CA2061730A1 - Stabilized polyolefins - Google Patents
Stabilized polyolefinsInfo
- Publication number
- CA2061730A1 CA2061730A1 CA 2061730 CA2061730A CA2061730A1 CA 2061730 A1 CA2061730 A1 CA 2061730A1 CA 2061730 CA2061730 CA 2061730 CA 2061730 A CA2061730 A CA 2061730A CA 2061730 A1 CA2061730 A1 CA 2061730A1
- Authority
- CA
- Canada
- Prior art keywords
- polyolefins
- stands
- phosphorous acid
- stabilized
- alpha
- 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.)
- Abandoned
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 26
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 C5-C7-cycloalkyl Chemical group 0.000 claims description 15
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229930185605 Bisphenol Natural products 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 5
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HWIMDFNWTQOINO-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(2-phenylethenyl)phenyl]methyl]-4-methyl-6-(2-phenylethenyl)phenol Chemical compound OC=1C(C=CC=2C=CC=CC=2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C=CC1=CC=CC=C1 HWIMDFNWTQOINO-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical class C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100097467 Arabidopsis thaliana SYD gene Proteins 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 101100495925 Schizosaccharomyces pombe (strain 972 / ATCC 24843) chr3 gene Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 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
- C08K5/527—Cyclic esters
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)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Stabilized polyolefins A b s t r a c t Polyolefins which have been stabilized by means of special phosphorous acid esters of bisphenols are distinguished by good processing stability and improved long term stability.
Le A 28 156 - Foreign Countries
Le A 28 156 - Foreign Countries
Description
23~7~
Stabilized polyolefins This invention relates to polyolefins stabilized with special phosphorous acid esters~
Organic poiymers such as polyolefins are subjected to thermal and oxidative degradation and decomposition by light. Numerous stabilizers are known for the various polymers. Their effectiveness depends both on the causes of decomposition and on the nature of the stabilized polymer. Some compounds which are effective long term antioxidants are relatively ineffective in processing operations such as extrusion, in which the heat to which the polymers are subjected is relatively high for a short period.
A combination of various stabilizers is generally used for obtaining sufficient stabilization of a polymer because the presence of only one stabilizer does not ensure sufficient protection against the various possible causes of damage to the polymer. Thus DE-OS 28 56 801, for example, describes alkylated 2,2'-~isphenylene-phosphites which ara capable of stabilizing polymers against processing conditions. The disadvantage of stabilizing with these phosphates, however, is their insufficient long Le A 28 156- Forei gn Countri es 2~f~3~
term stabilizing effect (see Comparison Example), which necessitates the addition of further stabilizers.
European Patent Application 395 030 describes certain organic phosphites which are suitable for stabilizing polyolefins still containing residues of a Ziegler catalyst, but even with these phosphites only insufficient long term stability of the polyolefins i5 achieved.
It has now surprisingly been found that by using special phosphorous acid esters of bisphenols, good processing stability is obtained and the long term stability of the resulting polyolefins is excellent and greatly improved compared with that obtained with bisphenylene phosphites.
As a result, polyolefins which have been stabilized according to the invention are also very durable in the absence of co-stabilizers such as diphenolic antioxidants.
The present invention therefore relates to polyolefins stabilized against processing and against long term deterioration, containing from 0.01 to 5% by weight of phosphorous acid esters corresponding to the following general formula OH
/ \
O O
R2~Y~R2 E~l R
Le A ~8 156 3 wherein ~1 stands for hydrogen or a C~-C18-alkyl, C5-C7-cycloalkyl, C7-C10-aralkyl or C6-C10-aryl group, R2 stands for a Cl-C8-alkyl, C5-C7-cycloalkyl, benzyl, ~-methylbenzyl or ~,~-dimethylbenzyl group and Y stands for sulphur or for CHR3 in which R3 stands for hydrogen, a Cl-C4-alkyl or a C5-C7-cycloalkyl group.
In the above formula, Rl preferably stands for a straight chained or branched alkyl group having 1 to 8 carbon atoms, for example methyl, ethyl, isopropyl or tertiary butyl, most preferably methyl or tertiary butyl~
R2 preferably stands for a branched alkyl group having 3 to 8 carbon atoms, e.g. isopropyl, isobutyl or tert.-butyl, cyclohexyl, benzyl, ~-methylbenzyl, ~ dimethyl benzyl or ~-methylcyclohexyl. Cyclohexyl, isopropyl, ben~yl, ~-methylbenzyl and ~ dimethylbenzyl are particularly preferred.
