GB1558775A - Non-flammable moulding compositions - Google Patents
Non-flammable moulding compositions Download PDFInfo
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- GB1558775A GB1558775A GB49369/76A GB4936976A GB1558775A GB 1558775 A GB1558775 A GB 1558775A GB 49369/76 A GB49369/76 A GB 49369/76A GB 4936976 A GB4936976 A GB 4936976A GB 1558775 A GB1558775 A GB 1558775A
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- flammable
- mixture
- molding compositions
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- 239000000203 mixture Substances 0.000 title claims description 48
- 238000000465 moulding Methods 0.000 title claims description 20
- 239000004615 ingredient Substances 0.000 claims description 48
- 229920000728 polyester Polymers 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920001634 Copolyester Polymers 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 claims description 3
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003007 phosphonic acid derivatives Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims 3
- 239000004800 polyvinyl chloride Substances 0.000 claims 3
- 150000003504 terephthalic acids Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 150000003503 terephthalic acid derivatives Chemical group 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 239000006077 pvc stabilizer Substances 0.000 description 3
- VUTICWRXMKBOSF-UHFFFAOYSA-N 2,5-dibromoterephthalic acid Chemical group OC(=O)C1=CC(Br)=C(C(O)=O)C=C1Br VUTICWRXMKBOSF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000003612 virological effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(54) NON-FLAMMABLE MOLDING COMPOSITIONS
(71) We, BASF AKTIENGESELLSCHAFT, A German Joint Stock
Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:- The present invention relates to non-flammable molding comositions of linear polyesters based on terephthalic acid and aliphatic saturated diols.
Methods of rendering linear polyesters flame-resistant are well known. One such method consists in manufacturing a polyester containing a flame retardant as an integral part of its chemical structure. An example of such an agent is 2,5dibromoterephthalic acid, which may be built into the molecular structure of the polyester to render the latter flame-resistant. However, this suffers from the drawback that a relatively large amount of halogen is necessary to render the polyester adquately flame-resistant. This is undesirable for physiological reasons.
Furthermore, high halogen contents lead to strong discoloration of the products at the high manufacturing temperatures normally used. Another method of increasing the flame resistance of polyesters is to incorporate into the polyester compounds such as halogen, phosphorus or metal compounds, e.g. by physical mixing or fixing methods. Thus it is known to blend linear polyesters with aromatic polyphosphates.
However, relatively high phosphorus contents are necessary to effect satisfactory flame retardance for most applications. When such high contents of phosphorus compounds are used, it is difficult to avoid impairment of the physical and chemical properties and the processability of the polyesters.
The present invention seeks to provide novel flame-retardant thermoplastic polyester molding compositions of improved properties over the prior art.
According to the present invention there is provided a non-flammable molding composition prepared by blending
(a) an ingredient A consisting of a copolyester or a mixture of polyesters, the acid component of the copolyester or the mixture consisting of from I to 99% molar of halogenated terephthalic acid units and from 99 to 1% molar of unsubstituted terephthalic acid units and the alcohol component of the copolyester or the mixture consisting of an aliphatic saturated diol or a mixture of aliphatic saturated diols; and
(b) from 0.1 to 10% by weight, based on ingredient A, of an ingredient B consisting of one or more polyphosphonates having a degree of polymerization of at least 6 and derived from at least one dihydric phenol or naphthol of the formula
where Y denotes alkyl or halogen, n is zero or an integer, the symbols Y being identical or different when n is more than 1, and X denotes SO2, SO, SO2NH, O, S,
CO, CONH or branched or unbranched alkyl of the formula
in which R and R' are the same or different and denote hydrogen or alkyl of from 1 to 6 carbon atoms, as diol component, and from at least one phosphonic acid derivative of the general formula
where R denotes alkyl, phenyl, or a heterocyclic radical which may or may not contain halogen,
V denotes halogen, an ester group or hydroxyalkyl, and
W denotes halogen, an ester group or hydroxyalkyl, as acid component.
Preferably, sufficient of the ingredient B is used that the composition contains 0.1 to 4 2n by weight of phosphorus.
According to a preferred process, the molding compositions of the invention are prepared by adding ingredient B to ingredient A only after polycondensation of the latter is complete. Ingredient B may thus be added to the melt after the polycondensation reaction by means of suitable equipment, the sucess of the process being independent of whether the said polycondensation of ingredient A is carried out by a continuous or batchwise process.
The ingredient A may be obtained by various methods. It may be prepared by forming a random copolyester by cocondensation of all the monomeric starting materials. This may be effected in known manner by reacting, say, bis(2hydroxyethyl)terephthalate or a polyester prepolymer thereof with 2,5dibromoterephthalic acid. Alternatively, a mixture of dimethyl terephthalate and 2,5-dibromodimethyl terephthalate may be transesterified- with an alkanediol, whereupon the transesterification product is subjected to condensation polymerization. The ingredient A may also be obtained by direct esterification between terephthalic acid, 2,5-dihaloterephthalic acid and diol. The reaction polyester formation may be assisted by the use of conventional catalyst systems, preferably tetraalkyl titanate esters.Another method of preparing ingredient A is to use a homopolyester based on unsubstituted terephthalic acid together with a homopolyester based on halo-substituted terephthalic acid. In a preferred process, the two polyesters are blended, after completion of their polycondensation, in the molten state at temperatures of from 250"C to 3000C in vacuo.
In a special embodiment of the invention, which is particularly preferred, conventional PVC-stabilizers are used in the preparation of ingredient A. The use of such stabilizers improves the manufacture of copolyesters based on, say, dimethyl terephthalate and nuclear-halogenated dimethyl terephthalate and also the manufacture of a homopolyester based on nuclear-halogenated dimethyl terephthalate alone, since the presence of these stabilizers substantially prevents damage to the product by free hydrogen halide or free halogen liberated during the end phase of the condensation under the influence of the temperatures used at that stage. Thus it is possible to produce polyesters of type A having high bromine contents and nevertheless high molecular weight.
The ingredient B may be a single polyphosphonate or a mixture of polyphosphonates. The polyphosphonates may be homopolymers or copolymers of a plurality of diols and/or a plurality of phosphonic acids. Where at least two diols are present a variety of preparative methods may be used. One such method comprises copolycondensation of all the various monomers to form a random copolyester having a degree of polymerization of at least 6. Another process involves formation of the ingredient B by blending two or more individual polyesters in the molten state.
Where only one diol is used, any of the well-known methods of preparing polyesters may be employed.
In a special embodiment the blending of the ingredients A and B is carried out in the presence of a PVC stabilizer. Conventional stabilizers may be used. This largely prevents damage to the material or destruction thereof.
The molding compositions of the invention may be converted to, say, fibers and films. Such processing operations are also advantageously carried out in the presence of PVC stabilizers. It is also possible, if desired, to add conventional additives such as delustrants or dyes or further flame retardants.
A particular advantage of the invention is that the halogen-containing ingredient
A and the phosphorus-containing ingredient B have a synergistic effect on each
other in achieving flame retardance. In order to obtain a given degree of flame
retardance, it is sufficient to tise relatively low concentrations of the two
flameproofing ingredients, i.e. the halogen-containing terephthalic units in A
together with phosphorus-containing units B, whereas if only one such
flameproofing ingredient is used, a much higher concentration is required in order
to achieve the same results.
Shaped articles prepared from the molding compositions of the invention are
distinguished by extremely good flame-retardant properties, the physical and
chemical properties of the polyester being unimpaired or only insignificantly
impaired.
The following Examples illustrate the invention.
The relative viscosities viral of the polyesters given in the Examples below are those determined on a 3:2 mixture of phenol and o-di-chlorobenzene. The melting
points were determined using a heated microscope, but can also be determined by
the DSC method.
The criterion used in the Examples for assessing the flame retardance of the
molding compositions of the invention and of the substances used for comparison
was the test method UL 94 proposed by Underwriters' Laboratories, In this test, a
flat test specimen is suspended vertically at its top end, whilst its bottom end is flamed twice for periods of ten seconds. The results of the burning tests are listed in
Table 1 below.
Percentage compositions in the Examples are by weight.
EXAMPLE 1 (a) Preparation of Ingredient A:
A mixture of 1843 parts of dimethyl terephthalate, 175.9 parts of 2,5dibromodimethyl terephthalate, 1240 parts of ethylene glycol, 0.4 part of
Mn(OAc)2, 1.2 parts of Sb(OAc)3 and 20 parts of lead stearate is heated at 2200C over a period of two hours, during which period methanol is distilled off.
This prepolymer is then polycondensed, the pressure Reing gradually reduced from atmospheric to less than 1 mm of Hg, whilst a condensation temperature of 260"C is reached.
There is obtained a polyester having a relative viscosity of 1.402 and a melting
point of 246"C. The bromine content is 3.1%.
(b) Preparation of Ingredient B:
A mixture of 195 parts of phenyldichlorophosphine oxide, 97 parts of dihydroxydiphenyl ether, 120 parts of bis(4-hldroxyphenyl)sulfone and 2.0 parts of Cadiz is heated at 1 800C under a stream of nitrogen over a period of 1.5 hours.
The mixture is then heated up to 2200C and further condensed under reduced pressure (1 mm Hg) while the temperature is raised to 2600C.
There is obtained a solid brown substance having a molecular weight of 10,800
and a relative viscosity of 1,140. Its melting point is l700-1800C and its
phosphorus content is 8.2%.
(c) Blending of Ingredients A and B:
50 parts of the pulverized ingredient B and 1.1 parts of lead stearate are added,
under nitrogen, to the fully polycondensed, molten ingredient A (1000 parts) and
are stirred into the melt for 5 minutes at atmospheric pressure and then for 5
minutes at a reduced pressure of less than 1 mm of Hg, the mixture being finally
cooled. There is obtained a flame-retardant polyethylene terephthalate having a
relative viscosity of 1.384 and a melting point of 241"C. The bromine content is 2.9 /n and the phosphorus content is 0.39%.
COMPARATIVE EXAMPLE IA
A mixture of 1,745 parts of dimethyl terephthalate, 351.8 parts of 2,5
dibromodimethyl terephthalate, 1,240 parts of ethylene glycol, 0.4 part of Mn(OAc)z, 1.2 parts of Sb(OAc)3 is heated at 2200C over a period of 2 hours,
during which period methanol is distilled off.
This prepolymer is then polycondensed, the pressure being gradually reduced
from atmospheric to less than 1 mm of Hg, while the condensation temperature
reaches a final value of 260 C. There is obtained a polyester having a relative
viscosity of 1.363 and a melting point of 231"C. The bromine content is 6.3S.
COMPARATIVE EXAMPLE 1B 100 parts of the ingredient B described under Example lb are added, in pulverized form, to 1000 parts of molten polyethylene terephthalate under nitrogen and are stirred into the melt for 5 minutes at atmospheric pressure and then for 5 minutes under a reduced pressure of less than 1 mm of Hg, the mixture being finally cooled. There is obtained a product having a relative viscosity of 1,372, a melting point of 245"C and phosphorus content of 0.74 zÓ.
EXAMPLE 2 (a) Preparation of Ingredient A:
585 parts of 2,5-dibromodimethyl terephthalate, 225 parts of ethylene glycol, 0.5 part of tetrabutyl ortho-titanate and 5.8 parts of lead stearate are heated at 220"C over 2 hours, during which period methanol is distilled off.
This prepolymer is then polycondensed, the pressure being gradually reduced from atmospheric to less than 1 mm of Hg. The final condensation temperature achieved is 225"C. There is obtained a polyester having a relative viscosity of 1.323 and a melting point of 200"C. The bromine content is 41.7 / 50 parts of the resulting polyester are added to 1000 parts of molten polyethylene terephthalate under nitrogen and are stirred into the melt for 5 minutes at atmospheric pressure and then for 5 minutes under a reduced pressure of less than 1 mm of Hg. The resulting ingredient A has a relative viscosity of 1.390 and a bromine content of 2%.
(b) Preparation of Ingredient B
A mixture of 195 parts of phenylphosphonic acid dichloride, 532 parts of 2,2bis(3,5-dibromo-4-hydroxyphenyl)propane and 1.0 part of CaCI2 in 0.5 1 of 1,1,2,2tetrachloroethane is heated over 4 hours to the boiling temperature of tetrachloroethane. The mixture is then heated under reflux for 15 hours, and after cooling added dropwise to about 4 1 methanol. The precipitate thus formed is filtered off and dried. The white powder obtained in this manner has a molecular weight of 6,400 and a melting point of 175"C. Its phosphorus content is 4.7% and its bromine content is 46.6%.
(c) Blending of Ingredients A and B:
50 parts of the pulverized ingredient B and 1.1 part of lead stearate are added to the fully polycondensed molten ingredient A (1000 parts) under nitrogen and are stirred into the melt for 5 minutes at atmospheric pressure and then for 5 minutes at a reduced pressure of less than 1 mm of Hg, the mixture being finally cooled. There is obtained a flame-retardant polyethylene terephthalate having a relative viscosity of 1.384. Its melting point is 241"C, its bromine content 2.9"' and its phosphorus content 0.39%.
TABLE 1
Result of burning test UL 94 (Underwriters' Laboratories)
Burning time
Ex. No. of specimen Remarks
1 0 Non-flammable, melts away from flame IA 8 releases burning drops I B 2 readily releases drops which burn for
a brief period
2 0 non-flammable, melts away from flame
WHAT WE CLAIM IS:
1. Non-flammable molding compositions prepared by blending
(a) an ingredient A, consisting of a copolyester or a mixture of polyesters, the acid component of the copolyester or the mixture consisting of from 1 to 99% molar of halogenated terephthalic acid units and from 99 to 1% molar of unsubstituted terephthalic acid units and the alcohol component of the copolyester or the mixture consisting of an aliphatic saturated diol or a mixture of aliphatic saturated diols; and
(b) from 0.1 to 10% by weight, based on ingredient A, or an ingredient B, consisting of one or more polyphosphonates having a degree of polymerization of at least 6 and derived from at least one dihydric phenol or naphthol of the formula
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (9)
1 0 Non-flammable, melts away from flame IA 8 releases burning drops I B 2 readily releases drops which burn for
a brief period
2 0 non-flammable, melts away from flame
WHAT WE CLAIM IS:
1.Non-flammable molding compositions prepared by blending
(a) an ingredient A, consisting of a copolyester or a mixture of polyesters, the acid component of the copolyester or the mixture consisting of from 1 to 99% molar of halogenated terephthalic acid units and from 99 to 1% molar of unsubstituted terephthalic acid units and the alcohol component of the copolyester or the mixture consisting of an aliphatic saturated diol or a mixture of aliphatic saturated diols; and
(b) from 0.1 to 10% by weight, based on ingredient A, or an ingredient B, consisting of one or more polyphosphonates having a degree of polymerization of at least 6 and derived from at least one dihydric phenol or naphthol of the formula
where Y denotes alkyl or halogen, n is zero or an integer, the symbols Y being identical or different when n is more than 1, and X denotes SO2, SO, SO2NH, O, S,
CO, CONH, or branched or unbranched alkyl of the formula
in which R and R' are the same or different and denote hydrogen or alkyl of from I to 6 carbon atoms, as diol component, and from at least one phosphonic acid derivative of the general formula
where R denotes alkyl, phenyl, or a heterocyclic radical, V denotes halogen, an ester group or hydroxyalkyl, W denotes halogen, an ester group or hydroxyalkyl, as the acid component.
2. Non-flammable molding compositions as claimed in claim 1, wherein ingredients A and B are prepared by cocondensation of the monomers to form the random copolyester or by preparing the copolyester by blending the homopolyesters in the molten state.
3. Non-flammable molding compositions as claimed in claim 1 or 2 which contain a stabilizer for polyvinyl chloride.
4. Non-flammable molding compositions as claimed in claim 3, wherein the ingredient A is prepared in the presence of a stabilizer for polyvinyl chloride.
5. Non-flammable molding compositions as claimed in claims 3 or 4, wherein a stabilizer for polyvinyl chloride is present during blending of ingredients A and B.
6. Non-flammable molding compositions as claimed in any of claims I to 5 which additionally contain a delustrant, a dye and/or a further flame retardant with or without other additives.
7. Non-flammable molding compositions as claimed in any of claims 1 to 6, wherein the amount of ingredient B present is sufficient to provide a phosphorus content of 0.1 to 4% by weight.
8. Non-flammable molding compositions as claimed in claim 1 and substantially as described in either of the foregoing Examples I and 2.
9. Non-flammable moldings made from molding compositions as claimed in any of claims 1 to 8.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752553208 DE2553208A1 (en) | 1975-11-27 | 1975-11-27 | FLAME RESISTANT MOLDING COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1558775A true GB1558775A (en) | 1980-01-09 |
Family
ID=5962735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB49369/76A Expired GB1558775A (en) | 1975-11-27 | 1976-11-26 | Non-flammable moulding compositions |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE848411A (en) |
| CH (1) | CH601417A5 (en) |
| DE (1) | DE2553208A1 (en) |
| FR (1) | FR2333020A1 (en) |
| GB (1) | GB1558775A (en) |
| IT (1) | IT1066716B (en) |
| NL (1) | NL7613157A (en) |
-
1975
- 1975-11-27 DE DE19752553208 patent/DE2553208A1/en not_active Withdrawn
-
1976
- 1976-11-16 FR FR7634470A patent/FR2333020A1/en active Granted
- 1976-11-17 BE BE172418A patent/BE848411A/en unknown
- 1976-11-24 IT IT52321/76A patent/IT1066716B/en active
- 1976-11-24 CH CH1479176A patent/CH601417A5/xx not_active IP Right Cessation
- 1976-11-25 NL NL7613157A patent/NL7613157A/en not_active Application Discontinuation
- 1976-11-26 GB GB49369/76A patent/GB1558775A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2333020B1 (en) | 1980-04-11 |
| DE2553208A1 (en) | 1977-06-16 |
| IT1066716B (en) | 1985-03-12 |
| BE848411A (en) | 1977-05-17 |
| CH601417A5 (en) | 1978-07-14 |
| NL7613157A (en) | 1977-06-01 |
| FR2333020A1 (en) | 1977-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |