CA2085668A1 - Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-retardant additive - Google Patents
Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-retardant additiveInfo
- Publication number
- CA2085668A1 CA2085668A1 CA002085668A CA2085668A CA2085668A1 CA 2085668 A1 CA2085668 A1 CA 2085668A1 CA 002085668 A CA002085668 A CA 002085668A CA 2085668 A CA2085668 A CA 2085668A CA 2085668 A1 CA2085668 A1 CA 2085668A1
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- Canada
- Prior art keywords
- copolyester
- linear
- formula
- carbon atoms
- previous
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—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
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
Abstract
LINEAR COPOLYESTER CONTAINING PHOSPHOROUS, PROCEDURE
FOR ITS PREPARATION AND ITS USE AS A FLAME-RETARDANT
ADDITIVE.
Abstract A linear copolyester is prepared by polycondensation of an aromatic bicarboxylic acid with an alkylene glycol and with a carboxyphosphinic acid or anhydride which produces monomeric units having the formula:
(I) wherein R1 is an alkylene or phenyl radical and R2 is an alkyl or phenyl radical.
This copolyester can be used as a flame-retardant additive for organic polymers.
FOR ITS PREPARATION AND ITS USE AS A FLAME-RETARDANT
ADDITIVE.
Abstract A linear copolyester is prepared by polycondensation of an aromatic bicarboxylic acid with an alkylene glycol and with a carboxyphosphinic acid or anhydride which produces monomeric units having the formula:
(I) wherein R1 is an alkylene or phenyl radical and R2 is an alkyl or phenyl radical.
This copolyester can be used as a flame-retardant additive for organic polymers.
Description
208~668 LINEAR COPOLYESTER CONTAINING PHOSPHOROUS, PROCEDURE
FOR ITS PREPARATION AND ITS USE AS A FLAME-RETARDANT
ADDITIVE.
The present invention relates to linear polyesters containing structural units based on phosphorous, the procedure for their preparation and their use as flame-retardant agents.
In the field of organic polymers there is a demand for ~lame-resistant products, especially in certain areas of application such as the textile industry.
Various flame-retardant additives, generally halogenated organic compounds or compounds containing phosphorous, are used and are applied by surface treatment of the product, for example in the finishing stage of a textile.
However, the use of these flame-retardant additives is not generally completely satisfactory, mainly because of their incompatibility with the organic polymers to which they are added, the release of the additive from the polymer and the high quantities of additive required to provide the 1.
.
FOR ITS PREPARATION AND ITS USE AS A FLAME-RETARDANT
ADDITIVE.
The present invention relates to linear polyesters containing structural units based on phosphorous, the procedure for their preparation and their use as flame-retardant agents.
In the field of organic polymers there is a demand for ~lame-resistant products, especially in certain areas of application such as the textile industry.
Various flame-retardant additives, generally halogenated organic compounds or compounds containing phosphorous, are used and are applied by surface treatment of the product, for example in the finishing stage of a textile.
However, the use of these flame-retardant additives is not generally completely satisfactory, mainly because of their incompatibility with the organic polymers to which they are added, the release of the additive from the polymer and the high quantities of additive required to provide the 1.
.
2~85668 necessary flame-retardant characteristics.
In accordance with another technique, the flame-retardant characteristics are obtained by introducing monomeric units containing phosphorous into the polymeric chain.
For example, flame-retardant linear polyesters are known in the art, obtained by polycondensing, in the presence of suitable catalysts, terephthalic acid, or its methyl diester, with an alkylene glycol, such as ethylene glycol, and with at least one monomeric unit containing phosphorous.
For example U.S. Patents 3.941.752 and 4.033.936 describe flame-retardant linear polyesters obtained by the polycondensation of a bicarboxylic acid, an alkylene glycol and a monomer deriving from a phosphinic carboxy acid, one of its esters or its cyclic anhydride (2,5-dioxo-1,2-oxaphospholane), the latter in quantities ranging ~rom 3 to 20 moles % with respect to the total quantity of acid components.
The use of these monomers containing phosphorous in the reaction for the preparation of the flame-retardant polymer may however cause disadvantages, due, for example, to the necessity of modifying the produc-tion plant o~ the polymer.
