NO783997L - SOLID, HYDROLY-RESISTANT PHOSPHORIC ACID STARTERS WITH IMPROVED STABILIZER EFFECT IN PLASTICS - Google Patents
SOLID, HYDROLY-RESISTANT PHOSPHORIC ACID STARTERS WITH IMPROVED STABILIZER EFFECT IN PLASTICSInfo
- Publication number
- NO783997L NO783997L NO783997A NO783997A NO783997L NO 783997 L NO783997 L NO 783997L NO 783997 A NO783997 A NO 783997A NO 783997 A NO783997 A NO 783997A NO 783997 L NO783997 L NO 783997L
- Authority
- NO
- Norway
- Prior art keywords
- wax
- phosphoric acid
- weight
- acid ester
- stabilizer
- Prior art date
Links
- 229920003023 plastic Polymers 0.000 title claims description 22
- 239000004033 plastic Substances 0.000 title claims description 22
- 239000003381 stabilizer Substances 0.000 title claims description 19
- 239000007787 solid Substances 0.000 title claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims description 6
- 230000001976 improved effect Effects 0.000 title claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims description 3
- 230000000694 effects Effects 0.000 title description 7
- 239000007858 starting material Substances 0.000 title 1
- 239000001993 wax Substances 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 24
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 17
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 230000009931 harmful effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000004611 light stabiliser Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 17
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OCSIKZYSDOXRPA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-octadecylhenicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC OCSIKZYSDOXRPA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QCEPBLYEWUSQMX-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphite;3-oxobutanoic acid Chemical compound CC(=O)CC(O)=O.OCC(CO)(CO)COP(O)O QCEPBLYEWUSQMX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- ANINPCIIERUOQH-AYNSAMJBSA-N (2S,3R)-butane-1,2,3,4-tetrol phosphorous acid Chemical compound P(O)(O)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O ANINPCIIERUOQH-AYNSAMJBSA-N 0.000 description 1
- SBPOXRJRVKTDMN-UHFFFAOYSA-N 1-dimethoxyphosphoryltriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCP(=O)(OC)OC SBPOXRJRVKTDMN-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical class CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RBJMENQYBKFGEN-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C1=CC(C(=O)O)=CC=C1)(=O)O.OCC(CO)(CO)CO RBJMENQYBKFGEN-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- NOCMYCSJUZYBNE-UHFFFAOYSA-N dioctadecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCCCCCCC NOCMYCSJUZYBNE-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- HHFDXDXLAINLOT-UHFFFAOYSA-N n,n'-dioctadecylethane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCNCCCCCCCCCCCCCCCCCC HHFDXDXLAINLOT-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Faste, hydrolysebestandige fosforsyrlingester-tll-beredninger med forbedret stabilisatorvirkning i kunststoffer. Solid, hydrolysis-resistant phosphoric acid ester-tll preparations with improved stabilizer action in plastics.
Fosforsyrlingestere får i økende grad betydning..som antioksydanter i stabilisatorsystemer for kunststoffer, spesielt for masseproduktene polyetylen, polypropylen og PVC. På grunn av den lettere doserings- og blandbarhet med kunststoffer, men også med de andre komponenter av den samlede stabilisering fore-trekker faste produkter i pulver- og skallform for de flytende. Deres graverende ulempe er imidlertid at de i fuktig luft, allerede delvis i innpakning ved forsendelse til forbrukeren, helt spesielt imidlertid ved lagring og åpning av disse hurtig hydro-lyserer og derved taper deres virkning som stabilisator. Hydro-lyseproduktene reagerer deretter med stabilisatorsysternets andre bestanddeler, som metallsåper, til uoppløselige forbindelser som gjør kunststoffene uklare og således følsomt kan forstyrre produk-sjonsforløpet, hvis det ikke helt avbrytes. Phosphoric acid esters are becoming increasingly important..as antioxidants in stabilizer systems for plastics, especially for the pulp products polyethylene, polypropylene and PVC. Due to the easier dosage and mixability with plastics, but also with the other components of the overall stabilization, solid products in powder and shell form are preferred to the liquid ones. However, their serious disadvantage is that in moist air, already partially wrapped when sent to the consumer, especially when stored and opened, they quickly hydrolyze and thereby lose their effect as a stabilizer. The hydrolysis products then react with the stabilizer system's other components, such as metal soaps, to form insoluble compounds that make the plastics cloudy and thus can sensitively disrupt the production process, if it is not completely interrupted.
Til grunn for oppfinnelsen lå den oppgave å eliminere disse ulemper ved faste fosforsyrlingestere-og å hindre deres hydrolyse resp. sterkt å nedsette den uten å påvirke dens virkning. The invention was based on the task of eliminating these disadvantages of solid phosphoric acid esters - and to prevent their hydrolysis or strongly to diminish it without affecting its effect.
Det har tidligere ikke manglet på forsøk til å for-bedre hydrolysestabiliteten av fosforsyrlingester-stabilisatorer. Således henvises i DOS 2.626.225 til en allerede tidligere fore-slått tilsetning av mindre mengder av et amin, idet imidlertid' ved siden av en bare korttidig virkning kan opptre meget uheldige misfarvninger, når det etter denne fremgangsmåte behandlede fosfit f.eks. anvendes i PVC. There has previously been no shortage of attempts to improve the hydrolysis stability of phosphoric acid ester stabilizers. Thus, reference is made in DOS 2,626,225 to an already previously proposed addition of smaller quantities of an amine, since, however, in addition to only a short-term effect, very unfortunate discolorations can occur, when the phosphite treated according to this method, e.g. used in PVC.
I"samme publikasjon anbefales som mer egnet forholdsregel å tilsette metallsalter av organiske syrer, hvorved imidlertid hydrolysen ikke lar seg hindre, men dens følge er å bekjempe, som f.eks. synliggjøres ved pH-senkning. Denne forholdsregel ute-lukker således ikke de ovennevnte foreteelser ved sikttilstopning ved forarbeidelse av kunststoff og dets uklarhet. In the same publication, it is recommended as a more suitable precaution to add metal salts of organic acids, whereby, however, the hydrolysis cannot be prevented, but its consequence is to be combated, which is for example made visible by lowering the pH. This precaution thus does not exclude the above-mentioned phenomena in the case of sieve clogging during the processing of plastic and its cloudiness.
ved laveresmeltende fosfiter. At det ved kombinasjonen av voks med en. fosfitstabilisator oppnås en hurtigere og grundigere for-deling i kunststoffet kunne heller ikke forutsees. in the case of lower-melting phosphites. That by the combination of wax with a. phosphite stabilizer, a faster and more thorough distribution in the plastic could not be predicted either.
Endelig er det i mange tilfeller ved tilsetning avFinally, in many cases it is by adding
få vekt% voks til fosfit å iaktta en tydelig økning av smelte-punktet. Denne effekt er overraskende, da normalt ved forurensning av et stoff, dets smeltepunkt synker. Smeltepunktøkningen er . spesielt av fordel når fosfitet skal anvendes til såkalt Bunker-stabilisering av polyolefinpulver. Ved denne prosess faller kunststoff pulveret ut fra polymerisasjonen med en temperatur på -ca. 60-80°C. Stabiliseringsblandinger som inneholder et lavtsmeltende fosfit, sammenbaker ved denne temperatur og kan da bare fordeles med meget høyt arbeide homogent til kunststoffpulver. Denne ulempe lar seg unngå ved anvendelse av ved hjelp av vokstilsetning i stivnepunkt forhøyede fosfiter. Slike fosfiter er videre lettere, å konfeksjonere ved forstøvning eller skjelldannelse, dessuten tenderer de ved innvirkning av varme og trykk mindre til sammenbakning enn ubehandlede fosfiter. few wt% wax to phosphite to observe a clear increase of the melting point. This effect is surprising, as normally when a substance is contaminated, its melting point drops. The melting point increase is . particularly advantageous when phosphite is to be used for so-called Bunker stabilization of polyolefin powder. In this process, the plastic powder falls out from the polymerization at a temperature of -approx. 60-80°C. Stabilizing mixtures containing a low-melting phosphite cake together at this temperature and can then only be distributed homogeneously into plastic powder with very high work. This disadvantage can be avoided by using phosphites whose solidification point is raised by the addition of wax. Such phosphites are also easier to confection by atomization or shell formation, moreover, they tend to stick together less when exposed to heat and pressure than untreated phosphites.
Overraskende er det videre at ved vokstilsetningen reduseres drastisk fosfitenes flyktighet i varmen, ja ved høyere voksmengde undertrykkes omtrent fullstendig. Denne effekt er derfor av stor betydning, fordi det derved sikres at under forarbeidelse av kunststoffet tilstedeværende personer ikke utsettes for eventuelle sunnhetsskadelige damper. It is also surprising that with the addition of wax, the volatility of the phosphites in the heat is drastically reduced, and with a higher amount of wax it is almost completely suppressed. This effect is therefore of great importance, because it ensures that during the processing of the plastic, persons present are not exposed to any fumes harmful to health.