Y preferably stands for sulphur or the methylene group, most preferably the methylene group.
The phosphorous acid esters used according to the invention are known and are prepared by known methods;
see in this connection European Patent Application No. 9115.
The phosphorous acid esters (stabilizers) according to the invention are preferably used in guantities ,of from Le A 28 156 4 17~
0.05 to 2% by weight, most preferably from 0.1 to 1% by weight, based on the polyolefins to be stabilized.
The following are mentioned as preferred polyolefins which can be stabilized with the phosphorous acid esters according to the invention: Polyethylene, polypropylene, polybutene-l, polypentene-l, polymethyl-pentene-1, polyisoprene, polybutadiene and mixtures of the above-mentioned polyolefins. Also to be mentioned are copolymers of polyolefins, such as propylene-butene-l copolymers, propylene-isobutylene copolymers, ethylene-butene-l copolymers, ethylene-propylene copolymers and tertiary polymers of ethylena and propylene with a diene such as hexadiene, cyclopentadiene or ethylene norbornene.
The stabilized polyolefins according to the invention may, of course, also contain other, conventional additives, such as W absorbents and light protective agents, metal inactivators, other phosphites, compounds which destroy peroxides, nucleating agents, plasticizers, lubricants, emulsifiers, fillers, carbon black, kaolin, talc, glass fibres, pigments, optical brightening agents, flame-protective agents, antistatic agents and other anti-oxidants.
Thio compounds may also be added to the polyolefins, for example those which produce a marked synergistic ef~ect, such as dilauryl thiodipropionate and distearyl thiodipro-pionate. These compounds are used at a concentration of from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, most preferably from 0.1 to 1% by weight, based on the polyolefins to be stabilized.
The phosphorous acid esters to be used according to the invention can easily be incorporated in the polyolefins by Le A 28 156 5 2 ~.3 i~
.
the usual methods at any phase during the preparation or processing of the polyolefins.
Polyolefins which have been stabilized by the phosphorous acid esters according to the invention are distinguished by their only slight discolouration when processed at high temperatures. The discolouration is only slight even if the polyolefin is extruded several times. Polyolefins which are particularly marked in this property are:
Polypropylene, polyethylene, polybutylene-l and the various ethylene-propylene copolymers.
Le A 28 lS6 6 ~ ~ ~ 1 7 r~ ~
Examples Example 1 Phosphorous acid ester of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane:
O H
/ \
A mixture of 392 g ~1 mol) of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane, 310 g (1 mol) of triphenyl-phosphite and 18 g (1 mol) of water is heated to 180C
under nitrogen at normal pressure. The reaction mixture is left to cool to 100C and is then heated from 100 to 200C
at 3333 Pa in 2.5 hours. 275 g of phenol distil over in this process. ~n almost colourless, slowly crystallizing product is left as residue (445 g).
Mp. 180-181~C (from toluene/hexane).
Exam~le 2 Phosphorous acid ester of bis-(2-hydroxy-3-styryl-5-methyl-phenyl)-methane:
Le A 28 156 7 ~) H
/ \
O O
Ph ~J~Ph A mixture of 218 g (0.5 mol) of bis-~2-hydroxy-3-styryl-5-methyl-phenyl)-methane and 68.7 g (0.5 mol) of phosphorus trichloride is heated to 60 70C in toluene for 3 hours.
9 g (0.5 mol) of water are then added and stirring is continued for 3 hours at 90~C. After removal of the solvent by distillation, 239 g of an almost colourless resin is obtained as residue.
Mp. 214~C (from tvluene/hexane).
Test of processing stability of polypropylene:
lo Unstabilized polypropylene (e.g. Hostalen PPK 0160 F) is homogenised with 0.15% of the stabilizer described in Example 1 in a high speed mixer, extruded as a strand in a single shaft extruder at 250C and granulated.
The granulate i5 passed through the extruder a further four times. A sample of granulate is removed a~ter each passage through the extruder and its melt index MVI-230/2.16 (cm3jlO min) is determined according to DIN 53 735. For this purpose, a sample of the granulate is heated to 230 C and pushed with a force of 2.16 kilopond through a nozzle having an opening of 2.095 mm. The volume of sample pressed through the nozzle in 10 minutes is measured.
Le A 28 156 8 ~Q~ 3'~
MVI-230C/2.16 tcm3/10 min]
Number of extrusions Polypropylene unstabilized 22.3 121 - -Irgaphos 168 (Ciba) 11~5 95.7 - -Substance from Example 1 1.2 4.8 9.9 16.1 This shows that the substances according to the invention have an excellent processing stabilizing effect as indicated by the comparatively slight lowering of the viscosity.
Oven ageing of polypropylene wafers containing phosphorous acid ester:
Unstabilized polypropylene powder (e.g. Hostalen PPK
0160 F) is carefully mixed with 0.2% by weight of the given stabilizer. In addition, samples containing 0.2% by weight of the same stabilizer and 0.1% by weight of distearyl-thiodipropionate are prepared. The mixed material is then ground in a two-roller mill for 10 minutes at room temperature. The stabilized polypropylene powder is then compressed in a hydraulic press under a pressure of 200 bar at 180C for 10 minutes. The resulting plates 0.1 mm in thickness are tested for their resistance to accelerated ageing in an oven at 150C. As soon as the platelets show the ~irst signs of friability, e.g. brown edges, they are regarded as decomposed.
Le A 28 156 9 2 ~ 7 c~ 1~
Hours until decomposition unstabilized 6 Stabilizer from Example 1 240 Stabilizer from Example 1 ~
5 0.1% distearyl thiodipropionate330 Stabilizer from Example 2 280 Stabilizer from Example 2 +
0.1% of distearyl thiodipropionate 350 Comparison ExamPle 10 6,6'-Di-(tert~-butyl-4,4'- 40 dimethyl-2,2'-biphenylene)-phosphite (substance from Example 3 and Claim 4 of DOS 2 856 801~
Le A 28 156 10
Stabilized polyolefins This invention relates to polyolefins stabilized with special phosphorous acid esters~
Organic poiymers such as polyolefins are subjected to thermal and oxidative degradation and decomposition by light. Numerous stabilizers are known for the various polymers. Their effectiveness depends both on the causes of decomposition and on the nature of the stabilized polymer. Some compounds which are effective long term antioxidants are relatively ineffective in processing operations such as extrusion, in which the heat to which the polymers are subjected is relatively high for a short period.
A combination of various stabilizers is generally used for obtaining sufficient stabilization of a polymer because the presence of only one stabilizer does not ensure sufficient protection against the various possible causes of damage to the polymer. Thus DE-OS 28 56 801, for example, describes alkylated 2,2'-~isphenylene-phosphites which ara capable of stabilizing polymers against processing conditions. The disadvantage of stabilizing with these phosphates, however, is their insufficient long Le A 28 156- Forei gn Countri es 2~f~3~
term stabilizing effect (see Comparison Example), which necessitates the addition of further stabilizers.
European Patent Application 395 030 describes certain organic phosphites which are suitable for stabilizing polyolefins still containing residues of a Ziegler catalyst, but even with these phosphites only insufficient long term stability of the polyolefins i5 achieved.
It has now surprisingly been found that by using special phosphorous acid esters of bisphenols, good processing stability is obtained and the long term stability of the resulting polyolefins is excellent and greatly improved compared with that obtained with bisphenylene phosphites.
As a result, polyolefins which have been stabilized according to the invention are also very durable in the absence of co-stabilizers such as diphenolic antioxidants.
The present invention therefore relates to polyolefins stabilized against processing and against long term deterioration, containing from 0.01 to 5% by weight of phosphorous acid esters corresponding to the following general formula OH
/ \
O O
R2~Y~R2 E~l R
Le A ~8 156 3 wherein ~1 stands for hydrogen or a C~-C18-alkyl, C5-C7-cycloalkyl, C7-C10-aralkyl or C6-C10-aryl group, R2 stands for a Cl-C8-alkyl, C5-C7-cycloalkyl, benzyl, ~-methylbenzyl or ~,~-dimethylbenzyl group and Y stands for sulphur or for CHR3 in which R3 stands for hydrogen, a Cl-C4-alkyl or a C5-C7-cycloalkyl group.
In the above formula, Rl preferably stands for a straight chained or branched alkyl group having 1 to 8 carbon atoms, for example methyl, ethyl, isopropyl or tertiary butyl, most preferably methyl or tertiary butyl~
R2 preferably stands for a branched alkyl group having 3 to 8 carbon atoms, e.g. isopropyl, isobutyl or tert.-butyl, cyclohexyl, benzyl, ~-methylbenzyl, ~ dimethyl benzyl or ~-methylcyclohexyl. Cyclohexyl, isopropyl, ben~yl, ~-methylbenzyl and ~ dimethylbenzyl are particularly preferred.