It has now been ~ound that linear copolyesters containing high quantities o~ phosphorous in the macromolecule can be prepared and can be used as flame-208~68 retardant additives in the stabilization of a wide range of organic polymers, without having any of the disadvantages of the known art.
The present invention consequently relates to a linear copolyester, a flame-retardant additive for organic polymers, composed of the product of the polycondensation of an aromatic bicarboxylic acid with an alkylene glycol containing from 2 to 6 carbon atoms and with a monomer which produces in the chain of said copolyester units having the formula:
fi -0-P-R1-C- (I) wherein R1 is a linear alkylene radical, branched or cyclic containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, R2 is an alkyl radical containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, said copolyester having a phosphorous content of at least 2.5% by weight, and preferably in the range of 3-6%.
Suitable bicarboxylic aromatic acids are, for example, terephthalic acid and isophthalic acid. Among these terephthalic acid is preferred.
Among the alkylene glycols containing from 2 to 6 carbon atoms, ethylene glycol, 1,4-butandiol, neo-pentylglycol and 1,4-cyclohexandiol are preferred.
Particularly pre~erred is ethylene glycol.
In accordance with another technique, the flame-retardant characteristics are obtained by introducing monomeric units containing phosphorous into the polymeric chain.
For example, flame-retardant linear polyesters are known in the art, obtained by polycondensing, in the presence of suitable catalysts, terephthalic acid, or its methyl diester, with an alkylene glycol, such as ethylene glycol, and with at least one monomeric unit containing phosphorous.
For example U.S. Patents 3.941.752 and 4.033.936 describe flame-retardant linear polyesters obtained by the polycondensation of a bicarboxylic acid, an alkylene glycol and a monomer deriving from a phosphinic carboxy acid, one of its esters or its cyclic anhydride (2,5-dioxo-1,2-oxaphospholane), the latter in quantities ranging ~rom 3 to 20 moles % with respect to the total quantity of acid components.
The use of these monomers containing phosphorous in the reaction for the preparation of the flame-retardant polymer may however cause disadvantages, due, for example, to the necessity of modifying the produc-tion plant o~ the polymer.
It has now been ~ound that linear copolyesters containing high quantities o~ phosphorous in the macromolecule can be prepared and can be used as flame-208~68 retardant additives in the stabilization of a wide range of organic polymers, without having any of the disadvantages of the known art.
The present invention consequently relates to a linear copolyester, a flame-retardant additive for organic polymers, composed of the product of the polycondensation of an aromatic bicarboxylic acid with an alkylene glycol containing from 2 to 6 carbon atoms and with a monomer which produces in the chain of said copolyester units having the formula:
fi -0-P-R1-C- (I) wherein R1 is a linear alkylene radical, branched or cyclic containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, R2 is an alkyl radical containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, said copolyester having a phosphorous content of at least 2.5% by weight, and preferably in the range of 3-6%.
Suitable bicarboxylic aromatic acids are, for example, terephthalic acid and isophthalic acid. Among these terephthalic acid is preferred.
Among the alkylene glycols containing from 2 to 6 carbon atoms, ethylene glycol, 1,4-butandiol, neo-pentylglycol and 1,4-cyclohexandiol are preferred.
Particularly pre~erred is ethylene glycol.
3.
208566~
In the units having formula (I), R1 is preferably an alkylene radical containing 2 carbon atoms, whereas R2 is preferably a methyl or phenyl.
Compounds which produce units having formula (I) in the copolyester chain are carboxy-phosphinic acids having the formula:
HO-P-R1-COOH (II) their esters with an alcohol containing from l to 4 carbon atoms or with a diol containing from 2 to 4 carbon atoms, in the latter case possibly in the form of oligomers containing up to 5 monomeric units, or it is also possible to use the corresponding cyclic anhydrides hav~ng the formula:
R2-P-R1 (III) ~-C=O
with R1 and R2 which, in both formulae (II3 and (III), have the meaning defined above.
The linear copolyesters of the present invention are prepared according to a me*hod, which is a further aspect of the present invention, and which consists in the polycondensation reaction of the respective comonomers, and i.e. of bicarboxylic aromatic acid, of alkylene glycol and of the carboxyphosphinic monomer which produce the units having formula (I).
2~85668 The above copolyesters may also be prepared by a precondensation of the carboxyphosphinic compound with alkylene glycol, and subsequent treatment of these glycol esters with a prepolymer of bicarboxylic aromatic acid and alkylene glycol.
