CA1335680C - Flameproofed polyethylene terephthalate moulding compounds - Google Patents
Flameproofed polyethylene terephthalate moulding compoundsInfo
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- CA1335680C CA1335680C CA000587912A CA587912A CA1335680C CA 1335680 C CA1335680 C CA 1335680C CA 000587912 A CA000587912 A CA 000587912A CA 587912 A CA587912 A CA 587912A CA 1335680 C CA1335680 C CA 1335680C
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- polymethanephosphonate
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- polyethylene terephthalate
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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
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The flameproofed polyethylene terephthalate moulding compounds according to the invention, which contain polyalkylphosphonates and reinforcing agents, may be used for the production of moulded articles, fibres and films.
Description
1335~8~
Flameproofed polyethylene terephthalate moulding compounds This invention relates to flameproofed polyethylene terephthalate moulding compounds containing polyalkyl-phosphonates and reinforcing agents.
Flame-resistant polyester compositions which contain a polyethylene terephthalate carrying linkage units based on brominated organic aromatic compounds in the main chain and high molecular weight organic phosphorus compounds are disclosed in DE-OS 24 58 967. The polyester compositions described in this said DE-OS 24 58 967 have the disadvantage that they always contain organically bound bromine in a copolymerised form (risk of dioxine formation in the event of fire) and that they are difficult to prepare since they are copolymers.
Flame-retardant thermoplastic polyester resin composi-tions containing a flammable high molecular weight linearpolyester resin as one of its components and arylphosphon-ates as flame-retardant additives are disclosed in DE-OS 22 53 207. DE-OS 21 11 202 also discloses flame repel~lent thermoplastic polyesters which contain phosphorus-containing additives. Polyarylphosphonates are mentionedthere as phosphorus-containing additives. Our own experi-ments have shown that the flame resistant thermoplastic polyesters described in the two Offenlegungsschriften mentioned above are not sufficiently flameproof and they have the further disadvantage that the polyarylphosphonates are difficult to incorporate in the thermoplastic poly-esters.
Phosphorus-containing polyester mixtures which have improved flame-resistant properties are disclosed in Le A 25 701 - 133~680 DE-OS 21 32 350. These substances may contain both poly-alkyl phosphonates and polyarylphosphonates as phosphorus-:
containing additives. The said DE-OS 21 32 350 also claims reinforced polyester moulding resin mixtures 5 (Claims 7 to 10) which contain polypropylene terephthalate or polybutylene terephthalate as polyesters and reinforcing fillers such as glass fibres and polyphosphonate or polyphosphonate phosphate. Our own experiments have shown that these reinforced polybutylene terephthalate 10 moulding resin mixtures containing polyalkylphosphonate as flame-retardant additives are not sufficiently flame-resistant.
The present invention relates to flameproofed poly-ethylene terephthalate moulding compounds composed of 5 A) from 4 5 to 80 parts by weight of polyethylene terephthalate, B) from 15 to 40 parts by weight of inorganic reinforcing agents, C) from 1 to 25 parts by weight of polyalkylphosphonates corresponding to the following formula 1l P-O-X-O-- E2 (I), -- n wherein R1 stands for C1 to C6-alkyl, X stands for the following formula:
~} Y{~ a in which Y denotes a single bond or C1-C3-alkylene, C5-C12-cycloalkylene or O, S, CO or SO2 and Le A 25 701 2 a stands for 0 or 1 or X denotes naphthylene, E1 stands for O-R2, OH or O-X-OH, R2 standing for C6-C10-aryl and X having the meaning indicated above, O O
Il 11 E2 denotes H, -P-OR2, or -P-OH
wherein R1 and R2 have the meanings indicated above and n stands for integers from 2 to 100 and D) optionally from 0.1 to 10 parts by weight of processing auxiliaries.
The polyethylene terephthalates used according to the invention are polycondensation products of aromatic dicarboxylic acids or reactive derivatives thereof (such as their dimethylesters) and ~liphatic diols or reactive derivatives thereof, at least 90 mol-%, based on the diol component, being ethylene glycol units and 10 mol-%, based on the diol component, being aliphatic or cyclo-aliphatic, branched or unbranched C3-C18-diol units or polyalkylene oxide units (see e.g. DE 25 07 776, 24 07 074 and 24 07 776). Preferred polyethylene terephthalates contain at least 95 mol-% of ethylene glycol units, based on the total diol component. Pure polyethylene terephthalate is particularly preferred.
The polyethylene terephthalates may be prepared by known methods (see e.g. Kunststoff Handbuch, Volume VIII, page 695 et seq, Carl-Hanser-Verlag, Munich 1973).
The polyethylene terephthalates used according to the invention have intrinsic viscosities of about 0.4 to 1.3 dl/g, preferably 0.5 to 0.9 dl/g, determined in phenol/o-dichlorobenzene (1:1 parts by weight) at a con-centration of 5 g/l at 25C.
Le A 25 701 3 The inorganic reinforcing agents used according to the invention include all known agents conventionally used for the reinforcement of polyalkylene terephthalates.
The following are examples: Glass fibres, glass balls and/or mineral fibres as described in Katz and Milewski, "Handbook of Fillers and Reinforcements for Plastics", publishers Nostrand, 1978. The inorganic reinforcing agents used are preferably glass fibres. The glass fibres generally have a diameter of about 6 to 15 ~m, preferably 8 to 13 ~m, and a ratio of length to thickness greater than 45, preferably from 50 to 200.
The following are examples of mineral fillers:
Kaolin, talc, mica, powdered quartz, powdered rock, alkaline earth metal carbonates, alkaline earth metal oxides, titanium dioxide and/or zinc sulphide. The mineral fillers used have average particle diameters of less than 20 ~m, preferably less than 10 ~m, in particular 2 to 8 ~m.
The inorganic reinforcing agents are normally used in quantities of from 15 to 40 parts by weight, preferably from 20 to 35 parts by weight, most preferably from 25 to 30 parts by weight.