Med for stabilisering av kunststoffer i og for seg kjente fosforsyrlingestere forstås faste, organiske fosfiter som f.eks. di-stearylfosfit, tri-stearylfosfit, fortrinnsvis penta-erytritylfosfit, slik de f.eks. omtales i de tyske Offenlegungs-schr^iften 2.219.695 , 2.347.997, 2 .621. 323, 2.630.257, 2.431.623 Phosphoric acid esters, known in and of themselves for stabilizing plastics, are understood to mean solid, organic phosphites such as e.g. di-stearyl phosphite, tri-stearyl phosphite, preferably penta-erythritol phosphite, as they e.g. is mentioned in the German Offenlegungs-schr^iften 2,219,695, 2,347,997, 2,621. 323, 2,630,257, 2,431,623
og de tyske patentskrifer 1.237.312 og 2.505.152, sukkeralkohol-fosfiter ifølge tyske Offenlegungsschriften 2.633.392 og 2.633.393, samt faste triarylfosfiter ifølge tysk Offenlegungsschrift 2.606.358. Ved sistnevnte lar det undertiden uønsket høye smeltepunkt seg ved vokstilsetning senke, samt den spesielt sterke sublimasjonstendehs av disse stoffer redusere ved høye temperaturer. and the German patents 1,237,312 and 2,505,152, sugar alcohol phosphites according to German Offenlegungsschriften 2,633,392 and 2,633,393, as well as solid triaryl phosphites according to German Offenlegungsschrift 2,606,358. With the latter, the sometimes undesirably high melting point can be lowered by the addition of wax, as well as the particularly strong sublimation tendency of these substances to be reduced at high temperatures.
Med voks forstås produkter med 20 til ca. 500, fortrinnsvis mellom 30 og 250 C-atomer i molekylet, som faller under den generelle definisjon av begrepet voks ifølge DGF-Einheits-methoden Mil (75) som parafiner, f.eks. raffinert bordparafin med smp. fra ca. 40 til ca. 80°C, mikroparafiner, synteseparafiner med Wax means products with 20 to approx. 500, preferably between 30 and 250 C atoms in the molecule, which fall under the general definition of the term wax according to the DGF-Einheits-methoden Mil (75) as paraffins, e.g. refined table paraffin with m.p. from approx. 40 to approx. 80°C, microparaffins, synthetic paraffins incl
smp. mellom'80 og 130°C, langkjedede plante- og insektvokser,m.p. between '80 and 130°C, long-chain plant and insect waxes,
som Carnauba-voks, Cadelillavoks, delsyntetisk 'estervoks, som f.eks. Montanvoksderivater, syntesevoks, som amidvoks, f.eks. distearyl-etylendiamid, polyolefinvoks, f.eks. polyetylen- og polypropylenvoks i molekylområdet fra ca. 2. 000 til 10.000, poly-<1>etylenvoksoksydater og estere herav, som er tilgjengelige ved addisjon av dialkylfosfiter til langkjedede a-olefiner i nærvær av radikal leverende katalysatorer. Også blandinger av de nevnte vokser kan anvendes. Foretrukket blir oppbygnings-polyetylenvoks og amidvoks, spesielt sistnevnte. I voks-fosforsyrlingester-tilberedningen ifølge oppfinnelsen skal mengden av voks utgjøre mellom 3% og 80%, fortrinnsvis mellom 5 og 40%. such as Carnauba wax, Cadelilla wax, semi-synthetic 'ester wax, such as e.g. Montane wax derivatives, synthetic waxes, such as amide waxes, e.g. distearyl-ethylenediamide, polyolefin wax, e.g. polyethylene and polypropylene wax in the molecular range from approx. 2,000 to 10,000, poly-<1>ethylene wax oxides and esters thereof, which are obtainable by the addition of dialkyl phosphites to long-chain α-olefins in the presence of radical-donating catalysts. Mixtures of the aforementioned waxes can also be used. Building polyethylene wax and amide wax are preferred, especially the latter. In the wax-phosphoric acid ester preparation according to the invention, the amount of wax should be between 3% and 80%, preferably between 5 and 40%.