The linear copolyesters of the present invention are used as flame-retardant additives, suitable for providing flame-resistant characteristics to a wide range of organic polymers, such as linear polyesters with an aliphatic and/or aromatic structure, polyolefins, polyamides, polycarbonates, polyphenylen-oxides, polystyrenes, di- and ter- styrene polymers such as SAN and ABS, elastomeric copolymers such as EPR, EPDM, EVA.
In particular, the flame-retardant copolyester of the present invention is mixed and homogenized during the processing of the organic polymer in the molten state, which can then be transformed into end-products such as fibres, films, moulded items, etc.
The polymeric additives of the present invention are extremely compatible with the above organic polymers, forming real polymeric binders with these, and are also able to remain for long time within the polymeric material in which they are incorporated.
The quantity of copolyester of the present invention which is necessary for giving flame-retardant characteristics should be sufficient to ensure a phosphorous content (evaluated as an element) in the organic polymer ranging from 0.3 to 3% by weight, and preferably from 0.6 to 1.5% by weight.
The following examples provide a better illustration of the present invention but do not limit it in any way.
Example 1 15 g of 1,2-oxaphospholane-5-one-2-methyl-2-oxide and 45 g of ethylene glycol are charged into a three-necked 250 cc flask equipped with a mechanical stirrer,nitrogen inlet and condenser.
The temperature is brought, under a N2 atmosphere, to 120-130C, at which temperature the anhydride passes into solution. These conditions are maintained for 90 minutes, after which the excess glycol is distilled at reduced pressure, thus dehydrating the reaction mass at the same time.
The latter is then reacted with 60 g of a poly-ethyleneterephthalate prepolymer (PET) having a viscosity index V.I. = 0.23 dl/g and containing 205 ppm of Sb (as Sb203). The reactor is evacuated and cleaned three times with N2, and the system is then put under forced vacuum for 20 minutes.
The N2 atmosphere is subsequently restored and the temperature brought to 250C by means of a heating fluid. After the homogeneous fusion of the mass, the temperature is brought to 275C and the pressure to 400 208~668 mm Hg over a period of 30 minutes. After an hour at constant temperature and continually increasing vacuum, a forced vacuum is applied and the system is sponta-neously brought to 0.2 mm Hg.
The reaction mass becomes more and more viscous and after a further 90 minutes the condensation operation is concluded and 73.8 g of a copolyester are recovered at room temperature with the following elemental analysis: C ~ 57.05%; H - 5.10%; P = 4.29~.
The characteristics of the above polyester are shown in Table I.
The value of the meltlng DH, expressed as J/g, and the peak melting point, expressed in degrees centi-grade, are determined by differential ~can calorimetry (DSC), operating with a METTLER DSC 30 apparatus in a nitrogen atmosphere, with a gradient of 10C/minute, withln a temperature range of 35 to 300C.
Exam~le 2 Using the same procedure described in example 1, 30 g of 1,2-oxaphospholane-5-one-2-methyl-2-oxide and 90 g of ethylene glycol are reacted at 120-130C for 60 minutes.
40 cc of excess glycol are distilled and 0.5 g of tin-dibutyl-dilaurate are added to the anhydried reaction mass. The mixture is condensed at a temperature ranging from 175-156C for 8 hours with a vacuum from 300 to 0.05 mm of Hg.
2~8~66~
.
32.4 g of a distillate of ethylene glycol are obtained, whereas the residual product is characterized and is found to be an oligo-methyl-phosphin-~-propionate of ethylene glycol having 16.3% of phosphorous and a condensation degree of 3.36.
36.2 g of the above oligomer are reacted with 160 g of a PET prepolymer having a V.I.= 0.40 dl/g and containing 245 ppm of Sb (as Sb203) at a constant temperature of 275C for two hours with a vacuum decreasing from 4 to 0.05 mm of Hg.
About 160 g of a copolyester are obtained with the following elemental analysis: C = 57.09%; H - 4.60%;
P= 3.09%.
Example 3 Using the same procedure described in example 1, 23.35 g of phenyl-phosphin-~-propionic acid, 70 g of ethylene glycol and 60 g of a PET prepolymer with a V.I. = 0.23 del~g containing 205 ppm of Sb (as Sb203), are made to react.
81.7 g of a copolyester are obtained with the following elemental analysis: C ~ 59.51%; H = 4.88%;
P= 4.03%.
Exam~le 4 Using the same procedure described in example 1, 32.42 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide and 97 g of ethylene glycol and, after esterification and anhydrification, 95.85 g of a PET prepolymer with a 20~668 V.I. = 0.23 del/g containing 205 ppm of Sb (as Sb203), are charged.
123 g of a copolyester are obtained with the following elemental analysis: C = 59.6%; H = 4.77%;
P= 3.76%.
ExamDle 5 Using the same procedure described in example 1, 43.89 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide, 97 g of ethylene glycol and 64.50 g of a PET prepolymer with a V.I. = 0.23 del/g containing 205 ppm of Sb (as Sb203), are charged.
111.2 g of a copolyester are obtained with the following elemental analysis: C = 59.26%; H = 4.80%;
P= 5.45%.
Example 6 Using the same procedure described in example 1, 120 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide, and 250 g of ethylene glycol are made to react at 120-130C
for 90 minutes.
106 g of glycol are distilled at reduced pressure and 145 g of oligo-phenyl-~-propionate of ethylene glycol are recovered as a residue having 12.51% of phosphorous and a condensation degree of 5.63.
72 g of the above oligomer are reacted with 123 g of a PET prepolymer having a V.I. = 0.40 dl/g and containing 245 ppm of Sb (as Sbz03) at a temperature of 270-275C for 70 minutes under a vacuum of 3 to 0.05 mm 208~6~
of Hg.
About 143 g of a copolyester are obtained with`the following elemental analysis: C = 59.26%; H = 4.80%;
P= 4.57%.
S Example 7 14 parts of pellets of copolyester of example 1 are mixed with 86 parts of pellets of a polyethylene-terephthalate having a V.I. = 0.65 dl/g and acidity of 20 meq/kg.
This blend is dried at 130-C for 4 hours and spun directly on an automatic semi-industrial machine equipped with an extruder having 38 mm screws and 4 spinnerets of 45 mm in diameter.
A 50 dtex ~ibre is obtained with 10 circular floss operating with a recovery rate of 1200 m/minute. The phosphorous content is 0.6%.
These ~ibres, wound onto a spool after ensambling, are used to obtain tubular "socks" having a diameter of 10 cm which, when subjected to the Limited Oxygen Index (L.O.I.) flammability test, give a value of 31%. The L.O.I. for an identical product obtained without the addition of PET is 22%.
Exam~le 8 Using the same procedure described in example 7 a PET containing 18.6% of the copolyester of example 4 is spun.
The textile samples obtained show a L.O.I. of 10 .
33.5%.
Exam~le 9 A pre-dried blend composed of chips of commercial (Pibiter N 100) polybutyleneterephthalate (PBT) and of the copolyester of example 5, with a weight ratio of 78:22, ls extruded in a Werner Pfleiderer ZSK 25 twin-screw extruder.
Test samples having a thickness of 1/16 inch are in~ection moulded with the extruded polymer for the UL94 vertical test.
The PBT with this additive is classified VO.
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208566~
In the units having formula (I), R1 is preferably an alkylene radical containing 2 carbon atoms, whereas R2 is preferably a methyl or phenyl.
Compounds which produce units having formula (I) in the copolyester chain are carboxy-phosphinic acids having the formula:
HO-P-R1-COOH (II) their esters with an alcohol containing from l to 4 carbon atoms or with a diol containing from 2 to 4 carbon atoms, in the latter case possibly in the form of oligomers containing up to 5 monomeric units, or it is also possible to use the corresponding cyclic anhydrides hav~ng the formula:
R2-P-R1 (III) ~-C=O
with R1 and R2 which, in both formulae (II3 and (III), have the meaning defined above.
The linear copolyesters of the present invention are prepared according to a me*hod, which is a further aspect of the present invention, and which consists in the polycondensation reaction of the respective comonomers, and i.e. of bicarboxylic aromatic acid, of alkylene glycol and of the carboxyphosphinic monomer which produce the units having formula (I).
