DD275249A5 - PROCESS FOR PREPARING POLYESTROLES CONTAINING CHEMICALLY BOUND BROMO - Google Patents
PROCESS FOR PREPARING POLYESTROLES CONTAINING CHEMICALLY BOUND BROMO Download PDFInfo
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- DD275249A5 DD275249A5 DD88313477A DD31347788A DD275249A5 DD 275249 A5 DD275249 A5 DD 275249A5 DD 88313477 A DD88313477 A DD 88313477A DD 31347788 A DD31347788 A DD 31347788A DD 275249 A5 DD275249 A5 DD 275249A5
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- German Democratic Republic
- Prior art keywords
- glycol
- polyestrol
- bromine
- general formula
- added
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 125000001246 bromo group Chemical class Br* 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 47
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 38
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 38
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000031709 bromination Effects 0.000 claims abstract description 8
- 238000005893 bromination reaction Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000002334 glycols Chemical class 0.000 claims description 18
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000008034 disappearance Effects 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 230000034659 glycolysis Effects 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 9
- 238000010438 heat treatment Methods 0.000 claims 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 abstract description 20
- 229910000042 hydrogen bromide Inorganic materials 0.000 abstract description 10
- 229920005862 polyol Polymers 0.000 abstract description 9
- 150000003077 polyols Chemical class 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 abstract 1
- 101150065749 Churc1 gene Proteins 0.000 abstract 1
- 102100038239 Protein Churchill Human genes 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 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
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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
- C08G63/91—Polymers modified by chemical after-treatment
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4607—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen having halogens
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von Polyestrolen, welche chemisch gebundenes Brom enthalten. Die Bromierung der Polyestrole, die verestertes oder ungebundenes Glykol der allgemeinen Formel HOCH2RCH2OH, in welcher R eine Gruppe mit der Formel CHCH oder CC bedeutet, enthaelt, wird bei Temperaturen von 10-100C, vorzugsweise von 20-40C, durchgefuehrt. Bei dem erfindungsgemaessen Verfahren wird kein Bromwasserstoff in Nebenreaktionen gebildet. Die erfindungsgemaess hergestellten bromierten Polyestrole sind somit frei von Bromwasserstoffverunreinigungen. Eine Korrosion der Metallreaktoren durch Bromwasserstoff wird ausgeschlossen. Bromierte Polyestrole werden zur Herstellung von schwerbrennbaren Polyurethanprodukten verwendet.The invention relates to a process for the preparation of polyestrols which contain chemically bound bromine. The bromination of the polyols, containing esterified or unbound glycol of the general formula HOCH 2 RCH 2 OH in which R is a group of the formula CHCH or CC, is carried out at temperatures of 10-100C, preferably 20-40C. In the process according to the invention, no hydrogen bromide is formed in side reactions. The brominated polyols prepared according to the invention are thus free from hydrobromic impurities. Corrosion of the metal reactors by hydrogen bromide is excluded. Brominated polyols are used to make flame resistant polyurethane products.
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Polyestrolen, welche chemisch gebundenes Brom enthalten und zur Herstellung von schwerbrennharen Polyurethanprodukten Anwendung Finden können.The invention relates to a process for the preparation of polyestrols which contain chemically bound bromine and can find application for the production of hard-to-reach polyurethane products.
Unter der Bezeichnung Polyestrole versteht man lineare oder verzweigte Polyoster, deren Makromoleküle vorwiegend mit Alkoholgruppen beendet sind.The term polyestrole is understood to mean linear or branched polyesters whose macromolecules are terminated predominantly with alcohol groups.