Y preferably stands for sulphur or the methylene group, most preferably the methylene group.
The phosphorous acid esters used according to the invention are known and are prepared by known methods;
see in this connection European Patent Application No. 9115.
The phosphorous acid esters (stabilizers) according to the invention are preferably used in guantities ,of from Le A 28 156 4 17~
0.05 to 2% by weight, most preferably from 0.1 to 1% by weight, based on the polyolefins to be stabilized.
The following are mentioned as preferred polyolefins which can be stabilized with the phosphorous acid esters according to the invention: Polyethylene, polypropylene, polybutene-l, polypentene-l, polymethyl-pentene-1, polyisoprene, polybutadiene and mixtures of the above-mentioned polyolefins. Also to be mentioned are copolymers of polyolefins, such as propylene-butene-l copolymers, propylene-isobutylene copolymers, ethylene-butene-l copolymers, ethylene-propylene copolymers and tertiary polymers of ethylena and propylene with a diene such as hexadiene, cyclopentadiene or ethylene norbornene.
The stabilized polyolefins according to the invention may, of course, also contain other, conventional additives, such as W absorbents and light protective agents, metal inactivators, other phosphites, compounds which destroy peroxides, nucleating agents, plasticizers, lubricants, emulsifiers, fillers, carbon black, kaolin, talc, glass fibres, pigments, optical brightening agents, flame-protective agents, antistatic agents and other anti-oxidants.
Thio compounds may also be added to the polyolefins, for example those which produce a marked synergistic ef~ect, such as dilauryl thiodipropionate and distearyl thiodipro-pionate. These compounds are used at a concentration of from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, most preferably from 0.1 to 1% by weight, based on the polyolefins to be stabilized.
The phosphorous acid esters to be used according to the invention can easily be incorporated in the polyolefins by Le A 28 156 5 2 ~.3 i~
.
the usual methods at any phase during the preparation or processing of the polyolefins.
Polyolefins which have been stabilized by the phosphorous acid esters according to the invention are distinguished by their only slight discolouration when processed at high temperatures. The discolouration is only slight even if the polyolefin is extruded several times. Polyolefins which are particularly marked in this property are:
Polypropylene, polyethylene, polybutylene-l and the various ethylene-propylene copolymers.
Le A 28 lS6 6 ~ ~ ~ 1 7 r~ ~
Examples Example 1 Phosphorous acid ester of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane:
O H
/ \
A mixture of 392 g ~1 mol) of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane, 310 g (1 mol) of triphenyl-phosphite and 18 g (1 mol) of water is heated to 180C
under nitrogen at normal pressure. The reaction mixture is left to cool to 100C and is then heated from 100 to 200C
at 3333 Pa in 2.5 hours. 275 g of phenol distil over in this process. ~n almost colourless, slowly crystallizing product is left as residue (445 g).
Mp. 180-181~C (from toluene/hexane).
Exam~le 2 Phosphorous acid ester of bis-(2-hydroxy-3-styryl-5-methyl-phenyl)-methane:
Le A 28 156 7 ~) H
/ \
O O
Ph ~J~Ph A mixture of 218 g (0.5 mol) of bis-~2-hydroxy-3-styryl-5-methyl-phenyl)-methane and 68.7 g (0.5 mol) of phosphorus trichloride is heated to 60 70C in toluene for 3 hours.
9 g (0.5 mol) of water are then added and stirring is continued for 3 hours at 90~C. After removal of the solvent by distillation, 239 g of an almost colourless resin is obtained as residue.
Mp. 214~C (from tvluene/hexane).
Test of processing stability of polypropylene:
lo Unstabilized polypropylene (e.g. Hostalen PPK 0160 F) is homogenised with 0.15% of the stabilizer described in Example 1 in a high speed mixer, extruded as a strand in a single shaft extruder at 250C and granulated.
The granulate i5 passed through the extruder a further four times. A sample of granulate is removed a~ter each passage through the extruder and its melt index MVI-230/2.16 (cm3jlO min) is determined according to DIN 53 735. For this purpose, a sample of the granulate is heated to 230 C and pushed with a force of 2.16 kilopond through a nozzle having an opening of 2.095 mm. The volume of sample pressed through the nozzle in 10 minutes is measured.