2~85668 The above copolyesters may also be prepared by a precondensation of the carboxyphosphinic compound with alkylene glycol, and subsequent treatment of these glycol esters with a prepolymer of bicarboxylic aromatic acid and alkylene glycol.
The linear copolyesters of the present invention are used as flame-retardant additives, suitable for providing flame-resistant characteristics to a wide range of organic polymers, such as linear polyesters with an aliphatic and/or aromatic structure, polyolefins, polyamides, polycarbonates, polyphenylen-oxides, polystyrenes, di- and ter- styrene polymers such as SAN and ABS, elastomeric copolymers such as EPR, EPDM, EVA.
In particular, the flame-retardant copolyester of the present invention is mixed and homogenized during the processing of the organic polymer in the molten state, which can then be transformed into end-products such as fibres, films, moulded items, etc.
The polymeric additives of the present invention are extremely compatible with the above organic polymers, forming real polymeric binders with these, and are also able to remain for long time within the polymeric material in which they are incorporated.
The quantity of copolyester of the present invention which is necessary for giving flame-retardant characteristics should be sufficient to ensure a phosphorous content (evaluated as an element) in the organic polymer ranging from 0.3 to 3% by weight, and preferably from 0.6 to 1.5% by weight.
The following examples provide a better illustration of the present invention but do not limit it in any way.
Example 1 15 g of 1,2-oxaphospholane-5-one-2-methyl-2-oxide and 45 g of ethylene glycol are charged into a three-necked 250 cc flask equipped with a mechanical stirrer,nitrogen inlet and condenser.
The temperature is brought, under a N2 atmosphere, to 120-130C, at which temperature the anhydride passes into solution. These conditions are maintained for 90 minutes, after which the excess glycol is distilled at reduced pressure, thus dehydrating the reaction mass at the same time.
The latter is then reacted with 60 g of a poly-ethyleneterephthalate prepolymer (PET) having a viscosity index V.I. = 0.23 dl/g and containing 205 ppm of Sb (as Sb203). The reactor is evacuated and cleaned three times with N2, and the system is then put under forced vacuum for 20 minutes.
The N2 atmosphere is subsequently restored and the temperature brought to 250C by means of a heating fluid. After the homogeneous fusion of the mass, the temperature is brought to 275C and the pressure to 400 208~668 mm Hg over a period of 30 minutes. After an hour at constant temperature and continually increasing vacuum, a forced vacuum is applied and the system is sponta-neously brought to 0.2 mm Hg.
The reaction mass becomes more and more viscous and after a further 90 minutes the condensation operation is concluded and 73.8 g of a copolyester are recovered at room temperature with the following elemental analysis: C ~ 57.05%; H - 5.10%; P = 4.29~.
The characteristics of the above polyester are shown in Table I.
The value of the meltlng DH, expressed as J/g, and the peak melting point, expressed in degrees centi-grade, are determined by differential ~can calorimetry (DSC), operating with a METTLER DSC 30 apparatus in a nitrogen atmosphere, with a gradient of 10C/minute, withln a temperature range of 35 to 300C.
Exam~le 2 Using the same procedure described in example 1, 30 g of 1,2-oxaphospholane-5-one-2-methyl-2-oxide and 90 g of ethylene glycol are reacted at 120-130C for 60 minutes.
40 cc of excess glycol are distilled and 0.5 g of tin-dibutyl-dilaurate are added to the anhydried reaction mass. The mixture is condensed at a temperature ranging from 175-156C for 8 hours with a vacuum from 300 to 0.05 mm of Hg.
2~8~66~
.
32.4 g of a distillate of ethylene glycol are obtained, whereas the residual product is characterized and is found to be an oligo-methyl-phosphin-~-propionate of ethylene glycol having 16.3% of phosphorous and a condensation degree of 3.36.
36.2 g of the above oligomer are reacted with 160 g of a PET prepolymer having a V.I.= 0.40 dl/g and containing 245 ppm of Sb (as Sb203) at a constant temperature of 275C for two hours with a vacuum decreasing from 4 to 0.05 mm of Hg.
About 160 g of a copolyester are obtained with the following elemental analysis: C = 57.09%; H - 4.60%;
P= 3.09%.
Example 3 Using the same procedure described in example 1, 23.35 g of phenyl-phosphin-~-propionic acid, 70 g of ethylene glycol and 60 g of a PET prepolymer with a V.I. = 0.23 del~g containing 205 ppm of Sb (as Sb203), are made to react.