Fremstillingen og tilberedningen foregår fortrinnsvis således at man oppsmelter voks og de faste fosforsyrlingestere, sammen. Smeiten konfeksjoneres deretter etter i<p>g for ség kjente fremgangsmåter, f.eks. ved skjelldannelse, ved sprøgjøring, ved slyngning eller maling etter avkjøling. Voks-fosfitsmelten kan også tilsettes enkelte eller alle deler av et samlestabilisator-system som fenoliske anitoksydanter, f.eks. substituerte tert.-butylfenoler, organiske sulfider, som f.eks. tioglykolsyreester eller distearylsulfid, metallsalter av fettsyrer, som f.eks. stearat, laurat, eller montanater av kalsium, barium, magnesium, kadmium, sink og bly, samt lysstabilisatorer som benzofenon, triazoler eller hindrede aminer. Da disse stabilisatorer ofte har en voksaktig karakter, kan de dessuten forsterke den hydrolyse-hindrende virkning av voksen. Fra rekken vokstyper velger man for tilfelle av et samlet stabilisatorsystem det individ ut som sikrer homogeniteten av den samlede blandings smelte. Ved denne fremgangsmåte oppnår man en ekstra fordel senere å kunne innblande samtlige stabilisatorer i en operasjon i kunststoffet. The production and preparation preferably takes place in such a way that wax and the solid phosphoric acid esters are melted together. The forge is then assembled according to methods known per se, e.g. by shell formation, by brittleness, by slinging or grinding after cooling. The wax-phosphite melt can also be added to some or all parts of a collection stabilizer system as phenolic antioxidants, e.g. substituted tert.-butylphenols, organic sulphides, such as e.g. thioglycolic acid ester or distearyl sulphide, metal salts of fatty acids, such as e.g. stearate, laurate, or montanates of calcium, barium, magnesium, cadmium, zinc and lead, as well as light stabilizers such as benzophenone, triazoles or hindered amines. As these stabilizers often have a waxy character, they can also enhance the hydrolysis-preventing effect of the wax. From the range of wax types, in the case of an overall stabilizer system, the individual is selected which ensures the homogeneity of the melt of the overall mixture. With this method, one obtains an additional advantage later on being able to mix all stabilizers in one operation in the plastic.
En annen mulighet til å fremstille tilberedningene består i å overtrekke fine partikler av fosforsyrlingesteren som skal beskyttes ved innhylling med en voksfilm. Dette kan eksempel-vis foregå ved at under eller etter forstøvningen eller skall-dannelsen av fosfitet, påføres voksen som smelte eller oppløst i et oppløsningsmiddel på fosfitpartiklene. Another possibility for preparing the preparations consists in coating fine particles of the phosphoric acid ester which is to be protected by enveloping with a wax film. This can, for example, take place by applying wax melted or dissolved in a solvent to the phosphite particles during or after the atomization or shell formation of the phosphite.
■Tilberedningen ifølge oppfinnelsen anvendes til stabilisering av. kunststoff masse på basis av jpolyolef iner eller av klorholdige polymere mot den skadelige innvirkning av lys og varme, nemlig-i mengder fra 0,01 til 5, fortrinnsvis .0,05. til 2 vskt%, ■The preparation according to the invention is used to stabilize plastic mass on the basis of jpolyolefins or of chlorine-containing polymers against the harmful effects of light and heat, namely-in amounts from 0.01 to 5, preferably .0.05. to 2% VAT,
referert til kunststoffmasse og fosforsyrlingester-mengde i tilberedningen. Det skal nevnes i enkelte masser av polyetylen, fortrinnsvis polypropylen, kopolymerisater av etylen med C^- til Cj--a-olefiner, polyvinylklorid, deres kopolymerisater med vinyliden-klorid og andre olefiner, klorerte polyolefiner, samt av blan- ' dinger av polymerisater. referred to plastic mass and phosphoric acid ester quantity in the preparation. Mention must be made in certain masses of polyethylene, preferably polypropylene, copolymers of ethylene with C^- to Cj--a-olefins, polyvinyl chloride, their copolymers with vinylidene chloride and other olefins, chlorinated polyolefins, as well as of mixtures of polymers .
Oppfinnelsen skal forklares nærmere ved hjelp av noen . eksempler: The invention shall be explained in more detail with the help of some . examples:
Eksempel 1 (fremstillingseksempel)Example 1 (production example)
a) 2 g parafin, smp. 58-60°C, oppløses i 100 ml heptan ved oppkokning, etter avkjøling til 80°C innrøres 18 g finmalt a) 2 g kerosene, m.p. 58-60°C, dissolve in 100 ml heptane by boiling, after cooling to 80°C stir in 18 g finely ground
isoftalsyre-di-pentaerytritfosfitester (fremstilt ifølge DOS 2. 506 . 207, Eks. 6), hvorpå man ved 30°C på rotasjonsfordamper fjerner, oppløsningsmidlet. b) Som under a) belegges 18 g isof talsyrepentaery trit^-ester med 2 g av en synteseparafin med smp. 102°C. c) Som under a) belegges 18 g isoftalsyrepentaerytrit-ester med 2 g av en avbygnings-polyetylenvoks med en kjedelengde isophthalic acid di-pentaerythritol phosphite ester (prepared according to DOS 2. 506 . 207, Ex. 6), after which the solvent is removed at 30°C on a rotary evaporator. b) As under a), 18 g of isophthalic acid pentaerythritol is coated with 2 g of a synthetic paraffin with m.p. 102°C. c) As under a) 18 g of isophthalic acid pentaerythritol ester are coated with 2 g of a decomposing polyethylene wax with a chain length
på ca. 200 C-atomer.of approx. 200 C atoms.
d) Som under a) has 18 g aceteddiksyrepentaerytritfosfitester (fremstilt ifølge DAS 2.505.152) til en heptanoppløsning av d) As under a) 18 g of acetoacetic acid pentaerythritol phosphite ester (prepared according to DAS 2.505.152) is added to a heptane solution of
2 g av en polyetylen-avbygningssvoks med en kjedelengde på ca.2 g of a polyethylene degradation wax with a chain length of approx.
200 C-atomer ved ca. 60°C og avkjøles. Den avkjølte oppløsning . trykkfiltreres og inndampes deretter. e) 20 g aceteddiksyrepentaerytritfosfitester innrøres i en smelte av 20 g synteseparafin med smp. 102°C og avkjøles deretter. f) 10 g di-stearyl-pentaerytrityl-difosfit innrøres i en ca. 50°C varm oppløsning av 2 g triacontylfosfonsyredimetylester 200 C atoms at approx. 60°C and cool. The cooled solution. pressure filtered and then evaporated. e) Stir 20 g of acetoacetic acid pentaerythritol phosphite ester into a melt of 20 g of synthetic paraffin with m.p. 102°C and then cooled. f) Stir 10 g of di-stearyl-pentaerythritol-diphosphite into an approx. 50°C hot solution of 2 g of triacontylphosphonic acid dimethyl ester
i heptan. Ved 30°C fjernes oppløsningsmidlet i rotasjonsfordamperen. in heptane. At 30°C, the solvent is removed in the rotary evaporator.
g) 20 g di-stearyl-pentaerytrityl-difosfit innrøres i en smelte av 20 g triaceontylfosfonsyre-dimetylester. Smeiten blir g) Stir 20 g of di-stearyl-pentaerythritol diphosphite into a melt of 20 g of triaceontylphosphonic acid dimethyl ester. The forging will be
dannet.formed.
Hver gang smeltes sammen 18 g di-stearyl-pentaerytrityl-difosfit med Each time, 18 g of di-stearyl-pentaerythrityl-diphosphite are fused with
h) -2 g synteseparafin, smp. 102°C, resp.h) -2 g synthetic paraffin, m.p. 102°C, resp.
i) 2 g polyetylenvoks, molekylvekt ca. 2000 resp.i) 2 g polyethylene wax, molecular weight approx. 2000 or
j) 2 g mikroparafin resp.j) 2 g microparaffin or
k) 2 g parafin, smp. 58-60°C.k) 2 g kerosene, m.p. 58-60°C.
Smeltene støpes.The melts are cast.
1) 18 g di-stearyl-(3-hydroksytriacontyl-sorbityl-trifosfit (fremstilt ifølge DOS 2.633.392, Eks. 6) forenes i smelte med 2 g av en synteseparafin med smp. 102°C. 1) 18 g of dis-stearyl-(3-hydroxytriacontyl-sorbityl-triphosphite (manufactured according to DOS 2,633,392, Ex. 6) are combined in melt with 2 g of a synthetic paraffin with m.p. 102°C.
m) 18 g di-stearyl-3-hydroksytriacontyl-sorbityl-trifosfit blandes i smelte med 2 g av en polyolefinvoks med en kjedelengde på ca. 200 C-atomer. Blandingen støtes. m) 18 g of di-stearyl-3-hydroxytriacontyl-sorbitol-triphosphite are mixed in melt with 2 g of a polyolefin wax with a chain length of approx. 200 C atoms. The mixture is stirred.
Eksempel 2Example 2
I dette eksempel skal det vises den forbedrede hydro-lysefasthet av fosfittilberedeningen ifølge oppfinnelsen. a) Hver'gang 5 g av ifølge Eks. 1 fremstilte stoff-prøver kokes , i 100 ml avsaltet vann i 20 minutter under tilbakeløp. Det filtreres ennu varmt gjennom et foldefilter. Fra den vandige fasé uttas hver gang 40 ml<1>s prøver og titreres med 0,1 molar KOH mot bromfenolblå. In this example, the improved hydrolysis resistance of the phosphityl preparation according to the invention shall be shown. a) Each time 5 g of according to Ex. 1 prepared substance samples are boiled in 100 ml of desalted water for 20 minutes under reflux. It is filtered while still warm through a folding filter. From the aqueous phase, 40 ml<1>s samples are taken each time and titrated with 0.1 molar KOH against bromophenol blue.
Av følgende tabell kan det sees den under disse be-tingelser fastslåtte hydrolysegrad som kvotient av faktisk lut-forbruk og teoretisk mulig lut-forbruk ved fullstendig hydrolyse. Til sammenligning er det angitt hydrolysestabiliteten av de til de enkelte tilberedninger til grunn liggende fosfiter. The following table shows the degree of hydrolysis determined under these conditions as a quotient of actual lye consumption and theoretically possible lye consumption with complete hydrolysis. For comparison, the hydrolysis stability of the phosphites underlying the individual preparations is indicated.
b) Vannopptak av en fosforsyrlingester-tilberedning ifølge oppfinnelsen sammenlignet med vannopptak av den til grunn liggende b) Water absorption of a phosphoric acid ester preparation according to the invention compared to water absorption of the underlying one
fosforsyrlingester ved lagring i vanndampmettet atmosfære. phosphoric acid esters when stored in a water vapor saturated atmosphere.
Fosfit: Di-stearyl-pentaerytrityl-difosfit 1 Prøvelegeme: Sirkelplater, diam.= 60 mm, høyde= 5 mm Lufttemperatur: 2 0°C i Phosphite: Di-stearyl-pentaerythrityl-diphosphite 1 Test body: Circular plates, diam.= 60 mm, height= 5 mm Air temperature: 2 0°C i
. Luftfuktighet: 100%. Humidity: 100%
Varighet: 24 timer.Duration: 24 hours.
Eksempel 3 . Example 3.
I dette eksempel skal det vises den,fordelaktige økning av stivningspunktet ved de ifølge oppfinnelsen behandlede organiske fosfiter. In this example, the advantageous increase in the solidification point of the organic phosphites treated according to the invention shall be shown.
a) Tristearyl-sorbityl-trifosfit (fremstilt ifølge DOS 2.633.393, eks. 1) med et flyte-/dråpepunkt (Fp/Tp) 52/53°C, blandes a) Tristearyl sorbitol triphosphite (prepared according to DOS 2,633,393, ex. 1) with a pour/drop point (Fp/Tp) 52/53°C, mix
med 3,5 vekt% av et polyetylen-oksidat (dråpepunkt 117°, syretall 19) with 3.5% by weight of a polyethylene oxide (dropping point 117°, acid number 19)
i smeiten. Det avkjølte produkt har et flyte-/dryppepunkt på 86/ 91°C. in the forge. The cooled product has a pour/drop point of 86/91°C.
b) Smelter man tristearyl-sorbityl-trifosfit med 4,5 vekt% av et polyetylenoksydat med syretall 9 og et dryppepunkt på > b) Tristearyl sorbitol triphosphite is melted with 4.5% by weight of a polyethylene oxide with an acid number of 9 and a dripping point of >
115°C sammen, får man en tilberedning med Fp/Tp på 76/80°C.115°C together, you get a preparation with Fp/Tp of 76/80°C.
. c) Av tilberedningene 1 h) til 1 k), bestående av 90 vekt% di-stearyl-pentaerytrityl-difosfit og 10 vekt% av forskjellige vokser, ble det bestemt ved flyte-/dryppepunktet og sammenl-i-gnet med Fp/Tp av ublandet fosfit. . c) Of the preparations 1 h) to 1 k), consisting of 90% by weight of dis-stearyl-pentaerythritol-diphosphite and 10% by weight of various waxes, it was determined by the pour/dropping point and compared with Fp/Tp of unmixed phosphite.