Le A 28 156 8 ~Q~ 3'~
MVI-230C/2.16 tcm3/10 min]
Number of extrusions Polypropylene unstabilized 22.3 121 - -Irgaphos 168 (Ciba) 11~5 95.7 - -Substance from Example 1 1.2 4.8 9.9 16.1 This shows that the substances according to the invention have an excellent processing stabilizing effect as indicated by the comparatively slight lowering of the viscosity.
Oven ageing of polypropylene wafers containing phosphorous acid ester:
Unstabilized polypropylene powder (e.g. Hostalen PPK
0160 F) is carefully mixed with 0.2% by weight of the given stabilizer. In addition, samples containing 0.2% by weight of the same stabilizer and 0.1% by weight of distearyl-thiodipropionate are prepared. The mixed material is then ground in a two-roller mill for 10 minutes at room temperature. The stabilized polypropylene powder is then compressed in a hydraulic press under a pressure of 200 bar at 180C for 10 minutes. The resulting plates 0.1 mm in thickness are tested for their resistance to accelerated ageing in an oven at 150C. As soon as the platelets show the ~irst signs of friability, e.g. brown edges, they are regarded as decomposed.
Le A 28 156 9 2 ~ 7 c~ 1~
Hours until decomposition unstabilized 6 Stabilizer from Example 1 240 Stabilizer from Example 1 ~
5 0.1% distearyl thiodipropionate330 Stabilizer from Example 2 280 Stabilizer from Example 2 +
0.1% of distearyl thiodipropionate 350 Comparison ExamPle 10 6,6'-Di-(tert~-butyl-4,4'- 40 dimethyl-2,2'-biphenylene)-phosphite (substance from Example 3 and Claim 4 of DOS 2 856 801~
Le A 28 156 10
Claims (3)
1. Polyolefins containing from 0.01 to 5% by weight of phosphorous acid ester corresponding to the following general formula wherein R1 stands for hydrogen, a C1-C18-alkyl, C5-C7-cycloalkyl, C7-C10-aralkyl or C6-C10-aryl group, R2 stands for a C1-C8-alkyl, C5-C7-cycloalkyl, benzyl, .alpha.-methylbenzyl or .alpha.,.alpha.-dimethylbenzyl group and Y stands for sulphur or for ?HR3 in which R3 stands for hydrogen, a C1-C4-alkyl group or a C5-C7-cycloalkyl group.
2. Polyolefins according to Claim 1, characterised in that they contain phosphorous acid esters in quantities of from 0.05 to 2% by weight.
Le A 28 156 11
Le A 28 156 11
3. Polyolefins according to Claims l and 2, containing phosphorous acid esters corresponding to the general formula of Claim l in which R1 stands for methyl, ethyl, isopropyl or tert.-butyl, R2 stands for isopropyl, isobutyl, tert.-butyl, cyclohexyl, benzyl, .alpha.-methylbenzyl or .alpha.-methylcyclohexyl and Y
stands for sulphur or the methylene group.
Le A 28 156 12
stands for sulphur or the methylene group.
Le A 28 156 12
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4106126.8 | 1991-02-27 | ||
| DE19914106126 DE4106126A1 (en) | 1991-02-27 | 1991-02-27 | STABILIZED POLYOLEFINE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2061730A1 true CA2061730A1 (en) | 1992-08-28 |
Family
ID=6425992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2061730 Abandoned CA2061730A1 (en) | 1991-02-27 | 1992-02-24 | Stabilized polyolefins |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0501248A1 (en) |
| JP (1) | JPH0578527A (en) |
| CA (1) | CA2061730A1 (en) |
| DE (1) | DE4106126A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3297631A (en) * | 1965-10-24 | 1967-01-10 | Exxon Research Engineering Co | Novel phenolic phosphorus stabilizers for polyolefins |
| US4929654A (en) * | 1988-10-04 | 1990-05-29 | Eastman Kodak Company | Cyclic phosphites and stabilized polymeric compositions |
-
1991
- 1991-02-27 DE DE19914106126 patent/DE4106126A1/en not_active Withdrawn
-
1992
- 1992-02-14 EP EP92102447A patent/EP0501248A1/en not_active Withdrawn
- 1992-02-21 JP JP7001792A patent/JPH0578527A/en active Pending
- 1992-02-24 CA CA 2061730 patent/CA2061730A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578527A (en) | 1993-03-30 |
| EP0501248A1 (en) | 1992-09-02 |
| DE4106126A1 (en) | 1992-09-03 |
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