81.7 g of a copolyester are obtained with the following elemental analysis: C ~ 59.51%; H = 4.88%;
P= 4.03%.
Exam~le 4 Using the same procedure described in example 1, 32.42 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide and 97 g of ethylene glycol and, after esterification and anhydrification, 95.85 g of a PET prepolymer with a 20~668 V.I. = 0.23 del/g containing 205 ppm of Sb (as Sb203), are charged.
123 g of a copolyester are obtained with the following elemental analysis: C = 59.6%; H = 4.77%;
P= 3.76%.
ExamDle 5 Using the same procedure described in example 1, 43.89 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide, 97 g of ethylene glycol and 64.50 g of a PET prepolymer with a V.I. = 0.23 del/g containing 205 ppm of Sb (as Sb203), are charged.
111.2 g of a copolyester are obtained with the following elemental analysis: C = 59.26%; H = 4.80%;
P= 5.45%.
Example 6 Using the same procedure described in example 1, 120 g of 1,2-oxaphospholan-5-one-2-phenyl-2-oxide, and 250 g of ethylene glycol are made to react at 120-130C
for 90 minutes.
106 g of glycol are distilled at reduced pressure and 145 g of oligo-phenyl-~-propionate of ethylene glycol are recovered as a residue having 12.51% of phosphorous and a condensation degree of 5.63.
72 g of the above oligomer are reacted with 123 g of a PET prepolymer having a V.I. = 0.40 dl/g and containing 245 ppm of Sb (as Sbz03) at a temperature of 270-275C for 70 minutes under a vacuum of 3 to 0.05 mm 208~6~
of Hg.
About 143 g of a copolyester are obtained with`the following elemental analysis: C = 59.26%; H = 4.80%;
P= 4.57%.
S Example 7 14 parts of pellets of copolyester of example 1 are mixed with 86 parts of pellets of a polyethylene-terephthalate having a V.I. = 0.65 dl/g and acidity of 20 meq/kg.
This blend is dried at 130-C for 4 hours and spun directly on an automatic semi-industrial machine equipped with an extruder having 38 mm screws and 4 spinnerets of 45 mm in diameter.
A 50 dtex ~ibre is obtained with 10 circular floss operating with a recovery rate of 1200 m/minute. The phosphorous content is 0.6%.
These ~ibres, wound onto a spool after ensambling, are used to obtain tubular "socks" having a diameter of 10 cm which, when subjected to the Limited Oxygen Index (L.O.I.) flammability test, give a value of 31%. The L.O.I. for an identical product obtained without the addition of PET is 22%.
Exam~le 8 Using the same procedure described in example 7 a PET containing 18.6% of the copolyester of example 4 is spun.
The textile samples obtained show a L.O.I. of 10 .
33.5%.
Exam~le 9 A pre-dried blend composed of chips of commercial (Pibiter N 100) polybutyleneterephthalate (PBT) and of the copolyester of example 5, with a weight ratio of 78:22, ls extruded in a Werner Pfleiderer ZSK 25 twin-screw extruder.
Test samples having a thickness of 1/16 inch are in~ection moulded with the extruded polymer for the UL94 vertical test.
The PBT with this additive is classified VO.
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Claims (10)
1. Linear copolyester which can be used as a flame retardant additive for organic polymers, composed of the polycondensation product of a bicarboxylic aromatic acid with an alkylene glycol containing from 2 to 6 carbon atoms and with a monomer which, in the chain of said copolyester, produces units having the formula:
(I) wherein R1 represents a linear, branched or cyclic alkylene radical, R2 represents an alkyl radical containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, said copolyester having a phosphorous content equal to at least 2.5% by weight.
(I) wherein R1 represents a linear, branched or cyclic alkylene radical, R2 represents an alkyl radical containing from 1 to 6 carbon atoms, or a substituted or non-substituted phenyl radical, said copolyester having a phosphorous content equal to at least 2.5% by weight.
2. Linear copolyester according to Claim 1, wherein the copolyester has a phosphorous content of 3-6%.
3. Linear copolyester according to any of the previous claims, wherein the bicarboxylic aromatic acid is terephthalic acid.