Eksempel 4 Example 4
I dette eksempel skal det vises den forbedrede virkning av f osf it-tilberedningen i forhold til de til grunn liggende fosfiter. Av måleverdiene fremgår at ved tilberedningen ifølge oppfinnelsen kan det oppnås en betraktelig økning såvel av varme-aldringsbestandigheten som også av forarbeidelsesbestandigheten, enskjønt fosfitinnholdet alltid ligger lavere enn ved sammenlig-ningsforsøkene. In this example, the improved effect of the phosphite preparation in relation to the underlying phosphites shall be shown. From the measured values, it appears that with the preparation according to the invention, a considerable increase can be achieved both in the heat aging resistance and also in the processing resistance, although the phosphite content is always lower than in the comparison tests.
a) Prøving av varmealdringsbestandigheta) Heat aging resistance testing
■ På en tovalse homogeniseres en blanding av■ On a two-roller, a mixture of
100 vektdeler ustabilisert polypropylenpulver av tett-het 0,90 (smelteindeks er ca. 6g/10 min. 100 parts by weight of unstabilized polypropylene powder of density 0.90 (melt index is approx. 6g/10 min.
bestemt i tilknytning, til ASTM D. 1238-62 T) determined in connection with ASTM D. 1238-62 T)
0,15 vektdeler 3',5'-di-tert-butyl-4'-hydroksyfenyl-propionsyre-oktacedylester og 0.15 parts by weight of 3',5'-di-tert-butyl-4'-hydroxyphenyl-propionic acid octacedyl ester and
hver gang 0,1 vektdeler av et fosfit resp. en fosfittilberedning ved 200°C i fem minutter. Kunststoffsmeiten presses deretter ved 200°C til en plate av 1 mm tykkelse. Av den avkjølte plate ut-stanses strimmelformede prøvelegemer (60 x 10. x 1 mm) og henges i et sirkulasjonstørkeskap på et motordrevet stativ med roterende •horder. Prøvene underkastes i kontrollert atmosfære (friskluft-tilførsel med definerte mengder) for en jevn temperaturbelastning på 140°C lufttemperatur. Som sluttpunkt gjelder det tidsrom, hvor det på noen steder inntrer en begynnende lokal sprøgjøring ifølge DIN 53.583,karakterisert veddannelsen av misfarvede, uklare, delvis avbrutte steder. I følgende tabell er dette tidsrom angitt i dager. each time 0.1 parts by weight of a phosphite or a phosphite preparation at 200°C for five minutes. The plastic ingot is then pressed at 200°C into a plate of 1 mm thickness. Strip-shaped specimens (60 x 10. x 1 mm) are punched out of the cooled plate and hung in a circulation drying cabinet on a motor-driven stand with rotating •hordes. The samples are subjected to a controlled atmosphere (fresh air supply with defined quantities) for a uniform temperature load of 140°C air temperature. As an end point, there is a period of time during which, in some places, an incipient local embrittlement occurs according to DIN 53.583, characterized by the formation of discolored, unclear, partially interrupted places. In the following table, this period is indicated in days.
b) Undersøkelse av forarbeidelsesbestandighetb) Examination of processing resistance
Av den under a) omtalte blanding ble det bestemt From the mixture referred to under a) it was determined
smelteindek<s>(<i>2/300^ ^r°^etter en 60-minutters termisk be-lastning ved 300°C. I tabellen er det angitt kvotienten av den således fastslåtte smelteindeksvidde —^—. Jo mindre denne melting index<s>(<i>2/300^ ^r°^after a 60-minute thermal load at 300°C. The table shows the quotient of the thus determined melting index range —^—. The smaller this
i etterin after
kvotient er, desto størr er den undergåtte termiske avbygning av kunststoffsmeiten, desto mindre således dens forarbeidelsesstabili-tet. quotient is, the greater the thermal degradation of the plastic melt, the less its processing stability.
Eksempel 5 Example 5
Dette eksempel viser at ved vokstilsetningen ifølge oppfinnelsen nedsettes flyktigheten av fosfiten. This example shows that the addition of wax according to the invention reduces the volatility of the phosphite.
Hver gang 1 g fosfit oppsmeltes med 2 g polyetylenvoks (molvekt 2000-3000). En nøyaktig avveid mengde av denne blanding lagrer man deretter i et varmeskap i 2 timer ved 200°C Each time 1 g of phosphite is melted with 2 g of polyethylene wax (mol weight 2000-3000). An accurately weighed amount of this mixture is then stored in a heating cabinet for 2 hours at 200°C
i luften og tilbakeveier derpå.in the air and then return.
I den følgende tabell er det oppstilt de således be-stemte flyktigheter, samt flyte-/dryppepunkt sammenlignet til ut-gangs f osf i ten. The following table lists the volatilities determined in this way, as well as the pour/drop point compared to the starting phosphate.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2753136A DE2753136B2 (en) | 1977-11-29 | 1977-11-29 | Solid phosphorous acid ester preparations with an improved stabilizing effect in plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO783997L true NO783997L (en) | 1979-05-30 |
Family
ID=6024859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO783997A NO783997L (en) | 1977-11-29 | 1978-11-28 | SOLID, HYDROLY-RESISTANT PHOSPHORIC ACID STARTERS WITH IMPROVED STABILIZER EFFECT IN PLASTICS |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0002243B1 (en) |
| JP (1) | JPS5483951A (en) |
| AT (1) | AT368769B (en) |
| AU (1) | AU522136B2 (en) |
| BR (1) | BR7807807A (en) |
| CA (1) | CA1113706A (en) |
| DE (2) | DE2753136B2 (en) |
| ES (1) | ES475321A1 (en) |
| IT (1) | IT1101440B (en) |
| NO (1) | NO783997L (en) |
| ZA (1) | ZA786674B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120793A (en) * | 1977-12-23 | 1982-03-30 | Ved K. Sahajpal | Encapsulated phosphites |
| US4402858A (en) * | 1982-04-14 | 1983-09-06 | Uniroyal, Inc. | Hydrolytically stable antioxidant composition |
| FR2647800A1 (en) * | 1989-05-31 | 1990-12-07 | Organo Synthese Ste Fse | Tris(2,4-di-tert-butylphenyl) phosphite having improved physical properties |
| DE102008020442A1 (en) | 2008-04-23 | 2009-10-29 | Merck Patent Gmbh | pigment preparations |
| DE102008064202A1 (en) | 2008-12-22 | 2010-06-24 | Merck Patent Gmbh | pigment granules |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1131943B (en) * | 1960-11-21 | 1962-06-20 | Deutsche Ges Schaedlingsbek | Moisture-protected metal phosphide |
| DE1768283B1 (en) * | 1968-04-25 | 1971-02-25 | Hoechst Ag | Process for the production of thermally stable carboxamides and their use as lubricants in plastics processing |
| US3666700A (en) * | 1970-12-03 | 1972-05-30 | Exxon Research Engineering Co | Polyvinyl chloride composition |
| US3755200A (en) * | 1972-02-14 | 1973-08-28 | Emery Industries Inc | Liquid stabilizer system for polyvinyl chloride |
| NL7506988A (en) * | 1975-06-12 | 1976-12-14 | Akzo Nv | ORGANIC TRIPHOSCYCLES WITH IMPROVED HYDROLYTIC STABILITY. |
-
1977
- 1977-11-29 DE DE2753136A patent/DE2753136B2/en not_active Withdrawn
-
1978
- 1978-11-23 ES ES475321A patent/ES475321A1/en not_active Expired
- 1978-11-25 DE DE7878101457T patent/DE2861885D1/en not_active Expired
- 1978-11-25 EP EP78101457A patent/EP0002243B1/en not_active Expired
- 1978-11-27 IT IT30238/78A patent/IT1101440B/en active
- 1978-11-28 AT AT0850078A patent/AT368769B/en not_active IP Right Cessation
- 1978-11-28 ZA ZA00786674A patent/ZA786674B/en unknown
- 1978-11-28 JP JP14612978A patent/JPS5483951A/en active Pending
- 1978-11-28 NO NO783997A patent/NO783997L/en unknown
- 1978-11-28 CA CA316,970A patent/CA1113706A/en not_active Expired
- 1978-11-28 AU AU41981/78A patent/AU522136B2/en not_active Expired
- 1978-11-28 BR BR7807807A patent/BR7807807A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AT368769B (en) | 1982-11-10 |
| DE2753136B2 (en) | 1981-04-02 |
| EP0002243B1 (en) | 1982-06-02 |
| EP0002243A1 (en) | 1979-06-13 |
| BR7807807A (en) | 1979-07-31 |
| ATA850078A (en) | 1982-03-15 |
| AU4198178A (en) | 1979-06-07 |
| IT7830238A0 (en) | 1978-11-27 |
| DE2861885D1 (en) | 1982-07-22 |
| DE2753136A1 (en) | 1979-06-07 |
| CA1113706A (en) | 1981-12-08 |
| JPS5483951A (en) | 1979-07-04 |
| IT1101440B (en) | 1985-09-28 |
| AU522136B2 (en) | 1982-05-20 |
| ZA786674B (en) | 1979-11-28 |
| ES475321A1 (en) | 1979-04-01 |
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