Polyestrole, weiche chemisch gebundenes Brom enthalten, werden nach den bekannten Verfahren durch Polykondensation von Dicarboxylsäuren oder deren Anhydriden mit Glykolen und gegebenenfalls mit mehrwertigen Alkoholen erhalten, wobei mindestens einer der eingesetzten Ausgangsstoffe gebundenes Brom enthält. Als Ausgangsrohstoff, welcher chemisch gebundenes Brom enthält, wird in den bekannten Verfahren beispielsweise Tetrabromphthalsäuroanhydrid, Dibromneopentylglykol oder ein Produkt der Anlagerung von zwei Molen Äthylen- oder Propylenoxid zum Tetrabrombisphenol A angewendet. Diese Polykondensation wird normalerweise bei einer Temperatur im Bereich von 180-2200C mit Abdestillieren vom Kondensationswasser bei molarem Überschuß von Alkoholgruppen im Verhältnis zu Säuregruppen im Reaktionsgemisch durchgeführt. Unter diesen Bedingungen besteht eine Gefahr von Nebenreaktionen, welche unter Abspaltung vom Bromwasserstoff, insbesondere in Gegenwart von kleinen Mengen mancher Verunreinigungen, zum Beispiel von Eisensalzen, verlaufen können.Polyols which contain chemically bound bromine are obtained by the known processes by polycondensation of dicarboxylic acids or their anhydrides with glycols and optionally with polyhydric alcohols, at least one of the starting materials used containing bound bromine. As starting material which contains chemically bound bromine, for example, tetrabromophthalic anhydride, dibromoneopentyl glycol or a product of the addition of two moles of ethylene oxide or propylene oxide to tetrabromobisphenol A is used in the known processes. This polycondensation is usually carried out at a temperature in the range of 180-220 0 C with distilling off the water of condensation at a molar excess of alcohol groups relative to acid groups in the reaction mixture. Under these conditions, there is a danger of side reactions which can proceed with elimination of the hydrogen bromide, in particular in the presence of small amounts of some impurities, for example iron salts.
Mit der Erfindung wird ein Verfahren zur Herstellung von Polyestrolen, die chemisch gebundenes Brom enthalten, bereitgestellt, das sich gegenüber herkömmlichen Verfahren dadurch auszeichnet, daß kein Bromwasserstoff in Nebenreaktionen entsteht. Die erfindungsgemäß hergestellten bromierten Polyestrole sind somit frei von Bromwasserstoffverunreinigungen. Eine Korrosion der Metallreaktoren durch Bromwasserstoff wird ausgeschlossen.The invention provides a process for the preparation of polyestrols containing chemically bound bromine, which is distinguished from conventional processes in that no hydrogen bromide is produced in side reactions. The brominated polyols prepared according to the invention are thus free from hydrobromic impurities. Corrosion of the metal reactors by hydrogen bromide is excluded.
Darlegung des Wesens der ErfindungExplanation of the essence of the invention
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Polyestrolen zu entwickeln, welche chemisch gebundenes Brom enthalten, unter solchen Bedingungen, welche eine Möglichkeit der Abspaltung vom Bromwasserstoff während der Synthese, der Verunreinigung des Produktes mit Bromwasserstoff sowie der Korrosion der Metallapparate unter Einwirkung vom Bromwasserstoff sowohl während der Synthese als auch während einer weiteren Verarbeitung des bromierten Polyestrols eliminieren.The present invention has for its object to provide a process for the preparation of polyestrols containing chemically bound bromine, under such conditions, which is a possibility of elimination of hydrogen bromide during the synthesis, the contamination of the product with hydrogen bromide and the corrosion of the metal apparatus Eliminate the effect of hydrogen bromide both during synthesis and during further processing of the brominated polyestrol.
Erfindungsgemäß werden Polyestrole, welche chemisch gebundenes Brom enthalten, unter milden Bedingungen, die eine Möglichkeit der Zersetzung unter Abspaltung vom Bromwasserstoff ausschließen, auf solche Weise hergestellt, daß bei der Temperatur von 10-1000C, vorteilhaft von 20-40°C, Brom zum Polyestrol zugegeben wird, welches verestertes oder ungebundenes Glykol der allgemeinen Formel HOCH2-R-CH2OH enthält, in welcher R eine Gruppe mit der Formel -CH=CH- oder -CsC- bedeutet, wobei Brom in einer Menge von 1-2 Grammatomen auf 1 Mol Gruppen mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, angewendet wird, und die Reaktion bis zum Verschwinden von freiem Brom im Reaktionsgemisch durchgeführt wird.According to the invention, polyols containing chemically bound bromine are prepared under mild conditions which preclude a possibility of decomposition with elimination of hydrogen bromide in such a way that at the temperature of 10-100 0 C, preferably from 20-40 ° C, bromine is added to the Polyestrol containing esterified or unbound glycol of the general formula HOCH2-R-CH2OH, in which R is a group of the formula -CH = CH- or -CsC-, wherein bromine in an amount of 1-2 gram atoms 1 mol of groups having the general formula HOCH 2 -R-CH 2 OH in which R has the meanings given above, is applied, and the reaction is carried out until the disappearance of free bromine in the reaction mixture.
Die Ausgangspolyestrole, welche in dem erfindungsgemäßen Verfahren angewendet werden, bestehen aus Resten von aliphatischen mehrbasischen Säuren und aus Resten von gesättigten Glykolen und gegebenenfalls von mehrwertigen Alkoholen und gegebenenfalls auch Glykolen mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat. Darüber hinaus können diese Polyestrole auch ungebundenes gesättigtes Glykol sowie ungebundenes Glykol mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, enthalten: das letztgenannte Glykol kann im Polyestrol in ungebundener Form, oder in ein- oder beidseitig veresterter Form sowie in diesen beiden Formen anwesend sein.The starting polyols, which are used in the process according to the invention consist of residues of aliphatic polybasic acids and residues of saturated glycols and optionally polyhydric alcohols and optionally also glycols having the general formula HOCH 2 -R-CH 2 OH, in which R the has the meanings given above. In addition, these polyols can also contain unbound saturated glycol and unbound glycol having the general formula HOCH 2 -R-CH 2 OH, in which R has the meanings given above: the last-mentioned glycol can be present in the polyestrol in unbound form, or in or esterified form on both sides as well as being present in these two forms.
Die im Polyestrol enthaltenen Reste aromatischer Polycarboxylsäuren kommen vorzugsweise aus dem Destillationsrückstand vom rohen Dimethylterephthalat, welcher aus Methylestern und Anhydriden von Benzenpolycarboxylsäuren und aus unbekannten Substanzen besteht. Um ein Polyestrol zu erhalten, wird dieses Gemisch der Umesterungsreaktion mit gesättigten Glyknlen und gegebenenfalls mit mehrwertigen Alkoholen sowie mit einem Glykol mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, unterworfen und im Produkt der Umesterungsreaktion wird ein Teil dos gesättigten Glykols oder des Glykols mit der allgemeinen Formel HOCH2-R-CH2OH in ungebundener Form zurückgelassen und zum fertigen Polyostrol wird ein aus einer oder aus dioson beiden Gruppen ausgewähltes Glykol oder gegebenenfalls ein mehrwertiger Alkohol zugegeben.The radicals of aromatic polycarboxylic acids contained in the polyestrol preferably come from the distillation residue of crude dimethyl terephthalate, which consists of methyl esters and anhydrides of benzene polycarboxylic acids and of unknown substances. In order to obtain a Polyestrol, this mixture of the transesterification reaction with saturated Glyknlen and optionally with polyhydric alcohols and with a glycol having the general formula HOCH 2 -R-CH 2 OH, in which R has the meanings given above, subjected and in the product of Transesterification reaction is left a part of the saturated glycol or the glycol having the general formula HOCH 2 -R-CH 2 OH in unbound form and to the finished Polyostrol is added a selected from one or dioson two groups glycol or optionally a polyhydric alcohol.
!n einer anderen Ausführungsform des Verfahrens zur Herstellung von Polyestrolen wird zur Bromierung ein Gemisch, welches die Reste aromatischer oder aliphatischor Polycarboxylsäuren enthält, zuerst der Umesterungsreaktion mit gesättigten Glykolen und gegebenenfalls mit gesättigten mehrwertigen Alkoholen zwecks Beseitigung von niedermolekularen Reaktionsprodukten unterworfen und dann, in der zweiten Stufe, wird die Glykolyse des erhaltenen gesättigten Polyestrols mit einem Glykol mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, durchgeführt. Als Roste aromatischer Polycarboxylsäuron können die Polyestrole auch die Roste der Phtalsäure und der Isophthalsäure sowie der Reste der Terephthalsäure enthalten.In another embodiment of the process for the preparation of polyestroles, for bromination, a mixture containing the radicals of aromatic or aliphatic polycarboxylic acids is first subjected to the transesterification reaction with saturated glycols and optionally with saturated polyhydric alcohols to remove low molecular weight reaction products and then in the second Stage, the glycolysis of the resulting saturated Polyestrols with a glycol having the general formula HOCH 2 -R-CH 2 OH, in which R has the meanings given above, is performed. As grates aromatic Polycarboxylsäuron the polyestroles may also contain the grids of phthalic acid and isophthalic acid and the residues of terephthalic acid.
Die im Polyestrol enthaltenen Reste aliphatischor Dicarboxylsäuren umfassen die Roste von Adipinsäure, Glutarsäure und Bernsteinsäure. Zur Erzeugung vom Polyestrol werden die Dicarboxylsäuren oder deren Methylesier der Polykondensationsreaktion mit gesättigten Glykolen und gegebenenfalls mit mehrwertigen Alkoholen sowie mit Glykolen mitThe radicals contained in the polyestrol aliphatischor dicarboxylic acids include the grids of adipic acid, glutaric acid and succinic acid. To produce the polyestrol, the dicarboxylic acids or their methyl ethers of the polycondensation reaction with saturated glycols and optionally with polyhydric alcohols and with glycols
der allgemeinen Formel HOCHr-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, unterworfen undgegebenenfalls wird zum fertigen Polyestrol ein Glykol mit der allgemeinen Formel HOCHr-R-CH2OH zugegeben.of the general formula HOCHr-R-CH 2 OH, in which R has the abovementioned meanings, and if appropriate, a glycol having the general formula HOCHr-R-CH 2 OH is added to the finished polyestrol.
werden.become.
umfassen eis- und trans-Buten-2-dioM,4- sowie Butin-2-diol-1,4.include cis and trans-butene-2-dioM, 4- and butyne-2-diol-1,4.
sowie die Veresterungsprodukte dieser Glykole im Falle, wenn Brom an ein ungesättigtes Polyestrol, welches veresterte Restevom Glykol mit der allgemeinen Formel HOCH2-R-CH2OH, in welcher R die oben angegebenen Bedeutungen hat, enthält,angelagert wird.and the esterification products of these glycols in the case when bromine is attached to an unsaturated polyestrol containing esterified residues of glycol of the general formula HOCH 2 -R-CH 2 OH in which R has the meanings given above.
zu 30Gew.-% betragen. Her Gehalt an Resten mit der allgemeinen Formel -0-CH2-R-CH2-O-, in welcher R die obenangegebenen Bedeutungen hat, im Polyestrol, welches zur Bromierung bestimmt ist, kann bis zu 40Gow.-% betragen. Der Gehaltan Brom in Polyestrolen, welche chemisch gebundenes Brom enthalten und die nach dem erfindungsgemäßen Verfahrenüi halten wurden, kann bis zu 36,3Gew.-% oder bis zu 39Gew.-%, entsprechend, betragen.to 30Gew .-% amount. The content of radicals having the general formula -O-CH 2 -R-CH 2 -O-, in which R has the meanings given above, in the polyestrol intended for bromination may be up to 40% by weight. The content of bromine in polyestrols which contain chemically bound bromine and which have been kept by the process according to the invention may be up to 36.3% by weight or up to 39% by weight, respectively.
einem gegenüber Brom neutralen organischen Lösungsmittel, zum Beispiel im Tetrachlorkohlenstoff, welcher nach dema bromine neutral organic solvent, for example in carbon tetrachloride, which after the
insbesondere mit Diisocyanates wobei entweder lineare oder vernetzte Polyurethane gebildet werden.in particular with diisocyanates, wherein either linear or crosslinked polyurethanes are formed.
In einem Reaktor, welcher mit Rührer, Thermometer, Rückflußkühler und Tropftrichter ausgestattet wurde, werden 200g Polyestrol (mit 0,44 Mol Doppelbindungen), welches durch Polykondensation von 116,8g (0,8 Mol) Adipinsäure, 39,6g (0,45 Mol) Buten-2-diol-1,4 und 74,7g (0,45 Mol) Triäthylenglykol erhalten wurde, untergebracht. Während 5 Stunden werden zum Polyestrol 22,3cm3 (0,88 Grammatom) Brom eingetropft und die Temperatur des Reaktionsgemisches im Bereich von 25-3O0C gehalten. Es werden 270g Produktes mit einem Gehaltan Brom gleich 25%, Hydroxylzahl 120 mg KOH/g und Säurezahl 1,3 mg KOH/g erhalten.In a reactor equipped with stirrer, thermometer, reflux condenser and dropping funnel, 200 g of polyestrol (with 0.44 moles of double bonds) obtained by polycondensation of 116.8 g (0.8 mol) of adipic acid, 39.6 g (0.45 Butene-2-diol-1,4 and 74,7g (0.45 mol) of triethylene glycol was obtained. For 5 hours 22,3cm 3 (0.88 gram atom) of bromine are added dropwise to Polyestrol and the temperature of the reaction mixture in the range of 25-3O 0 C. There are obtained 270 g of product with a content of bromine equal to 25%, hydroxyl number 120 mg KOH / g and acid number 1.3 mg KOH / g.
dreifacher Bindungen), welches durch Polykondensation von ?48g (2,68 Mol) Butin-2-diol-1,4,804g (3,67 Mol) Diäthylenglykolund 1227,6g Rückstand nach der Destillation von rohem Dimethylterephthalat, welcher hauptsächlich Methylester undtriple bonds) formed by polycondensation of? 48g (2.68 moles) of butyne-2-diol-1,4,804g (3.67 moles) of diethylene glycol and 1227.6 grams of residue after the distillation of crude dimethyl terephthalate, which is mainly methyl ester and
untergebracht. Dieser Rückstand wird durch Säurezahl 12 mg KOH/g, Verseifungszahl 464 mg KOH/g und Viskosität bei deraccommodated. This residue is acid value 12 mg KOH / g, saponification number 464 mg KOH / g and viscosity at the
gleich 23%, Hydroxyizahl 275mg KOH/g und Säurezahl 2,7mg KOH/g erhalten.23%, hydroxy number 275 mg KOH / g and acid number 2.7 mg KOH / g.
eines gesättigten Polyestrols, welches durch Polykondensation von 400g (3,22 Mol) Äthylenglykol, 1250g (3,22 Mole)of a saturated polyestrol obtained by polycondensation of 400 g (3.22 mol) of ethylene glycol, 1250 g (3.22 mol)
eingetropft.dripped.
125mg KOH/g erhalten.125 mg KOH / g.
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL1987264530A PL149676B1 (en) | 1987-03-09 | 1987-03-09 | Method for manufacturing polyestrols containing chemically bounded bromium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD275249A5 true DD275249A5 (en) | 1990-01-17 |
Family
ID=20035343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD88313477A DD275249A5 (en) | 1987-03-09 | 1988-03-07 | PROCESS FOR PREPARING POLYESTROLES CONTAINING CHEMICALLY BOUND BROMO |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH01221422A (en) |
| DD (1) | DD275249A5 (en) |
| DE (1) | DE3807581A1 (en) |
| IT (1) | IT1216022B (en) |
| PL (1) | PL149676B1 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1263297B (en) * | 1960-10-27 | 1968-03-14 | Huels Chemische Werke Ag | Manufacture of flame-retardant polyester molded parts |
-
1987
- 1987-03-09 PL PL1987264530A patent/PL149676B1/en unknown
-
1988
- 1988-03-07 DD DD88313477A patent/DD275249A5/en not_active IP Right Cessation
- 1988-03-08 DE DE3807581A patent/DE3807581A1/en not_active Ceased
- 1988-03-08 IT IT8819690A patent/IT1216022B/en active
- 1988-03-09 JP JP63053886A patent/JPH01221422A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PL264530A1 (en) | 1988-10-13 |
| JPH01221422A (en) | 1989-09-04 |
| DE3807581A1 (en) | 1988-09-22 |
| IT1216022B (en) | 1990-02-22 |
| IT8819690A0 (en) | 1988-03-08 |
| PL149676B1 (en) | 1990-03-31 |
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