The polyalkylphosphonates to be used according to the invention are described, for example, in US 26 82 522, DE-OS 29 25 207 and DE-OS 29 44 093.
The polyalkylphosphonates preferably used correspond to the following formula (II) E3 P-O-X-o E4 (II) -- n in which R3 denotes methyl or ethyl, X stands for phenylene, bisphenylene, C1-C3-alkylbis-phenylene, C5-C12-cycloalkylbisphenylene, sulphonyl bisphenylene, oxobisphenylene, thiobisphenylene, Le A 25 701 4 133~680 carbonylbisphenylene or naphthylene, E3 denotes -O- ~ , -OH or -O-X-OH
wherein X has the meaning indicated above, O O
Il \ 11 E4 stands for -H, -P-O ~ or -P-OH
wherein R3 has the meanings indicated above and n stands for an integer from 5 to 80.
It is particularly preferred to use polyalky]
phosphonates which correspond to the general formula (II) and in which.
E3 stands for -O
E4 denotes -'-O
R3 denotes methyl and X stands for ~ S2 ~ ; ~ \ ~ -;
CH3 or - ~ and n has a value from 5 to 50.
Le A 25 701 5 --~ 133~680 The following are mentioned as examples of polyalkyl-phosphonates:
Bisphenol-F-polymethanephosphonate, bisphenol-A-polymethanephosphonate, dioxidiphenyl polymethanephosphonate, dioxidiphenyl sulphone polymethanephosphonate, pyrocatechol polymethanephosphonate, resorcinol polymethanephosphonate and/or hydroquinone polymethanephosphonate, the following being preferred:
Bisphenol-F-polymethanephosphonate, dioxidiphenyl polymethanephosphonate and/or hydroquinone polymethanephosphonate.
The following are suitable catalysts for the trans-esterification: Alkaline catalysts such as alkali metalphenolates, alkali metal hydrides, alkaline earth metal hydrides, alkali metal amides and alkaline earth metal amides; neutral catalysts such as tetraalkyltitanates, trialkyl tin acylates, dialkyl tin oxides and dialkyl tin acylates; but also imidazole and alkaline earth metal halides.
The polyphosphonates to be used according to the invention may be branched with small quantities of poly-functional compounds. The quantity of branching agents used is <3 mol.-%, based on the quantity of bisphenol.
The branching agents used are trifunctional or tetra-functional hydroxy compounds, e.g. 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)heptane; 1~3~5-tri-(4-hydroxyphenyl) benzene and 1,4-bis-(4,4'-dihydroxytriphenylmethyl)-benzene, trifunctional or tetrafunctional carboxylicacid aryl esters such as trimesic acid triphenylester and pyromellitic acid tetraphenylester and phosphoric acid triarylesters such as triphenylphosphate.
The polyalkylphosphonates to be used according to the invention generally have a relative solution viscosity of from 1.05 (corresponding to an average molar mass of 2000 [n approximately 8 monomer units]) to 1.40 Le A 25 701 6 (corresponding to an average molar mass of 22,000 [n approximately 90 monomer units]). Determination of the solution viscosity was carried out in methylene chloride (0.5 g/100 ml solution) at 25C.
According to the invention, the polyalkylphosphonates are used in quantities of from 1 to 25 parts by weight, preferably from 3 to 20 parts by weight, most preferably from 5 to 15 parts by weight.
The following may be added as processing auxiliaries to the moulding compounds according to the invention:
The known crystallisation aids, mould release agents, stabilizers, fluidizing auxiliaries, colouring agents and/or colour pigments. The crystallisation aids used may be, for example, inorganic crystalline, high melting compounds which act as nucleating agents, such as micro-talc, metal salts of aliphatic and/or aromatic low molecular weight or high molecular weight carboxylic acids as describ-ed in WO 85(03717, EP O 029 285, EP O 037 666, EP O 034 773, EP O 112 167, EP O 021 648 and EP O 102 768) and metal salts of aliphatic and/or aromatic sulphonic acids (EP 1 78 807).
The mould release agents used may be any of the known - products, such as ester waxes (e.g. montan wax), amide waxes such as Rhenax(R) and/or oligoethylenes. Aliphatic oligomeric polyesters, for example, may be used as plast-icizers (see EP 29 931 and DE 27 06 128).
The processing auxiliaries may be added to the poly-ethylene terephthalate moulding compounds in quantities of from 0.1 to 10 parts by weight, preferably from 0.3 to 5 parts by weight, most preferably from 0.4 to 2 parts by weight.
The mixtures of thermoplastic polyethylene terephthal-ate, reinforcing agents, polyalkylphosphonate and option-ally other processing auxiliaries may be prepared in the usual mixing apparatus, such as rollers, kneaders or single shaft or multishaft extruders. The processing auxiliaries may be added as concentrates in thermoplastic Le A 25 701 7 133~6~0 polyesters in a granular form or as a powder mixture when compounding the components. The temperature employed for the preparation of the mixtures is generally at least 20 degrees Centigrade and should not be more than 70 degrees Centigrade above the melting point of the polyester.
The process of preparation may be carried out batch-wise or continuously under conditions which virtually exclude oxidation, i.e. under a protective gas atmosphere.
Nitrogen, carbon dioxide and/or argon, for example, may be used as protective gas.
The polymer mixtures may be subjected to a thermal after-treatment in the solid phase at temperatures from 100 to 220C, preferably from 180 to 210C.
Thermoplastic processing of the moulding compounds according to the invention to produce moulded products may be carried out at reaction temperatures of up to 40 degrees Centigrade above the polyester melting point (250 to 290C) and with residence times of the melt in the mould of up to 9 minutes (1 to 9 minutes). Process-ing is preferably carried out at reaction temperaturesnot higher than 270C and with residence times not greater than 9 minutes. Under particularly preferred processing conditions, the reaction temperatures are not higher than 260C and the residence times not greater than 6 minutes.
The flameproofed polyethylene terephthalate moulding compounds according to the invention may be used for the production of moulded articles, fibres or films.
The flameproofed polyethylene terephthalate moulding compounds according to the invention have the following advantages over flameproofed, reinforced polyethylene terephthalate moulding compounds known in the art:
They have a higher degree of flame resistance than the moulding compounds which have previously been flame-proofed with polyphosphonates and the risk of toxic gases(dioxines) being released is less than in moulding compounds which are flameproofed with Sb/Br compounds.
Le A 25 701 8 13~5680 Examples I. Components used in the process:
1. Polybutylene terephthalate having an intrinsic viscosity of 1.20 dl/g determined in a phenol/o-dichlorobenzene mixture (ratio by weight 1:1), 25C, Ubbelohde viscosi-meter (for comparison, see Example III,b).
2. Polyethylene terephthalate having an intrinsic viscosity of 1.20 dl/g determined as described under 1. (according to the invention).
Flameproofed polyethylene terephthalate moulding compounds This invention relates to flameproofed polyethylene terephthalate moulding compounds containing polyalkyl-phosphonates and reinforcing agents.
Flame-resistant polyester compositions which contain a polyethylene terephthalate carrying linkage units based on brominated organic aromatic compounds in the main chain and high molecular weight organic phosphorus compounds are disclosed in DE-OS 24 58 967. The polyester compositions described in this said DE-OS 24 58 967 have the disadvantage that they always contain organically bound bromine in a copolymerised form (risk of dioxine formation in the event of fire) and that they are difficult to prepare since they are copolymers.
Flame-retardant thermoplastic polyester resin composi-tions containing a flammable high molecular weight linearpolyester resin as one of its components and arylphosphon-ates as flame-retardant additives are disclosed in DE-OS 22 53 207. DE-OS 21 11 202 also discloses flame repel~lent thermoplastic polyesters which contain phosphorus-containing additives. Polyarylphosphonates are mentionedthere as phosphorus-containing additives. Our own experi-ments have shown that the flame resistant thermoplastic polyesters described in the two Offenlegungsschriften mentioned above are not sufficiently flameproof and they have the further disadvantage that the polyarylphosphonates are difficult to incorporate in the thermoplastic poly-esters.
Phosphorus-containing polyester mixtures which have improved flame-resistant properties are disclosed in Le A 25 701 - 133~680 DE-OS 21 32 350. These substances may contain both poly-alkyl phosphonates and polyarylphosphonates as phosphorus-:
containing additives. The said DE-OS 21 32 350 also claims reinforced polyester moulding resin mixtures 5 (Claims 7 to 10) which contain polypropylene terephthalate or polybutylene terephthalate as polyesters and reinforcing fillers such as glass fibres and polyphosphonate or polyphosphonate phosphate. Our own experiments have shown that these reinforced polybutylene terephthalate 10 moulding resin mixtures containing polyalkylphosphonate as flame-retardant additives are not sufficiently flame-resistant.
The present invention relates to flameproofed poly-ethylene terephthalate moulding compounds composed of 5 A) from 4 5 to 80 parts by weight of polyethylene terephthalate, B) from 15 to 40 parts by weight of inorganic reinforcing agents, C) from 1 to 25 parts by weight of polyalkylphosphonates corresponding to the following formula 1l P-O-X-O-- E2 (I), -- n wherein R1 stands for C1 to C6-alkyl, X stands for the following formula:
~} Y{~ a in which Y denotes a single bond or C1-C3-alkylene, C5-C12-cycloalkylene or O, S, CO or SO2 and Le A 25 701 2 a stands for 0 or 1 or X denotes naphthylene, E1 stands for O-R2, OH or O-X-OH, R2 standing for C6-C10-aryl and X having the meaning indicated above, O O
Il 11 E2 denotes H, -P-OR2, or -P-OH
wherein R1 and R2 have the meanings indicated above and n stands for integers from 2 to 100 and D) optionally from 0.1 to 10 parts by weight of processing auxiliaries.
The polyethylene terephthalates used according to the invention are polycondensation products of aromatic dicarboxylic acids or reactive derivatives thereof (such as their dimethylesters) and ~liphatic diols or reactive derivatives thereof, at least 90 mol-%, based on the diol component, being ethylene glycol units and 10 mol-%, based on the diol component, being aliphatic or cyclo-aliphatic, branched or unbranched C3-C18-diol units or polyalkylene oxide units (see e.g. DE 25 07 776, 24 07 074 and 24 07 776). Preferred polyethylene terephthalates contain at least 95 mol-% of ethylene glycol units, based on the total diol component. Pure polyethylene terephthalate is particularly preferred.
The polyethylene terephthalates may be prepared by known methods (see e.g. Kunststoff Handbuch, Volume VIII, page 695 et seq, Carl-Hanser-Verlag, Munich 1973).
The polyethylene terephthalates used according to the invention have intrinsic viscosities of about 0.4 to 1.3 dl/g, preferably 0.5 to 0.9 dl/g, determined in phenol/o-dichlorobenzene (1:1 parts by weight) at a con-centration of 5 g/l at 25C.
Le A 25 701 3 The inorganic reinforcing agents used according to the invention include all known agents conventionally used for the reinforcement of polyalkylene terephthalates.
The following are examples: Glass fibres, glass balls and/or mineral fibres as described in Katz and Milewski, "Handbook of Fillers and Reinforcements for Plastics", publishers Nostrand, 1978. The inorganic reinforcing agents used are preferably glass fibres. The glass fibres generally have a diameter of about 6 to 15 ~m, preferably 8 to 13 ~m, and a ratio of length to thickness greater than 45, preferably from 50 to 200.
The following are examples of mineral fillers:
Kaolin, talc, mica, powdered quartz, powdered rock, alkaline earth metal carbonates, alkaline earth metal oxides, titanium dioxide and/or zinc sulphide. The mineral fillers used have average particle diameters of less than 20 ~m, preferably less than 10 ~m, in particular 2 to 8 ~m.
The inorganic reinforcing agents are normally used in quantities of from 15 to 40 parts by weight, preferably from 20 to 35 parts by weight, most preferably from 25 to 30 parts by weight.
The polyalkylphosphonates to be used according to the invention are described, for example, in US 26 82 522, DE-OS 29 25 207 and DE-OS 29 44 093.
The polyalkylphosphonates preferably used correspond to the following formula (II) E3 P-O-X-o E4 (II) -- n in which R3 denotes methyl or ethyl, X stands for phenylene, bisphenylene, C1-C3-alkylbis-phenylene, C5-C12-cycloalkylbisphenylene, sulphonyl bisphenylene, oxobisphenylene, thiobisphenylene, Le A 25 701 4 133~680 carbonylbisphenylene or naphthylene, E3 denotes -O- ~ , -OH or -O-X-OH
wherein X has the meaning indicated above, O O
Il \ 11 E4 stands for -H, -P-O ~ or -P-OH
wherein R3 has the meanings indicated above and n stands for an integer from 5 to 80.
It is particularly preferred to use polyalky]
phosphonates which correspond to the general formula (II) and in which.
E3 stands for -O
E4 denotes -'-O
R3 denotes methyl and X stands for ~ S2 ~ ; ~ \ ~ -;
CH3 or - ~ and n has a value from 5 to 50.
Le A 25 701 5 --~ 133~680 The following are mentioned as examples of polyalkyl-phosphonates:
Bisphenol-F-polymethanephosphonate, bisphenol-A-polymethanephosphonate, dioxidiphenyl polymethanephosphonate, dioxidiphenyl sulphone polymethanephosphonate, pyrocatechol polymethanephosphonate, resorcinol polymethanephosphonate and/or hydroquinone polymethanephosphonate, the following being preferred:
Bisphenol-F-polymethanephosphonate, dioxidiphenyl polymethanephosphonate and/or hydroquinone polymethanephosphonate.
The following are suitable catalysts for the trans-esterification: Alkaline catalysts such as alkali metalphenolates, alkali metal hydrides, alkaline earth metal hydrides, alkali metal amides and alkaline earth metal amides; neutral catalysts such as tetraalkyltitanates, trialkyl tin acylates, dialkyl tin oxides and dialkyl tin acylates; but also imidazole and alkaline earth metal halides.
The polyphosphonates to be used according to the invention may be branched with small quantities of poly-functional compounds. The quantity of branching agents used is <3 mol.-%, based on the quantity of bisphenol.
The branching agents used are trifunctional or tetra-functional hydroxy compounds, e.g. 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)heptane; 1~3~5-tri-(4-hydroxyphenyl) benzene and 1,4-bis-(4,4'-dihydroxytriphenylmethyl)-benzene, trifunctional or tetrafunctional carboxylicacid aryl esters such as trimesic acid triphenylester and pyromellitic acid tetraphenylester and phosphoric acid triarylesters such as triphenylphosphate.
The polyalkylphosphonates to be used according to the invention generally have a relative solution viscosity of from 1.05 (corresponding to an average molar mass of 2000 [n approximately 8 monomer units]) to 1.40 Le A 25 701 6 (corresponding to an average molar mass of 22,000 [n approximately 90 monomer units]). Determination of the solution viscosity was carried out in methylene chloride (0.5 g/100 ml solution) at 25C.
According to the invention, the polyalkylphosphonates are used in quantities of from 1 to 25 parts by weight, preferably from 3 to 20 parts by weight, most preferably from 5 to 15 parts by weight.
The following may be added as processing auxiliaries to the moulding compounds according to the invention:
The known crystallisation aids, mould release agents, stabilizers, fluidizing auxiliaries, colouring agents and/or colour pigments. The crystallisation aids used may be, for example, inorganic crystalline, high melting compounds which act as nucleating agents, such as micro-talc, metal salts of aliphatic and/or aromatic low molecular weight or high molecular weight carboxylic acids as describ-ed in WO 85(03717, EP O 029 285, EP O 037 666, EP O 034 773, EP O 112 167, EP O 021 648 and EP O 102 768) and metal salts of aliphatic and/or aromatic sulphonic acids (EP 1 78 807).
The mould release agents used may be any of the known - products, such as ester waxes (e.g. montan wax), amide waxes such as Rhenax(R) and/or oligoethylenes. Aliphatic oligomeric polyesters, for example, may be used as plast-icizers (see EP 29 931 and DE 27 06 128).
The processing auxiliaries may be added to the poly-ethylene terephthalate moulding compounds in quantities of from 0.1 to 10 parts by weight, preferably from 0.3 to 5 parts by weight, most preferably from 0.4 to 2 parts by weight.
The mixtures of thermoplastic polyethylene terephthal-ate, reinforcing agents, polyalkylphosphonate and option-ally other processing auxiliaries may be prepared in the usual mixing apparatus, such as rollers, kneaders or single shaft or multishaft extruders. The processing auxiliaries may be added as concentrates in thermoplastic Le A 25 701 7 133~6~0 polyesters in a granular form or as a powder mixture when compounding the components. The temperature employed for the preparation of the mixtures is generally at least 20 degrees Centigrade and should not be more than 70 degrees Centigrade above the melting point of the polyester.
The process of preparation may be carried out batch-wise or continuously under conditions which virtually exclude oxidation, i.e. under a protective gas atmosphere.
Nitrogen, carbon dioxide and/or argon, for example, may be used as protective gas.
The polymer mixtures may be subjected to a thermal after-treatment in the solid phase at temperatures from 100 to 220C, preferably from 180 to 210C.
Thermoplastic processing of the moulding compounds according to the invention to produce moulded products may be carried out at reaction temperatures of up to 40 degrees Centigrade above the polyester melting point (250 to 290C) and with residence times of the melt in the mould of up to 9 minutes (1 to 9 minutes). Process-ing is preferably carried out at reaction temperaturesnot higher than 270C and with residence times not greater than 9 minutes. Under particularly preferred processing conditions, the reaction temperatures are not higher than 260C and the residence times not greater than 6 minutes.
The flameproofed polyethylene terephthalate moulding compounds according to the invention may be used for the production of moulded articles, fibres or films.
The flameproofed polyethylene terephthalate moulding compounds according to the invention have the following advantages over flameproofed, reinforced polyethylene terephthalate moulding compounds known in the art:
They have a higher degree of flame resistance than the moulding compounds which have previously been flame-proofed with polyphosphonates and the risk of toxic gases(dioxines) being released is less than in moulding compounds which are flameproofed with Sb/Br compounds.
Le A 25 701 8 13~5680 Examples I. Components used in the process:
1. Polybutylene terephthalate having an intrinsic viscosity of 1.20 dl/g determined in a phenol/o-dichlorobenzene mixture (ratio by weight 1:1), 25C, Ubbelohde viscosi-meter (for comparison, see Example III,b).
2. Polyethylene terephthalate having an intrinsic viscosity of 1.20 dl/g determined as described under 1. (according to the invention).
3. Polyalkylphosphonates:
a) Dioxydiphenyl polymethanephosphonate, high molecular weight; POP I, b) Bisphenyl-A polymethanephosphonate, low molecular weight, POP II.
II. Preparation of the polyalkylphosphonates 1. POP I
mol (4650 g) of 4,4'-dioxodiphenyl, 0.125 mol (40.7 g) of triphenylphosphate, 25.1 mol (6215 g) of diphenylmethanephosphonate and 4.31 mmol (0.5 g) of sodium phenolate are vigorously mixed in an autoclave under nitrogen at 250C. In the course of 3 hours, phenol i5 distilled off through a column heated to 100C under a vacuum rising from 250 to 100 mbar and a temperature increasing from 250C to 265C. Transesterification is then continued for 5 hours under a pressure which gradually drops to 0.3 mbar and a temperature rising to 310C, the viscosity of the melt at the same time increasing. Nitrogen is then introduced and the polymer is left to settle while the stirrer is brought to a standstill, and 5.3 kg of polyphosphonate are obtained by spinning under pressure and granulating the molten strand . The polyphosphonate has a relative viscosity of ~rel = 1.28 (determined in methylene chloride, 0.5 g/100 ml solution).
Le A 25 701 9 :13~5680 , . : .
2. POP II
`~ol (3800 g) of bisphenol-A, .
25.25 mol (6262 g) of diphe~ylmethanephosphonate and 4.31 mmol (0.5 g) of sodium phenolate r~
are~reacted together as under 1. 4.8 kg of polyphosphonate having a relative viscosity of 1.10 (determined in methylene chloride, 0.5 g/100 ml solution) are obtained.
III. Preparation, processing and testing of the moulding compounds The polyethylene terephthalate is used in the form of a granulate. The polyalkylphosphonates (POP I and ~ -POP II) are used as powders. The components introduced are melted in a two-shaft extruder, mixed, extruded as strands and granulated. Preparation of the moulding compounds may be carried out, for example, with an extruder ZSK 32 of Werner and Pfleiderer, at reaction temperatures from 270 to 280C and at a speed of rotation of the screw of 130 revs/min and a throughput of 8 kg per hour.-When the moulding compounds have sufficiently dried (e.g. 3 to 4 hours at 120C), they are worked up into -moulded products or standard test rods in conventional injection moulding machines at reaction temperatures - of from 250 to 270C, a mould temperature of 80 to 130-C
and a residence time in th~e mould of not more than 9 minutes.
Testing for flame resistance was carried out accord- -ing to the guidelines of the Underwriter Laboratories~ ~
(U1-94-Test). The results are summarized in the following~
Table. The quantities of the components put into the -30 process are given in parts by weight.
a) Examples according to the invention using various - polyalkylphosphonates , ~-;
,' - ..
Lc A 25 /01 lO
:
Table I: ;
E x a m p l e s . 1 2 3 4 5 6 POP I 10 15 20 - - - .
POP II - . - - 10 15 20 Glass fibres 30 30 30 30 30 30 UL-94 Test (1.6 mm) 2 day value Total after-burning time (S) 54 0: 0 29 22 3 Response to 1st flaming nd nd nd db nd nd 2nd flaming db db dwb nd db dwb nd Assessment V2 V0 V0 V2 V0 V0 7 day value Total after-burning time (S) 20 4 0 79 17 5 Response to 1st flaming nd nd nd db nd nd 2nd flaming db dwb nd db db nd Assessment V2 V0 V0 V2 V2 V0 UL-94-Test (0.8 mm) 2 days value Total after-burning time (5) 30 2 0 27 25 14 Response to 1st flaming .db dwb nd db nd nd 2nd ~laming ; .db dwb dwb db db db Assessment V2 V0 V0 V2 V2 V2 7 day value Total after-burning time (S) 3 7 0 29 34 6 Response to 1st flaming db dwb nd db db nd 2nd flaming db db dwb db db db Assessment V2 V2 V0 V2 V2 V0 Scale of assessment: V0 > V1 > V2 > f (fail) .
Abbreviations: db = drlps with burning nd = no dripping d~Tb -drips without burning .
Le A 25 701 ll . .
~ ~33S680 : b) Comparison of polyalkylphosphonates (according to the invention) with polyarylphosphonates (state of the art) Table II:
Example Comparison (according to the Example invention ~-- Example 1) 10 POP I ~ 10 10 (Polyaryl-phosphonate corresponding to the formula given below) 15 Glass fibres ~ 30 30 UL-94-test . 1.6 mm/0.8 mm 1.6 mm/0.8 mm 2-day value Total after- .
burning time (s) 54/3 118/145 20 Response to ~ ~
1stflaming nd/db db/db 2nd flaming ; db/db db/db Assessment V2/V2 V2/f 7-day value 25 Total after- ~ .
burning time (s) 20/30 96/57 Response to 1st flaming nd/db db/db : 2nd flaming db/db db/db 30 Assessment ~ V2/V2 V2/V2 :`
.: ' ' ' Le A 25 70i 12 ~.
r 3L33~6~
- . ~ ................................................ , The Comparison Example contains the polyarylphosphonate corresponding to the following formula:
O O
~ ~n n = 2 to 100 (prepared according to the method for POP I) relative viscosity: 1.17.
The experiments with polyalkylphosphonates and polyaryl-phosphonates showed that polyarylphosphonate could only be compounded with up to 10 parts by weight but not with 15 parts by weight.
. 10 Table II clearly shows the improved fire character-lstlcs of PET mixed with POP I, a polyalkylphosphonate.
c) Comparison between unreinforced PET and PET reinforced with glass fibres and unreinforced PET and PBT re-inforced with glass fibres . , :
:
1e A 25 701 13 --13356~0 :
.
Q 'i:~ O F
U~ ~ O ~ Q Q ~ Q ~5 ~ ~ ~ E ~ ~
E~ ~ ,1 0 ~ ~D O ~ ~ o~
m ~ x - - O Q ~ ~ ~D Q Q ~
A
A
~ .
C) ~ O
O U~
~ ,1 _ ~
a) Q~ Q~ o Q Q ~l Q Q ~
m ~ c, x ~ QQ~ ~ QQ~
O
Q~ ~^ ~
Q Q
I ~ Q 3 Q ~
O 3 ~ O ~ ~: O
~ X ~~5 3 c ~ ~ 3 o '13 _~ O
U~
~J-~ _I _ , s~ ' Q
~ ~ o Q 3 ~ Q
O ~ ~ ~~ ~ ~ Q
- ~ ~5 0 X ~Q Q ~ t-- 3 Q ~`
:
C) a~ o U~ U~
:
o ~ ~ ~ o ~ ~ -~ a ~ ~ ~ 3 Q I ~ ~ ' :` ~ ~ u, ~ ~ ~ .- ~ ~ UJ
~ ~ I O ~ ; U2 ~ U I O _ Ul .C U.
- E~ ~ ~ E~ Q e ~ ~ r~ Q ~
.
Le A 25 701 ~ 14 .
~: `
~ ~3~0 Scale of assessment: VO V1 V2 f (failed) Abbreviations: db = drips with burning nd = no dripping dwb = drips wi~hout burning :
All samples contain 15 parts by weight of POP I.
The reinforced samples contain 30 parts by weight of glass fib-res.
: Results:
The difference between PET and PBT is demonstrated.:
Whereas an assessment of V2 is obtained for all the unreinforced samples, the addition of glass fibres ralses the assessment of PET to VO but lowers that of PBT to "failed".
.
~ ~ .
;
, .
` Le A 25 701 ~ 15 ,
a) Dioxydiphenyl polymethanephosphonate, high molecular weight; POP I, b) Bisphenyl-A polymethanephosphonate, low molecular weight, POP II.
II. Preparation of the polyalkylphosphonates 1. POP I
mol (4650 g) of 4,4'-dioxodiphenyl, 0.125 mol (40.7 g) of triphenylphosphate, 25.1 mol (6215 g) of diphenylmethanephosphonate and 4.31 mmol (0.5 g) of sodium phenolate are vigorously mixed in an autoclave under nitrogen at 250C. In the course of 3 hours, phenol i5 distilled off through a column heated to 100C under a vacuum rising from 250 to 100 mbar and a temperature increasing from 250C to 265C. Transesterification is then continued for 5 hours under a pressure which gradually drops to 0.3 mbar and a temperature rising to 310C, the viscosity of the melt at the same time increasing. Nitrogen is then introduced and the polymer is left to settle while the stirrer is brought to a standstill, and 5.3 kg of polyphosphonate are obtained by spinning under pressure and granulating the molten strand . The polyphosphonate has a relative viscosity of ~rel = 1.28 (determined in methylene chloride, 0.5 g/100 ml solution).
Le A 25 701 9 :13~5680 , . : .
2. POP II
`~ol (3800 g) of bisphenol-A, .
25.25 mol (6262 g) of diphe~ylmethanephosphonate and 4.31 mmol (0.5 g) of sodium phenolate r~
are~reacted together as under 1. 4.8 kg of polyphosphonate having a relative viscosity of 1.10 (determined in methylene chloride, 0.5 g/100 ml solution) are obtained.
III. Preparation, processing and testing of the moulding compounds The polyethylene terephthalate is used in the form of a granulate. The polyalkylphosphonates (POP I and ~ -POP II) are used as powders. The components introduced are melted in a two-shaft extruder, mixed, extruded as strands and granulated. Preparation of the moulding compounds may be carried out, for example, with an extruder ZSK 32 of Werner and Pfleiderer, at reaction temperatures from 270 to 280C and at a speed of rotation of the screw of 130 revs/min and a throughput of 8 kg per hour.-When the moulding compounds have sufficiently dried (e.g. 3 to 4 hours at 120C), they are worked up into -moulded products or standard test rods in conventional injection moulding machines at reaction temperatures - of from 250 to 270C, a mould temperature of 80 to 130-C
and a residence time in th~e mould of not more than 9 minutes.
Testing for flame resistance was carried out accord- -ing to the guidelines of the Underwriter Laboratories~ ~
(U1-94-Test). The results are summarized in the following~
Table. The quantities of the components put into the -30 process are given in parts by weight.
a) Examples according to the invention using various - polyalkylphosphonates , ~-;
,' - ..
Lc A 25 /01 lO
:
Table I: ;
E x a m p l e s . 1 2 3 4 5 6 POP I 10 15 20 - - - .
POP II - . - - 10 15 20 Glass fibres 30 30 30 30 30 30 UL-94 Test (1.6 mm) 2 day value Total after-burning time (S) 54 0: 0 29 22 3 Response to 1st flaming nd nd nd db nd nd 2nd flaming db db dwb nd db dwb nd Assessment V2 V0 V0 V2 V0 V0 7 day value Total after-burning time (S) 20 4 0 79 17 5 Response to 1st flaming nd nd nd db nd nd 2nd flaming db dwb nd db db nd Assessment V2 V0 V0 V2 V2 V0 UL-94-Test (0.8 mm) 2 days value Total after-burning time (5) 30 2 0 27 25 14 Response to 1st flaming .db dwb nd db nd nd 2nd ~laming ; .db dwb dwb db db db Assessment V2 V0 V0 V2 V2 V2 7 day value Total after-burning time (S) 3 7 0 29 34 6 Response to 1st flaming db dwb nd db db nd 2nd flaming db db dwb db db db Assessment V2 V2 V0 V2 V2 V0 Scale of assessment: V0 > V1 > V2 > f (fail) .
Abbreviations: db = drlps with burning nd = no dripping d~Tb -drips without burning .
Le A 25 701 ll . .
~ ~33S680 : b) Comparison of polyalkylphosphonates (according to the invention) with polyarylphosphonates (state of the art) Table II:
Example Comparison (according to the Example invention ~-- Example 1) 10 POP I ~ 10 10 (Polyaryl-phosphonate corresponding to the formula given below) 15 Glass fibres ~ 30 30 UL-94-test . 1.6 mm/0.8 mm 1.6 mm/0.8 mm 2-day value Total after- .
burning time (s) 54/3 118/145 20 Response to ~ ~
1stflaming nd/db db/db 2nd flaming ; db/db db/db Assessment V2/V2 V2/f 7-day value 25 Total after- ~ .
burning time (s) 20/30 96/57 Response to 1st flaming nd/db db/db : 2nd flaming db/db db/db 30 Assessment ~ V2/V2 V2/V2 :`
.: ' ' ' Le A 25 70i 12 ~.
r 3L33~6~
- . ~ ................................................ , The Comparison Example contains the polyarylphosphonate corresponding to the following formula:
O O
~ ~n n = 2 to 100 (prepared according to the method for POP I) relative viscosity: 1.17.
The experiments with polyalkylphosphonates and polyaryl-phosphonates showed that polyarylphosphonate could only be compounded with up to 10 parts by weight but not with 15 parts by weight.
. 10 Table II clearly shows the improved fire character-lstlcs of PET mixed with POP I, a polyalkylphosphonate.
c) Comparison between unreinforced PET and PET reinforced with glass fibres and unreinforced PET and PBT re-inforced with glass fibres . , :
:
1e A 25 701 13 --13356~0 :
.
Q 'i:~ O F
U~ ~ O ~ Q Q ~ Q ~5 ~ ~ ~ E ~ ~
E~ ~ ,1 0 ~ ~D O ~ ~ o~
m ~ x - - O Q ~ ~ ~D Q Q ~
A
A
~ .
C) ~ O
O U~
~ ,1 _ ~
a) Q~ Q~ o Q Q ~l Q Q ~
m ~ c, x ~ QQ~ ~ QQ~
O
Q~ ~^ ~
Q Q
I ~ Q 3 Q ~
O 3 ~ O ~ ~: O
~ X ~~5 3 c ~ ~ 3 o '13 _~ O
U~
~J-~ _I _ , s~ ' Q
~ ~ o Q 3 ~ Q
O ~ ~ ~~ ~ ~ Q
- ~ ~5 0 X ~Q Q ~ t-- 3 Q ~`
:
C) a~ o U~ U~
:
o ~ ~ ~ o ~ ~ -~ a ~ ~ ~ 3 Q I ~ ~ ' :` ~ ~ u, ~ ~ ~ .- ~ ~ UJ
~ ~ I O ~ ; U2 ~ U I O _ Ul .C U.
- E~ ~ ~ E~ Q e ~ ~ r~ Q ~
.
Le A 25 701 ~ 14 .
~: `
~ ~3~0 Scale of assessment: VO V1 V2 f (failed) Abbreviations: db = drips with burning nd = no dripping dwb = drips wi~hout burning :
All samples contain 15 parts by weight of POP I.
The reinforced samples contain 30 parts by weight of glass fib-res.
: Results:
The difference between PET and PBT is demonstrated.:
Whereas an assessment of V2 is obtained for all the unreinforced samples, the addition of glass fibres ralses the assessment of PET to VO but lowers that of PBT to "failed".
.
~ ~ .
;
, .
` Le A 25 701 ~ 15 ,
Claims (6)
1. A flameproofed polyethylene terephthalate moulding composition comprising A) from 45 to 80 parts by weight of polyethylene terephthalate, B) from 15 to 40 parts by weight of an inorganic reinforcing agent and C) from 1 to 25 parts by weight of a polyalkyl-phosphonate corresponding to the following formula:
wherein R1 stands for C1-C6-alkyl, X stands for the following formula:
wherein Y denotes a single bond or C1-C3-alkylene, C5-C12-cycloalkylene or O, S, CO or SO2 and a stands for 0 or 1 or X denotes naphthylene, E1 stands for O-R2, OH, or O-X-OH, R2 denoting C6-C10-aryl and X having the meaning indicated above, E2 denotes H, , or wherein R1 and R2 have the meanings indicated above and n stands for an integer from 2 to 100.
wherein R1 stands for C1-C6-alkyl, X stands for the following formula:
wherein Y denotes a single bond or C1-C3-alkylene, C5-C12-cycloalkylene or O, S, CO or SO2 and a stands for 0 or 1 or X denotes naphthylene, E1 stands for O-R2, OH, or O-X-OH, R2 denoting C6-C10-aryl and X having the meaning indicated above, E2 denotes H, , or wherein R1 and R2 have the meanings indicated above and n stands for an integer from 2 to 100.
2. A moulding composition according to claim 1, wherein the reinforcing agent comprises glass fibres, glass balls or mineral filler.
3. A moulding composition according to claim 1, wherein the reinforcing agent comprises glass fibres.
4. A moulding composition according to claim 1, 2 or 3, wherein the polyalkylphosphonate comprises:
bisphenol-F-polymethanephosphonate, bisphenol-A-polymethanephosphonate, dioxidiphenyl-polymethanephosphonate, dioxidiphenyl-sulphone polymethanephosphonate, pyrocatechol polymethanephosphonate, resorcinol polymethanephosphonate or hydroquinone polymethanephosphonate.
bisphenol-F-polymethanephosphonate, bisphenol-A-polymethanephosphonate, dioxidiphenyl-polymethanephosphonate, dioxidiphenyl-sulphone polymethanephosphonate, pyrocatechol polymethanephosphonate, resorcinol polymethanephosphonate or hydroquinone polymethanephosphonate.
5. A moulding composition according to claim 1, 2 or 3, further comprising from 0.1 to 10 parts by weight of crystallising agents, mould release agents, stabilizers, fluidizing agents, colouring agents, colour pigments or plasticizers.
6. A use of a flameproofed polyethylene terephthalate moulding composition according to claim 1, 2 or 3, for the production of a moulded article, fibre or film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3800672.3 | 1988-01-13 | ||
| DE3800672A DE3800672A1 (en) | 1988-01-13 | 1988-01-13 | FLAME-RETARDED POLYETHYLENE TEREPHTHALATE MOLDINGS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335680C true CA1335680C (en) | 1995-05-23 |
Family
ID=6345139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000587912A Expired - Fee Related CA1335680C (en) | 1988-01-13 | 1989-01-11 | Flameproofed polyethylene terephthalate moulding compounds |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0324356B1 (en) |
| JP (1) | JPH0277465A (en) |
| CA (1) | CA1335680C (en) |
| DE (2) | DE3800672A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7427652B2 (en) * | 2002-11-08 | 2008-09-23 | Supresta Llc | Composition of epoxy resin, OH-terminated phosphonate oligomer and inorganic filler |
| US7449526B2 (en) | 2001-10-04 | 2008-11-11 | Supresta U.S. Llc | Oligomeric, hydroxy-terminated phosphonates |
| US20140000751A1 (en) * | 2012-06-29 | 2014-01-02 | Frx Polymers, Inc. | Polyester co-phosphonates |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3833694A1 (en) * | 1988-10-04 | 1990-04-05 | Bayer Ag | FLAME-RETARDED, WELL CRYSTALLIZING POLYETHYLENE TEREPHTHALATE MOLDINGS |
| DE4113157A1 (en) * | 1990-09-06 | 1992-03-12 | Bayer Ag | MELAMINE BASED BRANCHED POLYPHOSPHONATES |
| DE4419569A1 (en) * | 1994-06-03 | 1995-12-07 | Bayer Ag | Mineral filled molding compounds based on polyalkylene terephthalate |
| GB9609606D0 (en) | 1996-05-08 | 1996-07-10 | T & N Technology Ltd | Fire-resistant monofilament |
| JP4602559B2 (en) * | 1999-02-19 | 2010-12-22 | サプレスタ エルエルシー | Phosphorus-containing flame retardant thermoplastic polyester composition |
| KR102250655B1 (en) * | 2013-09-20 | 2021-05-12 | 도아고세이가부시키가이샤 | Flame-retardant adhesive composition, coverlay film using same, and flexible copper-clad laminate |
| JP6926477B2 (en) * | 2017-01-05 | 2021-08-25 | 三菱ケミカル株式会社 | Transparent flame-retardant polyester film and dimming film |
| KR102405379B1 (en) * | 2017-10-16 | 2022-06-08 | 에프알엑스 폴리머스, 인코포레이티드 | Phosphonate oligomers and blends of polymers and polyesters |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA945285A (en) * | 1970-03-09 | 1974-04-09 | Yukito Masai | Fireproof, thermoplastic polyester composition |
| US3987008A (en) * | 1971-12-17 | 1976-10-19 | Celanese Corporation | Flame retardant polyester |
| JPS5313226B2 (en) * | 1973-09-06 | 1978-05-09 | ||
| JPS5091651A (en) * | 1973-12-17 | 1975-07-22 | ||
| JPS51145561A (en) * | 1976-06-04 | 1976-12-14 | Toyobo Co Ltd | Flame retardant polyester composition |
| EP0133641A1 (en) * | 1983-06-28 | 1985-03-06 | General Electric Company | Flame retardant thermoplastic polyester compositions |
-
1988
- 1988-01-13 DE DE3800672A patent/DE3800672A1/en not_active Withdrawn
-
1989
- 1989-01-04 EP EP89100063A patent/EP0324356B1/en not_active Expired - Lifetime
- 1989-01-04 DE DE8989100063T patent/DE58903987D1/en not_active Expired - Fee Related
- 1989-01-10 JP JP1002168A patent/JPH0277465A/en active Pending
- 1989-01-11 CA CA000587912A patent/CA1335680C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7449526B2 (en) | 2001-10-04 | 2008-11-11 | Supresta U.S. Llc | Oligomeric, hydroxy-terminated phosphonates |
| US7427652B2 (en) * | 2002-11-08 | 2008-09-23 | Supresta Llc | Composition of epoxy resin, OH-terminated phosphonate oligomer and inorganic filler |
| US20140000751A1 (en) * | 2012-06-29 | 2014-01-02 | Frx Polymers, Inc. | Polyester co-phosphonates |
| US9695278B2 (en) * | 2012-06-29 | 2017-07-04 | Frx Polymers, Inc. | Polyester co-phosphonates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0277465A (en) | 1990-03-16 |
| EP0324356B1 (en) | 1993-04-07 |
| DE3800672A1 (en) | 1989-07-27 |
| DE58903987D1 (en) | 1993-05-13 |
| EP0324356A1 (en) | 1989-07-19 |
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