4. Linear copolyester according to any of the previous claims, wherein the alkylenic glycol is ethylene glycol.
5. Linear copolyester according to any of the previous claims, wherein R1 is an alkylene radical 13.
containing 2 carbon atoms.
containing 2 carbon atoms.
6. Linear copolyester according to any of the previous claims, wherein R2 is a radical selected from methyl and phenyl.
7. Linear copolyester according to any of the previous claims, wherein the monomer which produces units having formula (I) in the copolyester chain is selected from carboxy-phosphinic acids having the formula:
(II) wherein R1 and R2 have the previously-defined meaning, their esters with an alcohol containing from 1 to 4 carbon atoms or with a diol containing from 2 to 4 carbon atoms, the oligomers of said esters containing up to 5 monomeric units, and the corresponding cyclic anhydrides having the formula:
(III) wherein R1 and R2 have the previously-defined meaning.
(II) wherein R1 and R2 have the previously-defined meaning, their esters with an alcohol containing from 1 to 4 carbon atoms or with a diol containing from 2 to 4 carbon atoms, the oligomers of said esters containing up to 5 monomeric units, and the corresponding cyclic anhydrides having the formula:
(III) wherein R1 and R2 have the previously-defined meaning.
8. Procedure for the preparation of a linear copolyester according to any of the previous claims, including a polycondensation reaction of 14.
a bicarboxylic aromatic acid with an alkylene glycol containing from 2 to 6 carbon atoms and with a monomer which produces units having formula (I) in the copolyester chain where R1 and R2 have the previously-defined meaning.
a bicarboxylic aromatic acid with an alkylene glycol containing from 2 to 6 carbon atoms and with a monomer which produces units having formula (I) in the copolyester chain where R1 and R2 have the previously-defined meaning.
9. Procedure according to claim 8, wherein the monomer which produces units having formula (I) in the copolyester chain is selected from carboxy-phosphinic acids having formula (II), where R1 and R2 have the previously-defined meaning, their esters with an alcohol containing from 1 to 4 carbon atoms or with a diol containing from 2 to 4 carbon atoms, the oligomers os said esters containing up to 5 monomeric units, and the corresponding cyclic anhydrides having formula (III), where R1 and R2 have the previously-defined meaning.
10. Procedure according to one of claims 8 and 9, wherein the bicarboxylic aromatic acid is terephthalic acid and the alkylene glycol is ethylene glycol.
ll. Organic polymers selected from linear polyesters having an aliphatic and/or aromatic structure, polyolefins, polyamides, polycarbonates, polyphenylenoxides, polystyrenes, di- and ter-styrene polymers such as SAN and ABS, elastomeric copolymers such as EPR, EPDM, EVA, flame-15.
stabilized by the addition of a linear copolyester according to any of the claims from 1 to 7, 16.
ll. Organic polymers selected from linear polyesters having an aliphatic and/or aromatic structure, polyolefins, polyamides, polycarbonates, polyphenylenoxides, polystyrenes, di- and ter-styrene polymers such as SAN and ABS, elastomeric copolymers such as EPR, EPDM, EVA, flame-15.
