, before the first step, the average number of C-C double bonds in structural elements of
- the reaction in the first step takes place with a catalyst.
- a catalyst is a chemical by the addition of a certain chemical cal reaction is only possible or in the presence of a reaction faster, since only a lower activation energy must be expended, as would be the case in the absence of the catalyst.
- the catalyst is selected from tertiary amines and tertiary amino bases, particularly preferred is triethylamine.
- the polymerization reaction is carried out in an emulsion or suspension, more preferably in toluene or xylene.
- the soluble in these Lö seffen soluble thermoplastic in pure form, so that only the solvent removed and the polymer must be dried.
- the number average molecular weight of the polymer, Af n is at least 5,000 g / mol, more preferably at least 10,000 g / mol, particularly preferably at least 20,000 g / mol.
- the number average molecular weight of the polymer ( s ) can be determined by the methods common to the person skilled in the art. Due to the high accuracy, in particular absolute methods of molecular weight determination are suitable for the determination. Examples include membrane osmosis and static light scattering.
- the present invention also encompasses a process for the preparation of the polymer according to the invention with the process measures described above.
- the second step is carried out with addition of one or more methacrylates and / or acrylates of general structure IV
- the invention further comprises a flame retardant composition containing the polymer of the invention. It has been found that the polymer can be used with advantage as or in a flame retardant, in particular for plastic compositions.
- the polymer can advantageously be used in combination with other flame retardants, for example those which, as a result of their decomposition at high temperatures, lead to a layer formation on the surface of the plastic matrix provided with the flame retardant. As a result, a further burning of the plastic matrix is possibly prevented.
- other flame retardants for example those which, as a result of their decomposition at high temperatures, lead to a layer formation on the surface of the plastic matrix provided with the flame retardant. As a result, a further burning of the plastic matrix is possibly prevented.
- flame retardants that cause flame retardance by another mechanism use. Due to the interaction of the polymer with other flame retardants, a synergistic effect can be achieved. Without being bound by theory, this seems to cause that in case of fire, the decomposition temperatures of the polymer and the other flame retardant, with which the polymer is combined, are lowered, and thus are closer to the decomposition temperature of the polymer matrix. As a result, the flame retardant effect can be increased.
- the polymer according to the invention can be used as a replacement for the harmful synergist antimony trioxide (Sb 2 0 3 ).
- the polymer has, as shown in the flame retardant, a synergistic effect in combination with halogenated flame retardants, in particular with bromine-containing flame retardants, such as the brominated polyacrylate FR 1025 Fa. ICL, the brominated polystyrene FR-803P Fa. ICL or polymerized bromine-containing epoxy F-2100 Fa. Bromine Compounds Ltd.
- a further advantage is that no additional anti-drip agent is necessary in these combinations, since the Po lymer-containing flame retardant composition itself prevents dripping or re Jerusalem.
- the flame retardant composition contains presents least one further flame retardant component, which is preferably selected from nitrogen bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and anor ganic phosphinates, organic and inorganic phosphonates and derivatives of the aforementioned compounds, preferably selected from Ammonium polyphosphate, with melamine, melamine resin, melamine derivatives, silanes, siloxanes, silicones or polystyrenes coated and / or coated and crosslinked ammonium polyphosphate particles, and 1, 3,5-triazine compounds, including melamine, melam, meiern, melon, ammeiin, ammelide, 2 Uridomelamine, acetoguanamine, benzoguanamine, diaminophenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyro
- the flame retardant composition preferably contains melamine polyphosphate as further flame retardant component.
- melamine polyphosphate as further flame retardant component. This can advantageously be used, for example, when used in a polyamide 6.6 plastic matrix, since the combination of flame retardant composition with melamine polyphosphate produces a synergistic system which has a decomposition temperature which falls within the decomposition temperature range of polyamide 6.6.
- the ratio of polymer to the at least one further flame retardant component in the flame retardant composition is from 1: 18 to 1: 4, preferably 1: 9 to 1: 4, and more preferably 1: 6 to 1: 4. These conditions also apply to the use of melamine polyphosphate as a further flame retardant component.
- the invention further includes the use of the polymer as a flame retardant or in a flame retardant composition in the manufacture of plastic compositions.
- polymers according to the invention have advantageous properties, in particular in the production of plastic compositions by the extrusion process. Without significantly affecting the processing properties of the different Kunststoffmatrizes, the polymers can be incorporated easily in these methods. When using the polymers, the thermal and mechanical properties of the plastic matrix are only slightly affected after processing.
- Plastic matrices in which the polymer can be used as a flame retardant or in a flame retardant composition are preferably selected from filled and unfilled vinyl polymers, olefin copolymers, olefin-based thermoplastic elastomers, crosslinked olefin-based thermoplastic elastomers, polyurethanes, filled and unfilled polyesters and copolyesters , Styrene block copolymers, filled and unfilled polyamides and copolyamides, polycarbonates and poly (meth) acrylates. Particularly preferred is the use in polymethacrylates and polyacrylates, most preferably in polymethyl methacrylates. In this context, it is particularly advantageous that the addition of the polymer according to the invention leads to a transparent polymethacrylate or polyacrylate.
- the polymer and polymer-containing flame retardant compositions are useful for any plastic matrices. They are useful as flame retardants for polyamides, polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyolefins such as polypropylene (PP), polyethylene (PE), polystyrene (PS), styrene block copolymers such as ABS, SBS, SEES, SEPS , SEEPS and MBS, polyurethanes (PU), in particular PU hard and Flexible foams, poly (meth) acrylates, polycarbonates, polysulfones, polyether ketone, polyphenylene oxide, polyphenylene sulfide, epoxy resins, polyvinyl butyral (PVB), polyphenylene oxide, polyacetal, polyoxymethylene, polyvinyl acetal, polystyrene, acrylic butadiene styrene (ABS), acrylonitrile Sty
- PBT
- polystyrene resin particularly suitable is the use of the polymer according to the invention in Kunststoffmatrizes that are processed at very high temperatures, such as polyamides or polyesters, particularly preferred is the use in PA 6.6 or PA 6 or in the high temperature tur polyamides, such as polyamide 4.6, partially aromatic polyamides and polyamide 12. Due to the high thermostability of the polymer, this can also be used for such plastics.
- the plastic matrix is selected from filled or un-filled and / or reinforced polyamides, polyesters, polyolefins and polycarbonates.
- a filled plastic matrix is understood as meaning a plastic matrix which contains one or more fillers, in particular those selected from the group consisting of metal hydroxides, in particular alkaline earth metal hydroxides, alkali metal hydroxides and aluminum hydroxides, silicates, in particular phyllosilicates and functionalized phyllosilicates such as nocompositen, bentonite, alkaline earth metal silicates and alkali metal silicates, carbonates, in particular calcium carbonate, and talc, clay, mica, silica, calcium sulfate, barium sulfate, alumi niumhydroxid, magnesium hydroxide, glass fibers, glass particles and glass beads, wood flour, Zellulo sepulver, carbon black, graphite, boehmite and dyes ,
- fillers in particular those selected from the group consisting of metal hydroxides
- All of the listed fillers can be used both in fillers of conventional shape and size known to those skilled in the art, as well as in nanoscale form, i. as particles with an average diameter in the range of about 1 to about 200 nm, and are used in the Kunststoffzu compositions.
- glass fibers are preferably added as filler.
- the polymer is in an amount of 1 to 20 wt .-%, preferably be between 1 and 15 wt .-%, more preferably 1 to 10 wt%, based on the total weight of the total weight of the plastic composition with polymer introduced , These proportions cause a good flame retardancy of the polymer and at the same time prevent a significant change in the properties of the plastic matrix both during processing and during use, in particular with regard to the mechanical properties and the heat stability.
- the polymer is introduced into the plastic matrix in a flame retardant composition with further flame retardants, the flame retardant composition preferably being used in an amount of from 2 to 30% by weight, preferably from 5 to 25% by weight, particularly preferably from 10 to 25 % By weight, most preferably 15 to 25% by weight, based on the total weight of the plastic composition having Flammtikstoffzusam composition, is contained in the plastic composition.
- plastic composition which contains the above-illustrated poly mer.
- the compound of formula III exactly a free CC-double bond in the structural units of the form rL "in.
- the second step is then a linear, unbranched polymer of structure V
- PETA Technical acrylate mixture from Arkema, consisting of pentaerythritol tetraacrylate and pentaerythritol trisacrylate. The determined by HPLC and 1 H-NMR analysis molar ratio of pentaerythritol tetraacrylate to pentaerythritol trisacrylate unge about 2: 1.
- THEICTA Tris [2- (acryloyloxy) ethyl] isocyanurate (CAS: 40220-08-4) from Sigma-Aldrich (product number: 407534) having an average acrylate functionality of about 2.9.
- DPEHA Technical acrylate mixture from Allnex from dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. The determined by HPLC and 1 H-NMR analysis Molver ratio of dipentaerythritol hexaacrylate to dipentaerythritol pentaacrylate is unge about 3: 2.
- SR 295 Technical acrylate mixture SR 295 from Arkema with the main constituent pentaerythritol tetraacrylate and an average acrylate functionality of about 3.5.
- TMP-TMA trimethylolpropane trimethacrylate (CAS: 3290-92-4) from Sigma-Aldrich (product number: 246840) with an average methacrylate functionality of about 2.9.
- DOPO 6H-dibenz [c, e] [1,2] -oxaphosphorine-6-oxide (CAS: 35948-25-5) from Euphos HCA.
- DDPO 5,5-dimethyl-1,3-dioxo-phosphorinane-2-oxide (CAS: 40901-60-2).
- DSC Differential Scanning Calorimetry
- Thermoqravimetric analyzes were carried out with a TGA Q500 V6.4 (TA Instruments, USA) in the range of 25 to 800 ° C under a nitrogen atmosphere at a heating rate of 10 K / min. The weight of the samples was 12-15 mg. To evaluate the TGA curves, the software TA Universal Analysis 2000, Version 4.2E (TA Instruments) was used.
- Example 0 Synthesis of a partially crosslinked polyacrylate based on PETA
- Example 1 Synthesis of a fusible polyacrylate based on DPEHA
- reaction mixture was heated under nitrogen supply (low boiling, heating bath temperature 1 15 ° C) and stirred for 2 hours at a constant temperature. Then, the heating bath temperature was raised to 125 ° C, so that more vigorous boiling occurred. Subsequently, 5 g of a 0.2 molar AIBN solution in toluene was added portionwise over 5 minutes. It was lively, so that both Phases mixed emulsion-like. Within about 10 minutes, a viscous sub stance separated, which became tougher in the course of further heating and at the piston bottom ansam melte. After the reaction mixture was heated to reflux for 90 minutes, the heating was turned off.
- the toluene phase was separated by decantation and transferred the viscous substance in a coated metal shell. First, it was dried in air, then heated in a vacuum oven for about 14 hours at 150 ° C, the pressure was slowly reduced to about 10 mbar (initially the substance foamed and ballooned on). It was then heated to 215 ° C for 4 hours at about 10-13 mbar. After cooling and milling, the thermoplastic was obtained as a white, chloroform-soluble solid (276 g, 95% yield).
- Example 3 Synthesis of a meltable polyacrylate based on THEICTA
- the mixture was stirred at 95 ° C for a further 1 h.
- the reflux condenser was equipped with a nitrogen supply line and turned off the heater.
- the product phase collected at the bottom of the flask.
- the product phase and the overlying phase were examined by NMR spectroscopy, whereby a complete conversion of the DOPOs was found.
- the contents of the flask were stored overnight at room temperature.
- reaction mixture was heated to 90 ° C over 30 minutes. Then it was stirred for 1.5 hours at 90-95 ° C under a nitrogen atmosphere. The flask contents were stirred vigorously to form a milky emulsion. After the reaction mixture was heated to reflux, 3.0 g (3.5 ml) of a 0.2 molar AIBN solution was added over 3 min. The polymerization started immediately. After 10 min was a add a second portion of AIBN (1 g) and after a further 5 min add a third portion (1 g). In the course of the polymerization process, the reaction mixture became increasingly viscous, but it could still be stirred (at reduced stirrer speed). Stirring was continued for a further 2 hours.
- Example 6 Synthesis of a meltable polymethacrylate based on TMP-TMA
- V-0 means that the total burning time of 5 test specimens tested was less than 50 seconds and the cotton ball was not ignited by dripping glowing or burning components of the specimen.
- the rating V-1 means that the total burning time of 5 test specimens tested was more than 50 seconds but less than 250 seconds and just if the cotton ball was not ignited.
- V-2 means that the total burning time of 5 tested specimens was less than 250 seconds, the cotton ball through dripping test specimen components was ignited in at least one of the 5 tests.
- NC stands for "not classifiable” and means that a total burning time of more than 250 seconds was measured. In many cases of non-classifiability, the specimen burned completely.
- plastic matrices were used in the examples below for the preparation of the flameproofed plastic compositions:
- MPP melamine polyphosphate Budit 342 from the company Chemische Fabrik Budenheim
- MC Melamine cyanurate Budit 315 from the company Chemische Fabrik Budenheim
- ZPP Zinc pyrophosphate Budit T34 from the company Chemische Fabrik Budenheim
- Exolit Exolit OP 1230, organic phosphinate from Clariant
- P-T P-containing thermoplastic according to the invention, prepared according to Example 5
- Example 7 Replacement of antimony oxide in flame-retardant glass fiber-reinforced PBT test bodies
- PBT 35GF Glass fiber reinforced PBT compounds (PBT 35GF) were produced using a twin-screw laboratory extruder Process 1 1 (Thermo Scientific) under the usual PBT extrusion conditions. The extrusion process was carried out at a rate of about 300 g per hour and a temperature of 260-265 ° C to obtain granules having a grain size of about 3x1x1 mm, from which good quality UL94 test specimens were produced by hot pressing. The thickness of the test specimens was 1, 6 mm.
- the DOPO-functionalized polyacrylate prepared according to Example 5 was incorporated together with the bromine-containing flame retardant poly (pentabromobenzyl acrylate) (FR1025, ICL Industrial).
- test specimens # 2 and # 3 show that a Flammschutzstoffkombi nation of the thermoplastic according to the invention with poly (pentabromobenzyl acrylate) the same VO classification as a flame retardant composition of poly (pentabromobenzylac- ryat) and the harmful Sb 2 Ü 3 achieved. Furthermore, no dripping can be observed when using the polymer according to the invention. This means that even the addition of anti-dripping agents such as PTFE can be dispensed with.
- the comparison of test specimen # 3 with the test specimens # 8 and # 9 shows that with the thermoplastic according to the invention a comparable flame-retardant effect as with the thermosets of the prior art can be achieved.
- test specimen # 1 The comparison of the results of the test specimens # 0 and # 2 shows that by the addition of the inventions to the invention thermoplastic PBT a similar high flame retardant effect as with the health-damaging Sb 2 0 3 ge can be achieved.
- the flameproofing effect of the prior art thermoset (test specimen # 1) clearly remains behind that of the thermoplasm according to the invention (test specimen # 2).
- Comparison of specimens # 3, # 5, and # 7 with specimens # 4, # 6, and # 8 illustrates that a flame retardant composition of a known flame retardant such as MC or MPP and the thermoplastic of the invention has better flame retardancy than the prior art flame retardant alone , This is obviously due to a synergistic effect.
- the burning time of the specimens is significantly shortened in all cases.
- Example 10 Flame-retardant properties of polycarbonate test specimens with polymer according to the invention in comparison to the prior art
- thermogravimetric and NMR spectroscopic measurements showing:
- FIG. 2 Thermogravimetric measurement of a polymer according to the invention (Example 5).
- FIG. 3 Thermogravimetric measurement of a polymer according to the invention (Example 6).
- FIG. 5 31 P-NMR spectrum of a polymer according to the invention (Example 6).
- Figure 1 shows the weight loss of a polymer according to the prior art (Example 0) as a function of temperature in a thermogravimetric measurement in the range of 20 ° C to 550 ° C, wherein the initial weight is given as 100%. Above 480 ° C, a nearly constant residual mass of approximately 13% of the original sample mass was established.
- FIG. 2 shows the course of a corresponding thermogravimetric measurement on a polymer sample according to the invention (Example 5). In the case of the polymer sample according to the invention, an almost constant residual mass of about 19% of the original sample mass was established above 480 ° C.
- FIG. 3 shows the course of a corresponding thermogravimetric measurement on a polymer sample according to the invention (Example 6).
- an almost constant residual mass of approximately 5% of the original sample mass was established above 450 ° C.
- Table 5 compares at which temperatures residual masses of 98, 96 and 94% by weight of the starting weight have been established in the sample according to the prior art (Example 0) and the sample according to the invention (Example 5).
- FIG. 4 shows the 1 H-NMR spectrum of a polymer according to the invention (Example 6) in the range from -0.5 to 9.0 ppm.
- the aromatic signals of the DOPO-functionalized repeat units can be recognized in the range from 7.0 to 8.5, whereas the aliphatic signals of the repeat units can be recognized as between 0.0 and 4.5 ppm. Due to the absence of olefinic signals in the range of about 5.5 to 6.5 ppm can be concluded that the compounds of formula III and IV in the second reaction step almost complete.
- FIG. 5 shows the 31 P-NMR spectrum of a polymer according to the invention (Example 6) in the range from -16 to 44 ppm. In the spectrum, only a broad polymer signal can be detected.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102018100984.4A DE102018100984A1 (de) | 2018-01-17 | 2018-01-17 | Phosphorhaltige thermoplastische Polymere |
PCT/EP2019/050482 WO2019141572A1 (de) | 2018-01-17 | 2019-01-10 | Phosphorhaltige thermoplastische polymere |
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EP3740516A1 true EP3740516A1 (de) | 2020-11-25 |
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EP19700367.6A Withdrawn EP3740516A1 (de) | 2018-01-17 | 2019-01-10 | Phosphorhaltige thermoplastische polymere |
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US (1) | US20200347161A1 (de) |
EP (1) | EP3740516A1 (de) |
JP (1) | JP2021511406A (de) |
KR (1) | KR20200104390A (de) |
CN (1) | CN111556879A (de) |
BR (1) | BR112020012036A2 (de) |
CA (1) | CA3085108A1 (de) |
DE (1) | DE102018100984A1 (de) |
MX (1) | MX2020007597A (de) |
RU (1) | RU2020126687A (de) |
TW (1) | TW201938605A (de) |
WO (1) | WO2019141572A1 (de) |
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DE102019219029B4 (de) | 2019-12-06 | 2022-04-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Flammhemmendes Polymer umfassend phosphorhaltige Wiederholungseinheiten, Flammschutz- und Kunststoffzusammensetzung umfassend das flammhemmende Polymer, Verfahren zur Herstellung des flammhemmenden Polymers sowie dessen Verwendung |
JP2023532201A (ja) | 2020-06-17 | 2023-07-27 | レノリット ソシエタス エウロパエア | 難燃性アクリレート |
DE102021116975A1 (de) * | 2021-07-01 | 2023-01-05 | R. Stahl Schaltgeräte GmbH | Kunststoffteil und Verfahren zu seiner Herstellung |
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FR1025E (fr) | 1902-09-08 | 1903-05-18 | Renfrew Crusher Company Ltd | Système de broyeur perfectionné |
DE102008012806A1 (de) | 2008-03-06 | 2009-09-10 | Schill + Seilacher Ag | Halogenfreie Flammschutzmittel |
TWI492974B (zh) * | 2009-08-24 | 2015-07-21 | Kaneka Corp | A flame retardant, a method for producing the same, and a flame retardant thermoplastic resin composition containing the same |
TWI519634B (zh) * | 2011-01-25 | 2016-02-01 | Kaneka Corp | Flame retardant resin composition |
EP2557085B1 (de) * | 2011-08-08 | 2014-10-22 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Neuartige Phosphoramidate - Synthese und flammhemmende Anwendungen |
DE102011116178A1 (de) * | 2011-10-14 | 2013-04-18 | Schill + Seilacher "Struktol" Gmbh | Halogenfreies, phosphorhaltiges Flammschutzmittel |
DE102013101487A1 (de) | 2013-02-14 | 2014-08-14 | Chemische Fabrik Budenheim Kg | Duromer, Herstellungsverfahren, Verwendung und Zusammensetzungen |
EP3087128B1 (de) * | 2013-12-27 | 2019-09-11 | Dow Global Technologies LLC | Flammhemmende copolymere von dialkyl(meth)acryloyloxyalkylphosphat- oder dialkyl(meth)acryloyloxyalkylphosphonat-monomeren und daraus hergestellte polymerschaumstoffe |
CN103936971B (zh) * | 2014-04-04 | 2016-04-06 | 北京市建筑工程研究院有限责任公司 | 一种有机高分子含磷阻燃剂 |
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2018
- 2018-01-17 DE DE102018100984.4A patent/DE102018100984A1/de not_active Withdrawn
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- 2019-01-09 TW TW108100824A patent/TW201938605A/zh unknown
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- 2019-01-10 BR BR112020012036-7A patent/BR112020012036A2/pt not_active Application Discontinuation
- 2019-01-10 EP EP19700367.6A patent/EP3740516A1/de not_active Withdrawn
- 2019-01-10 CA CA3085108A patent/CA3085108A1/en not_active Abandoned
- 2019-01-10 KR KR1020207022244A patent/KR20200104390A/ko unknown
- 2019-01-10 WO PCT/EP2019/050482 patent/WO2019141572A1/de active Search and Examination
- 2019-01-10 CN CN201980007339.5A patent/CN111556879A/zh active Pending
- 2019-01-10 US US16/962,649 patent/US20200347161A1/en not_active Abandoned
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BR112020012036A2 (pt) | 2020-11-24 |
CN111556879A (zh) | 2020-08-18 |
CA3085108A1 (en) | 2019-07-25 |
WO2019141572A1 (de) | 2019-07-25 |
KR20200104390A (ko) | 2020-09-03 |
JP2021511406A (ja) | 2021-05-06 |
US20200347161A1 (en) | 2020-11-05 |
TW201938605A (zh) | 2019-10-01 |
RU2020126687A (ru) | 2022-02-17 |
DE102018100984A1 (de) | 2019-07-18 |
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