DE1148751B - Process for the production of flame-retardant, self-extinguishing resins - Google Patents
Process for the production of flame-retardant, self-extinguishing resinsInfo
- Publication number
- DE1148751B DE1148751B DER29218A DER0029218A DE1148751B DE 1148751 B DE1148751 B DE 1148751B DE R29218 A DER29218 A DE R29218A DE R0029218 A DER0029218 A DE R0029218A DE 1148751 B DE1148751 B DE 1148751B
- Authority
- DE
- Germany
- Prior art keywords
- flame
- retardant
- production
- self
- ester
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 12
- 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 title claims description 8
- 239000003063 flame retardant Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011347 resin Substances 0.000 title claims description 4
- 229920005989 resin Polymers 0.000 title claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Chemical group 0.000 claims description 2
- 239000001257 hydrogen Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- -1 3-methacryloxy-2-chloropropyl Chemical group 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- FSKLCMXEFITTQW-UHFFFAOYSA-N dichlorophosphoryl(dimethoxy)-lambda3-chlorane Chemical compound COCl(P(=O)(Cl)Cl)OC FSKLCMXEFITTQW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Verfahren zur Herstellung von schwer entflammbaren, selbstlöschenden Harzen Zur Herabsetzung der Entflammbarkeit werden bekanntlich in Kunststoffe Ester von Phosphorsäuren eingearbeitet. Da zur Erzielung eines ausreichenden flammhemmenden Effektes große Zusätze an Estern erforderlich sind, werden die physikalischen Eigenschaften, insbesondere die Wärmeformbeständigkeit, solcher Kunststoffe stark herabgesetzt. Process for the production of flame retardant, self-extinguishing Resins As is known, esters are used in plastics to reduce flammability incorporated by phosphoric acids. Because to achieve a sufficient flame retardant Effect, large additions of esters are required, the physical properties, especially the heat resistance, such plastics greatly reduced.
Es ist ein Verfahren bekannt, nach dem die Entflammbarkeit von Kunststoffen durch Vinylgruppen enthaltende Phosphorsäureester herabgesetzt wird. A method is known by which the flammability of plastics is reduced by phosphoric acid esters containing vinyl groups.
Dieses Verfahren hat den Nachteil, daß diese bekannten Ester sehr langsam polymerisieren. Beispielsweise erhält man bei der Polymerisation von Diäthylvinylphosphonat in Gegenwart von organischen Peroxyden nach 40 Stunden langem Erhitzen auf 1000 C ein Polymerisat von öliger Konsistenz.This process has the disadvantage that these known esters are very polymerize slowly. For example, diethyl vinyl phosphonate is polymerized in the presence of organic peroxides after heating to 1000 for 40 hours C a polymer with an oily consistency.
Ferner wurde bereits vorgeschlagen, phosphorhaltige Polykondensationsprodukte aus mit Hydroxylgruppen umsatzfähigen Derivaten der phosphorigen Säure und Hydroxylgruppen aufweisenden Polyestern herzustellen. Nach dem genannten Verfahren werden flammfeste Produkte erhalten, die in organischen Lösungsmitteln unlöslich sind und in der Wärme nicht verformt werden können. Furthermore, phosphorus-containing polycondensation products have already been proposed from derivatives of phosphorous acid and hydroxyl groups capable of reacting with hydroxyl groups containing polyesters. After the above procedure they become flame retardant Obtain products that are insoluble in organic solvents and in heat cannot be deformed.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von schwer entflammbaren, selbstlöschenden Harzen durch Polymerisation von ungesättigten Estern einer Phosphorsäure allein oder in Mischung mit Methacrylsäuremethylester in der Wärme in Gegenwart von Katalysatoren mit dem Kennzeichen, daß man als ungesättigten Ester einer Phosphorsäure einen Ester der Orthophosphorsäure der allgemeinen Formel X = Methyl oder Wasserstoff; R = Alkyl) verwendet, und zwar in einer Menge von 20 bis 40 O/o (bezogen auf das Mischpolymerisat).The invention relates to a process for the production of flame-retardant, self-extinguishing resins by polymerizing unsaturated esters of phosphoric acid alone or in a mixture with methacrylic acid methyl ester in the presence of catalysts with the characteristic that the unsaturated ester of a phosphoric acid is an ester of orthophosphoric acid general formula X = methyl or hydrogen; R = alkyl) is used, specifically in an amount of 20 to 40 O / o (based on the copolymer).
Die nach dem erfindungsgemäßen Verfahren erhaltenen Polymeren sind farblose, glasklare, thermoplastische Produkte, die sich nach den üblichen Methoden in der Wärme verformen lassen. The polymers obtained by the process of the invention are colorless, crystal clear, thermoplastic products, which are made according to the usual methods let it deform in the heat.
Die erfindungsgemäß zu verwendenden Phosphorsäureester polymerisieren allein und in Mischung mit Methacrylsäuremethylester sehr rasch, so daß die Herstellung flammfester Gegenstände unter wirtschaftlich günstigen Bedingungen durchgeführt werden kann. Ein erheblicher Vorzug des erfindungsgemäßen Verfahrens ist darin zu sehen, daß Gegenstände aus Mischpolymerisaten aus Methacrylsäuremethylester und den erfindungsgemäßen ungesättigten Phosphorsäureestern die gleichen hohen Festigkeitseigenschaften besitzen wie solche, die aus Polymethylmethacrylat bestehen, sofern der Gehalt an Phosphat im Mischpolymerisat 40 O/o nicht überschreitet. The phosphoric esters to be used according to the invention polymerize alone and in a mixture with methyl methacrylate very quickly, so that the production flame-retardant objects carried out under economically favorable conditions can be. A significant advantage of the method according to the invention is to be found therein see that objects made from copolymers of methyl methacrylate and the unsaturated phosphoric acid esters according to the invention have the same high strength properties have such as those made of polymethyl methacrylate, provided that the content of Phosphate in the copolymer does not exceed 40%.
Man gewinnt die erfindungsgemäß zu verwendenden substituierten Propyldialkylphosphate, nämlich 3 Methacryloxy - 2 - chlorpropyldialkylphosphat und 3 - Acryloxy -2 - chlorpropyldialkylphosphat dadurch, daß man Glycidylmethacrylat bzw. Glycidylacrylat in Gegenwart von katalytischen Mengen Titantetrachlorid mit Dialkoxyphosphoroxychlortd in benzolischer Lösung umsetzt, den Katalysator nach beendeter Reaktion mit der äquivalenten Menge Pyridin ausfällt, das Reaktionsprodukt filtriert und aus dem Filtrat das Lösungsmittel im Vakuum abdampft. Für dieses Herstellungsverfahren wird jedoch kier kein Schutz beansprucht. The substituted propyl dialkyl phosphates to be used according to the invention are obtained, namely 3-methacryloxy-2-chloropropyl dialkyl phosphate and 3-acryloxy -2-chloropropyl dialkyl phosphate in that one glycidyl methacrylate or glycidyl acrylate in the presence of catalytic Reacts quantities of titanium tetrachloride with dialkoxyphosphoroxychloride in a benzene solution, the catalyst precipitates after the end of the reaction with the equivalent amount of pyridine, the reaction product is filtered and the solvent is evaporated from the filtrate in vacuo. However, no protection is claimed for this manufacturing process.
Nach dem erfindungsgemäßen Verfahren werden zur Herstellung schwer entflammbarer Produkte vorzugsweise 3-Methacryloxy- bzw. 3-Acryloxy-2-chlor- propyldimethylphosphat verwendet, weil diese den höchsten möglichen Phosphorgehalt enthalten. According to the method of the present invention, it becomes difficult to manufacture Flammable products preferably 3-methacryloxy or 3-acryloxy-2-chloro propyl dimethyl phosphate used because they contain the highest possible phosphorus content.
Schwerentflammbarkeit und selbstlöschende Eigenschaften werden erzielt, wenn der Gehalt an 3-Methacryloxy- bzw. 3- Acryloxy -2 - chlorpropyldimethylphosphat in den Mischpolymerisaten mit Methacrylsäuremethylester 20 bis 40 O/o beträgt. Flame retardancy and self-extinguishing properties are achieved, if the content of 3-methacryloxy- or 3-acryloxy -2 - chloropropyldimethyl phosphate in the copolymers with methyl methacrylate is 20 to 40%.
In Abhängigkeit von der Konzentration der erfindungsgemäßen ungesättigten Phosphate lassen sich die Eigenschaften, wie Entflammbarkeit, hydrophile und elektrische Eigenschaften, von Mischpolymeren aus diesen Monomeren und Methacrylsäuremethylester zweckentsprechend modifizieren. Depending on the concentration of the unsaturated according to the invention Phosphates can have properties such as flammability, hydrophilic and electrical Properties of copolymers made from these monomers and methyl methacrylate modify appropriately.
Zur Herstellung von erfindungsgemäß zu verwendendem Ausgangsmaterial nach hier nicht beanspruchtem Verfahren wird eine Mischung aus 245 g Dimethoxyphosphoroxychlorid, 4,75 g Titantetrachlorid und 300 ml über Natriumdraht getrocknetem Benzol in einem Rundkolben vorgelegt und in die Mischung innerhalb von 6 Stunden 240 g Glycidylmethacrylat mit einer solchen Geschwindigkeit eingetropft, daß die Temperatur im Reaktionskolben +100 C nicht überschreitet. Die anfangs gelbe Farbe der benzolischen Lösung verschwindet nach der Zugabe des Methacrylats. Unter Rühren werden dann 3,95 g Pyridin hinzugesetzt, woraufhin sich ein feinkörniger weißer Niederschlag bildet, der in der Zentrifuge durch Filtration abgetrennt wird. For the production of starting material to be used according to the invention according to the method not claimed here, a mixture of 245 g of dimethoxyphosphorus oxychloride, 4.75 g of titanium tetrachloride and 300 ml of benzene dried over sodium wire in one Submitted round bottom flask and in the mixture within 6 hours 240 g of glycidyl methacrylate added dropwise at such a rate that the temperature in the reaction flask Does not exceed +100 C. The initially yellow color of the benzene solution disappears after adding the methacrylate. 3.95 g of pyridine are then added with stirring, whereupon a fine-grained white precipitate forms, which in the centrifuge is separated by filtration.
Anschließend wird die Lösung über Aktivkohle filtriert und das Lösungsmittel im Vakuum abgedampft Beispiel 1 Aus dem wie oben beschrieben gewonnenen Kondensat erhält man nach Zugabe von 0,05 O/o Azoiso- buttersäuredinitril durch Polymerisation in der Wärme ein glasklares flammfestes Produkt, das in chlorierten aliphatischen Kohlenwasserstoffen löslich und in aromatischen Kohlenwasserstoffen unlöslich ist. The solution is then filtered through activated charcoal and the solvent evaporated in vacuo. Example 1 From the condensate obtained as described above obtained after the addition of 0.05 O / o azoiso- butyric acid dinitrile by polymerization in the heat a crystal clear flame retardant product that in chlorinated aliphatic Is soluble in hydrocarbons and insoluble in aromatic hydrocarbons.
Beispiel 2 Einer Mischung, die aus 75 Gewichtsteilen Methacrylsäuremethylester und 25 Gewichtsteilen 3-Methacryl-(acryl)-oxy-2-chlorpropyldimethylphosphat besteht, werden 0,05 Gewichtsteile Azoisobuttersäuredinitril zugesetzt, und das Gemisch wird 4 Stunden lang auf 500 C und durch Steigerung der Temperatur um 100 C/Std. auf 1000 C erhitzt. Anschließend wird das Gemisch 6 Stunden lang bei 1000 C auspolymertsiert. Example 2 A mixture composed of 75 parts by weight of methyl methacrylate and 25 parts by weight of 3-methacryl- (acrylic) -oxy-2-chloropropyldimethylphosphate, 0.05 parts by weight of azoisobutyric acid dinitrile are added and the mixture is 4 hours to 500 C and by increasing the temperature by 100 C / hour. to 1000 C heated. The mixture is then polymerized out at 1000 ° C. for 6 hours.
Man erhält ein glasklares Mischpolymerisat, das die Festigkeitseigenschaften des reinen Polymethylmethacrylats besitzt, das aber die Verbrennung nicht unterhält. A crystal-clear copolymer is obtained which has the strength properties of pure polymethyl methacrylate, but which does not sustain the combustion.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER29218A DE1148751B (en) | 1960-12-03 | 1960-12-03 | Process for the production of flame-retardant, self-extinguishing resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER29218A DE1148751B (en) | 1960-12-03 | 1960-12-03 | Process for the production of flame-retardant, self-extinguishing resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1148751B true DE1148751B (en) | 1963-05-16 |
Family
ID=7402939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER29218A Pending DE1148751B (en) | 1960-12-03 | 1960-12-03 | Process for the production of flame-retardant, self-extinguishing resins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1148751B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5444123A (en) * | 1991-09-06 | 1995-08-22 | Basf Aktiengesellschaft | Halogen-free flameproofed thermoplastic molding materials based on polyphenylene ethers and polystyrene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1045649B (en) * | 1957-03-28 | 1958-12-04 | Hoechst Ag | Process for the production of hardened phosphorus-containing synthetic resins |
-
1960
- 1960-12-03 DE DER29218A patent/DE1148751B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1045649B (en) * | 1957-03-28 | 1958-12-04 | Hoechst Ag | Process for the production of hardened phosphorus-containing synthetic resins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5444123A (en) * | 1991-09-06 | 1995-08-22 | Basf Aktiengesellschaft | Halogen-free flameproofed thermoplastic molding materials based on polyphenylene ethers and polystyrene |
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