stabilized by the addition of a linear copolyester according to any of the claims from 1 to 7, 16.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI91A003399 | 1991-12-18 | ||
| ITMI913399A IT1252236B (en) | 1991-12-18 | 1991-12-18 | LINEAR COPOLYESTER CONTAINING PHOSPHORUS, PREPARATION PROCEDURE AND USE AS AN ANTI-FLAME ADDITIVE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2085668A1 true CA2085668A1 (en) | 1993-06-19 |
Family
ID=11361370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002085668A Abandoned CA2085668A1 (en) | 1991-12-18 | 1992-12-17 | Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-retardant additive |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US5550207A (en) |
| EP (1) | EP0547701B1 (en) |
| JP (1) | JPH05331274A (en) |
| AT (1) | ATE169315T1 (en) |
| CA (1) | CA2085668A1 (en) |
| DE (1) | DE69226503T2 (en) |
| DK (1) | DK0547701T3 (en) |
| ES (1) | ES2120986T3 (en) |
| GR (1) | GR3027726T3 (en) |
| IT (1) | IT1252236B (en) |
| MX (1) | MX9207434A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4404365A1 (en) * | 1994-02-11 | 1995-08-17 | Cassella Ag | Polycondensates containing phosphine and phosphonic acid groups |
| US5399429A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant recycled polyester copolymers |
| US5399428A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant polyester copolymers |
| WO1995024445A2 (en) * | 1994-03-11 | 1995-09-14 | Monsanto Company | Flame-retardant recycled polyester compositions |
| DE19537700A1 (en) * | 1995-10-11 | 1997-04-17 | Hoechst Trevira Gmbh & Co Kg | Seat belt, especially for motor vehicles, woven from high strength yarns |
| EP0773313B1 (en) * | 1995-10-11 | 2000-08-09 | ARTEVA TECHNOLOGIES S.à.r.l. | Flame retardant safety belts containing phosphorous-modified polyester fibres |
| DE19635489C2 (en) | 1996-09-02 | 1998-11-26 | Clariant Gmbh | Flame-retardant, unsaturated polyester resins, processes for their production and their use for the production of moldings, laminates or coatings |
| DE19739852B4 (en) * | 1997-09-11 | 2006-03-16 | Zimmer Ag | Process for the preparation of flame-resistant polyesters |
| US20060240217A1 (en) * | 2005-04-21 | 2006-10-26 | Foss Manufacturing Co., Inc. | Fire-retardant, lightweight aircraft carpet |
| JP5596457B2 (en) * | 2010-07-29 | 2014-09-24 | 三菱樹脂株式会社 | Flame retardant polyester resin composition and molded article using the same |
| US8604105B2 (en) | 2010-09-03 | 2013-12-10 | Eastman Chemical Company | Flame retardant copolyester compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH380953A (en) * | 1956-11-30 | 1964-08-15 | Hoechst Ag | Process for the production of phosphorus-containing polyesters |
| DE2346787C3 (en) * | 1973-09-17 | 1980-05-08 | Hoechst Ag, 6000 Frankfurt | Flame retardant linear polyesters, processes for their manufacture and their use |
| DE2454189C3 (en) * | 1974-11-15 | 1980-08-14 | Hoechst Ag, 6000 Frankfurt | Process for the production of flame-retardant linear polyesters |
| US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| US5180793A (en) * | 1991-12-31 | 1993-01-19 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
-
1991
- 1991-12-18 IT ITMI913399A patent/IT1252236B/en active IP Right Grant
-
1992
- 1992-12-12 EP EP92203902A patent/EP0547701B1/en not_active Expired - Lifetime
- 1992-12-12 DE DE69226503T patent/DE69226503T2/en not_active Expired - Fee Related
- 1992-12-12 DK DK92203902T patent/DK0547701T3/en active
- 1992-12-12 AT AT92203902T patent/ATE169315T1/en not_active IP Right Cessation
- 1992-12-12 ES ES92203902T patent/ES2120986T3/en not_active Expired - Lifetime
- 1992-12-17 JP JP4337116A patent/JPH05331274A/en active Pending
- 1992-12-17 CA CA002085668A patent/CA2085668A1/en not_active Abandoned
- 1992-12-18 MX MX9207434A patent/MX9207434A/en not_active IP Right Cessation
-
1994
- 1994-05-23 US US08/247,525 patent/US5550207A/en not_active Expired - Fee Related
-
1996
- 1996-05-28 US US08/653,848 patent/US5602212A/en not_active Expired - Fee Related
-
1998
- 1998-08-26 GR GR980401906T patent/GR3027726T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US5602212A (en) | 1997-02-11 |
| ES2120986T3 (en) | 1998-11-16 |
| ITMI913399A1 (en) | 1993-06-18 |
| ITMI913399A0 (en) | 1991-12-18 |
| ATE169315T1 (en) | 1998-08-15 |
| DE69226503D1 (en) | 1998-09-10 |
| DK0547701T3 (en) | 1999-02-15 |
| DE69226503T2 (en) | 1999-03-25 |
| EP0547701A2 (en) | 1993-06-23 |
| EP0547701B1 (en) | 1998-08-05 |
| JPH05331274A (en) | 1993-12-14 |
| EP0547701A3 (en) | 1993-10-13 |
| IT1252236B (en) | 1995-06-05 |
| US5550207A (en) | 1996-08-27 |
| MX9207434A (en) | 1993-06-01 |
| GR3027726T3 (en) | 1998-11-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |