AU2022203873A1 - Stabilized polyolefin compositions comprising benzofuranones and organophosphorus stabilizers - Google Patents

Stabilized polyolefin compositions comprising benzofuranones and organophosphorus stabilizers Download PDF

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AU2022203873A1
AU2022203873A1 AU2022203873A AU2022203873A AU2022203873A1 AU 2022203873 A1 AU2022203873 A1 AU 2022203873A1 AU 2022203873 A AU2022203873 A AU 2022203873A AU 2022203873 A AU2022203873 A AU 2022203873A AU 2022203873 A1 AU2022203873 A1 AU 2022203873A1
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Werner Hoelzl
Roswell E. King Iii
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BASF SE
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BASF SE
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    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract

Polyolefin compositions comprising i) a polyolefin, ii) one or more phosphorus containing benzofuranone compounds and iii) one or more organophosphorus stabilizers are provided excellent protection against discoloration and enhanced thermal stability during melt processing as exhibited by improved retention of molecular weight and maintenance of polymer molecular architecture.

Description

Stabilized Polyolefin Compositions Comprising Benzofuranones and Organophosphorus Stabilizers
The disclosure relates to polyolefin compositions comprising 3-phenyl-benzofuran-2-one compounds containing phosphorus and certain organophosphorus stabilizers. The polyolefin compositions exhibit excellent color performance and enhanced thermal stability during melt processing.
Traditional phenolic/phosphite antioxidant blends have been used successfully for decades to provide good melt flow control and acceptable color maintenance to polyolefins. However, there is a growing demand for lower color of polyolefin articles and improved color maintenance.
The entire disclosure in the complete specification of our Australian Patent Application No. 2018298021 is by this cross-reference incorporated into the present specification.
Summary
Accordingly, disclosed are polyolefin compositions comprising i) a polyolefin, ii) one or more phosphorus-containing benzofuranone compounds and iii) one or more organophosphorus stabilizers. The phosphorus-containing benzofuranone compounds may be of formula I-p1, I-p2, 1-ol, 1-o2, I-m1 or 1-m2, further described herein below. Also disclosed are additive compositions comprising the phosphorus-containing benzofuranone compounds and the organophosphorus stabilizers.
Also disclosed are methods of stabilizing a polyolefin against deleterious effects of heat, light and oxygen, the method comprising incorporating into the polyolefin ii) one or more benzofuranone compounds selected from the group consisting of formula I-p1, I-p2, 1-ol, 1-o2, I ml and 1-m2 and iii) one or more organophosphorus stabilizers. Deleterious effects of heat, light and oxygen may lead to undesired color.
Detailed Disclosure
The 3-phenyl-benzofuran-2-one compounds containing phosphorus may be of formula I p1, I-p2, 1-ol, 1-o2, I-m1 or 1-m2 (also referred to herein as "benzofuran-2-one" or "benzofuranone" compounds).
WO 2019/010166
0 -o
0
\ R'p5 2 / R 'p5
-p2 -p1
H H
o 6 R6
Rio 7 0
Rio o R6 00
RR 00 0\ 0 R R4 H /R \4 /H// \-o2 2 5 R ' R0 Ro / \ R
Rl R0 6 I-ol Rol Ro
O-Rlm
O-Z 0
Rlm /R2m 0 /O Nyym
/ Rm5 ' Rms
/m3Rm 6 Rm 3 Rm RRm1 Rm1
0 Rmi 0 Rmi
H I-m1 H 1-m2 4 R4 0 R O
| | R7 R5 R7 R5
wherein X and Z are independently P or P=O; YP, Y'and Ym are oxygen or represent a covalent bond; when YP, Y'and Ym are oxygen, R1Prepresents one of subformulae II-p, ll-o or I1-m
Ros R°66 Rp3 RpR0
/p2Rp 5 ROl
Ro2 ORP16
H H |1-o O R4 O R4
RI R RI R
Rms
m3 Rm RRm1
O Rl
0 R
R
R° represents one of subformulae II-o or Il-m, Rm represents subformula ll-m, or R'P together with R 2p, R° together with R 2°and Rl together with R 2m represent one of subformulae Ill, IV or V
Ra1 Ra4
Ill H H H H
Ra2 Ra3
Rb6
Rb1 Rb4
IV H H H H
Rb 2 Rb3
Rc1 S Rc4
H #H H H
Rc2 Rc3 or R'P, R"°and R"are C 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C C 8-alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 -cycloalkyl, C 7-C1 3-aralkyl, C2-C18 alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 1 -alkyl, which is interrupted by one sulfur atom, R2 P represents one of subformulae II-p, ll-o orI-m, R 2° represents one of subformulae II-o or Il-m, R2"'represents subformula ll-m, or R2p together with R'P, R 2° together with R'°and R 2" together with R" represent one of subformulae Ill, IV or V, or R2p, R 2° and R 2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, CC 1 -alkyl, C3-C16 cycloalkyl, C 7-C 13-aralkyl, C 2-C 1-alkenyl, C 2-C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16-alkyl, which is interrupted by one sulfur atom; when YP, Y'and Y' represent a covalent bond, R'P represents one of subformulae II-p, ll-o orI-m, R° represents one of subformulae II-o orI-m, R represents subformula ll-m, or R 1P, R"°and R" are C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, CrC8 alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 -cycloalkyl, C 7-C1 3-aralkyl, C 2-C18 -alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom, R2 p, R 2° and R2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C-C 8-alkyl, C-C 8-alkoxy, halogen or one phenyl, or halogen; R 4 , R5 , R6 and Rare each independently hydrogen or C-C8 -alkyl, Rp2 , Rp3 , Rp5 and Rp 6 are each independently hydrogen or C-C8 -alkyl, R° 1, R02, R05 and R0 6are each independently hydrogen or C-C8 -alkyl, R", R", R"'and Rm are each independently hydrogen or C-C8 -alkyl, R , R, Ra and Ra4 are each independently hydrogen or C-C8 -alkyl, R, R 2 , R, R 4 , R and R are each independently hydrogen or C-C8 -alkyl and R°, R 2, RC3 and R4 are each independently hydrogen or C-C8 -alkyl.
The one point of attachment at subformulae II-p, ll-o or Il-m is denoted by the end of the line which does not carry a character and is blank. The two points of attachment at subformulae Ill, IV or V are denoted each by the end of the respective line which does not carry a character and is blank. When RP together with R 2p, Rl° together with R 20 and R" together with R 2"'represent one of subformulae Ill, IV or V, then R 2ptogether with R'P, R 20 together with R 1°and R 2"'together with R" represent the same subformula.
A compound of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or 1-m2 possesses at least one asymmetric carbon atom, i.e. a carbon atom at the 3-position of the benzofuran-2-one structural unit. Further asymmetric carbon atoms can be present in alkyl substituents with at least four carbon atoms. A phosphorus atom, which is substituted with three different substituents, can show a hindered inversion, which can lead dependent on temperature to an asymmetric phosphorus atom. The invention relates to any one of these enantiomers, resulting diastereomers or mixtures thereof.
C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl,isforexamplephenyl,2-methyl-phenyl, 3-methyl-phenyl, 4-methyl phenyl, 2,4-dimethyl-phenyl, 3,5-dimethyl-phenyl, 4-(1,1-dimethylethyl)-phenyl, 4-(1,1,3,3 tetramethylpentyl)-phenyl, naphthalen-1-yl, naphthalen-2-yl, 6-methylnaphthalen-2-yl, 4 phenyl-phenyl, 2-methoxy-phenyl, 3-methoxy-phenyl, 4-methoxy-phenyl, 2-ethoxyphenyl, 3 ethoxy-phenyl, 3-(n-propoxy)-phenyl, 4-(1,1-dimethylethoxy)-phenyl, 2-chloro-phenyl, 3 chlorophenyl, 4-chlorophenyl, 2-chloro-4-methylphenyl. In some embodiments, C-C1 o-aryl is unsubstituted or substituted by C-C8 -alkyl or C-C8 -alkoxy. In certain embodiments, aryl is phenyl which is unsubstituted or substituted by C-C8 -alkyl. In other embodiments, aryl is phenyl.
Cl-C 8-alkyl is linear or branched and for example methyl, ethyl, n-propyl, 1-methyl ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl, n heptyl, 1-methyl-hexyl, n-octyl, 1-methyl-heptyl, 2-ethyl-hexyl, 5,5-dimethyl-hexyl or 1,1,3,3 tetramethyl-butyl. In some embodiments, alkyl is C-C 4-alkyl or C-alkyl, for example methyl, ethyl, 1-methyl-ethyl, 1-methyl-propyl 1,1-dimethyl-ethyl or 1,1,3,3-tetramethyl-butyl. In certain embodiments, alkyl is C-C 4-alkyl, such as methyl, ethyl, 1-methyl-ethyl, 1-methyl propyl 1,1-dimethyl-ethyl and in certain other embodiments is methyl, 1-methyl-propyl or 1,1 dimethyl-ethyl.
Cl-C 8-alkoxy is linear or branched and for example methoxy, ethoxy, n-propoxy, 1 methyl-ethoxy, n-butoxy, 1-methyl-propoxy, 1,1-dimethyl-ethoxy, n-pentoxy, 2-methyl pentoxy, 2-ethyl-butoxy, 1-methyl-hexoxy, n-octyloxy, 1-methyl-heptoxy, 2-ethyl-hexoxy, 1,1,3,3-tetramethyl-butoxy. In some embodiments, alkoxy isC-C 4-alkoxy such as methoxy.
Halogen is for example a fluorine atom (fluoro), chlorine atom (chloro), a bromine atom (bromo) or an iodine atom (iodo). In certain embodiments, halogen is a chlorine atom or a fluorine atom, in some embodiments, halogen is a fluorine atom.
C-C 1 -alkyl is linear or branched and for example methyl, ethyl, n-propyl, 1-methyl ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl, n heptyl, 1-methyl-hexyl, n-octyl, 1-methyl-heptyl, 2-ethyl-hexyl, 5,5-dimethyl-hexyl, 1,1,3,3 tetramethyl-butyl, n-nonyl, 2-ethyl-heptyl, n-decyl, undecyl, n-dodecyl, tridecyl, tetradecyl, pentadecyl, n-hexadecyl or n-octadecyl. In some embodiments, C-C 18 -alkyl is a linear or branchedC1 -C1 2-alkyl.
C-C 1 -cycloalkyl is unsubstituted or substituted byC-C 4-alkyl and is for example cyclobutyl, cyclopentyl, 3,4-dimethyl-cyclopentyl, cyclohexyl, 4-methyl-cyclohexyl, 4-(1 methylethyl)-cyclohexyl, 4-(1,1-dimethylethyl)-cyclohexyl, 3,5-dimethyl-cyclohexyl, 5-methyl 2-(1-methyl-ethyl)-cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. In certain embodiments, C3 -C 16-cycloalkyl is C5 -C-cycloalkyl such as cyclohexyl.
C 7-C 13-aralkyl is for example benzyl, 4-methyl-benzyl, 2-phenyl-ethyl, 3,5 dimethylbenzyl, 1-phenyl-1,1-dimethyl-methyl, 3-phenyl-propyl, 3-phenyl-2-methyl-propyl, 3,5-di-tert-butyl-benzyl or 4-phenyl-phenyl-methyl. In certain embodiments, aralkyl is benzyl. C 2 -C 1 -alkenyl is linear or branched and for example vinyl, allyl, Z- or E-but-2-ene-yl, or E but-3-ene-yl, Z- or E-pent-2-ene-yl, pent-4-ene-yl, Z- or E-2-methyl-but-2-ene-yl, Z- or E-3 methyl-but-3-ene-yl, Z- or E-hex-1-ene-yl, Z- or E-hexadec-9-ene-yl or Z- or E-octadec-9 ene-yl, (9Z,12Z)-octadeca-9,12-diene-yl or (9Z,12Z,15Z)-octadeca-9,12,15-triene-yl. In certain embodiments, alkenyl is allyl.
C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, is linear or branched and for example methoxy-methyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-(2-methoxy-ethoxy) ethyl, 2-n-butoxy-ethyl, 2-[2-(2-methoxy-ethoxy)-ethoxy]-ethyl, 2-[2-[2-(2-methoxy-ethoxy) ethoxy]-ethoxy]-ethyl, 2-(2-methoxy-1-methyl-ethoxy)-1-methyl-ethyl, 3-(n-propoxy)-propyl, 2-[2-[2-(2-n-butoxy-ethoxy)-ethoxy]-ethoxy]-ethyl, 2-[2-(2-n-butoxy-2-methyl-ethoxy)-2 methyl-ethoxy]-2-methyl-ethyl or 2-[(2-n-lauryl)-ethoxy]-ethyl. In some embodiments, alkyl interrupted by one or more oxygen atoms is 2-methoxy-ethyl or 2-ethoxy-ethyl.
C 2 -C 1 -alkyl, which is interrupted by one sulfur atom, is linear or branched and for example 2-(methyl-sulfanyl)-ethyl, 3-thiaundecyl or 3-thiapentadecyl.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-m1 or I m2, wherein R 4 and R6 are hydrogen and R 5 and R7 are each independently hydrogen or C C 8-alkyl, for instance hydrogen orC-C 4-alkyl. In certain embodiments, R 4 , R6 and R7 are hydrogen and R5 is hydrogen or C-C8 -alkyl, for example hydrogen orC-C 4-alkyl. In some embodiments, Rp2 and Rp 6 are each independently hydrogen or C-alkyl, Rp3 and Rp 5 are each independently hydrogen orC-C 4-alkyl, R 1and R° 6are each independently hydrogen or Cr
C 8-alkyl, R is hydrogen or C-alkyl and R°5 is hydrogen orC-C 4-alkyl, R"" is hydrogen or C-alkyl, R" 3and R" 'are 5 each independently hydrogen orC-C 4-alkyl and Rm 6 is hydrogen or C1-C 8-alkyl.
In certain embodiments, benzofuranones are of formula1-p1, 1-p2, 1-ol, 1-o2, I-m1 or I-m2, wherein Rp2 and RP 6 are hydrogen and RP 3 and RP 5 are each independently hydrogen or C 1-C 4-alkyl, R° is hydrogen or C 1 -C 8-alkyl, R°2 is hydrogen, R°5 and R0 6 are each independently hydrogen orC-C 4-alkyl, R"" and R" 3 are hydrogen or C-alkyl, R" 5 is hydrogen orC -C 3-alkyl and Rm 6is hydrogen or C-C 8-alkyl. In other embodiments, Rp2 and RP6are hydrogen and RP3 and RP5 are each independently hydrogen orC-C 4-alkyl, wherein one of RP3 and RP5 is notC 4 -alkyl, R°1 is hydrogen or C-C8 -alkyl, R0 2 is hydrogen, R0 5 is hydrogen orC -C 3 -alkyl and R 06 is hydrogen orC-C 4-alkyl and R"" and R" 3 are hydrogen or C-alkyl, R" 5 is hydrogen or Cl-C 3-alkyl and Rm 6 is hydrogen or C-C8 -alkyl.
In some embodiments, Rp2 and RP 6 are hydrogen and one of RP3 and RP5 is hydrogen, whereas the other one is hydrogen orCrC 4-alkyl, R 1 is hydrogen or C-C8 -alkyl, R0 2 is hydrogen, R0 5 is hydrogen or C-alkyl and R0 6 is hydrogen orCrC 4-alkyl and R", R"3 and R"5are hydrogen and R 6 is hydrogen or C-C8 -alkyl. In certain embodiments, Ra, R, R 3 and Ra 4 are each independently hydrogen orCrC 4-alkyl, Rbl, Rb 2, RW, Rb 4 , Rb 5 and Rb6 are each independently hydrogen orCr-C 4-alkyl and R°, R 2 , Rand R 4 are each independently hydrogen orCrC 4-alkyl.
In some embodiments, Ra, Ra2, R 3 and Ra4 are each independently hydrogen or C C 4-alkyl, Rbl, Rb2, RbW, Rb4 are each independently hydrogen orC-C 4-alkyl and one of Rbs and Rb 6 is C-C 4-alkyl, whereas the other one is hydrogen and R°, R 2 , R 3 and R4 are each independently hydrogen orC-C 4-alkyl. In certain embodiments, YP, Yoand Y' are oxygen or represent a covalent bond; when YP, Yoand Y"'are oxygen, R'P represents one of subformulae II-p, ll-o or Il-m, Rl° represents one of subformulae II-o or Il-m, R"' represents subformula ll-m, or RPtogether with R 2p, R°together with R20 and R 'together with R 2 "
represent one of subformulae Ill, IV or V, or R'P, R'°and R' areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CC 1 -alkyl, C-C 1 -cycloalkyl orC 2-C18 -alkenyl and R2 Prepresents one of subformulae II-p, ll-o or I-m, R 2° represents one of subformulae II o or I-m, R 2"'represents subformula l-m, or Rtogether with RP, R2° together with Rl° and R 2"'together with Rl' represent one of subformulae Ill, IV or V, or R 2p, R20 and R 2"'areC6 C 1o-aryl, which is unsubstituted or substituted byl-C 6 -alkyl, CC 1 -alkyl, C-C 1 -cycloalkyl or C 2-C 1 -alkenyl; when YP, Yoand Y' represent a covalent bond, R'P represents one of subformulae II-p, Il-o or Il-m, R° represents one of subformulae II-o orI-m, Rm represents subformula ll-m, or R'P, R° and R" areC6 -C1 2-aryl, which is unsubstituted or substituted by Cl-C 8-alkyl, C-C1-alkyl, C-C1-cyoakyI orC 2-C1-alkenyl and R 2p, R2°and R2 areC6-CO aryl, which is unsubstituted or substituted by C1-C8 -alkyl, or halogen, which is chloro or fluoro.
In some embodiments, YP, Y'and Ym are oxygen or represent a covalent bond; when YP, Y'and Ym are oxygen, RPrepresents subformula ll-p, R"°represents the formulae II-o, R"represents subformula ll-m, or RPtogether with R 2p, R°together with R 2°and R together with R represent one of subformulae Ill, IV or V, or RP, R"°and R"areC6-CO aryl, which is unsubstituted or substituted by C1-C-alkyl, CC18 -alkyl, C-C16 -cycloakyl or C 2-C1-alkenyl and R 2Prepresents subformula ll-p, R 2° represents subformula ll-o, R 2
represents subformula ll-m, or RP t ogether with RP, R 2°together with R"°and R 2together with Ri represent one of subformulae Ill, IV or V, or R 2p, R 2°and 2R areC 6 -Clo-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CC1 8 -alkyl, C-C16 -cycloalkyl orC2-C1 alkenyl; when YP, Y'and Ym represent a covalent bond, RP represents subformulall-p, R° represents subformulae II-o, R"represents subformula l-m, or RP, R°and R"areC6-CO aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CC18 -alkyl, C-C16 -cycloakyl or
C 2-C1-alkenyl and R 2p, R2°and R2areC 6-ClO-aryl, which is unsubstituted or substituted by Cl-C 8-alkyl, or halogen, which is chloro or fluoro.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I m2, wherein YP, Y'and Ymare oxygen or represent a covalent bond; when YP, Y'and Ym are oxygen, R 1P represents subformula ll-p, R° represents the formulae II-o, R" represents subformula ll-m, or RPtogether with R 2p, R"°together with R2°and Rtogether with R2m represent one of subformulae Ill, IV or V, or RP, R"°and R areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CC 1 -alkyl, C-C 1 -cycloalkyl orC 2-C 1 8 -alkenyl and RP 2is R1P, R 20is R10, R2is Rm, or RP t ogether with R1P, R20 together with R10and R 2
together with Ri represent one of subformulae Ill, IV or V; when YP, YOand Ym represent a covalent bond, R1 P represents subformula ll-p, R10 represents subformulae II-o, R" represents subformula ll-m and R2 p, R 20 and R 2areC6 -Clo-aryl, which is unsubstituted or substituted by C-C 8-alkyl, or halogen, which is chloro or fluoro.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I m2, wherein YP, YOand Ymare oxygen or represent a covalent bond; when YP, YOand Ym are oxygen, RiP represents one of subformulae II-p, ll-o or II-m, R° represents one of subformulae II-o or II-m, R represents subformula Il-m, or RP together with R2 p, R° together with R 2 0and R" together with R represent one of subformulae Ill, IV or V, or R'P, R'° and R" areC 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 1 -alkyl or C3 -C 1 -cycloalkyl and R 2P represents one of subformulae II-p, ll-o or I-m, R 20 represents one of subformulae II-o orI-m, R represents subformula l-m, or Rtogether with R'P, R02 together with R 10and R together with R" represent one of subformulae Ill, IV or V, or RP, R 2 0and R 2 areC 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 1 -alkyl or C3 -C 1 -cycloalkyl; when YP, YOand Ymrepresent a covalent bond, R1P represents one of subformulae II-p, ll-o or Il-m, R10 represents one of subformulae II-o orI-m, R represents subformula ll-m, or R'P, R 10 and R" areC6 -C 1O-aryl, which is unsubstituted or substituted by Cl-C 8-alkyl, C-C 1 -alkyl or C-C 1 -cycloalkyl and R 2p, R 2 0and R2 areC6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl or fluoro.
In certain embodiments, YP, Y° and Ym are oxygen or represent a covalent bond; when YP, YOand Ym are oxygen, R1Prepresents one of subformulae II-p, ll-o orI-m, R10 represents one of subformulae 11-o orI-m, R" represents subformula l-m, or RPtogether with R2p, R 1°together with R 2 0and R"together with R2 represent subformula Ill, or R'P, R10 and R1 areC 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or C-C 1 -alkyl and R 2Prepresents one of subformulae II-p, ll-o or I-m, R 2° represents one of subformulae II o or Il-m, R represents subformula l-m, or Rtogether with R'P, R2° together with R10 and R t ogether with R" represent subformula Ill, or R 2p, R 20 and R2 areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or C-C18 -alkyl; when YP, YOand Ym represent a covalent bond, R 1Prepresents one of subformulae II-p, ll-o or Il-m, R10 represents one of subformulae II-o or I-m, R" represent subformula or Il-m, or R'P, R10 and R" areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or C-C 18 -alkyl and R 2p, R20 and R2 areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or fluoro.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol or I-o2, wherein YP and YOare oxygen or represent a covalent bond; when YP and YOare oxygen, R'P, R 2p, R 10or R 2 0does not represent subformula ll-m; when YP and YOrepresent a covalent bond, R 1Por R 10does not represent subformula ll-m. In certain embodiments in compounds of formula 1-p1 or I-p2, YP is oxygen or represents a covalent bond; when YP is oxygen, RPor R 2Pdoes not represent subformulae II-o or II-m; when YP represents a covalent bond, RP does not represent subformulae II-o or I-m.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I m2, wherein YP, YOand Ymare oxygen or represent a covalent bond; when YP, YOand Ym are oxygen, R'P represents one of subformulae II-p, Il-o or I-m, R° represents one of subformulae II-o or II-m, R represents subformula l-m, or R'P, R"°and R" are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C1 -C 8 -alkoxy, halogen or one phenyl, C1-C 1 -alkyl, C-C 1 -cycloalkyl, C 7-C 13-aralkyl, C 2-C 1 -alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom, R 2P represents one of subformulae II-p, ll-o or I-m, R 2°represents one of subformulae II-o or Il-m, R2 m represents subformula l-m, or R2 p, R 2°and Rm2 are C-C1 o-aryl, which is unsubstituted or substituted by C1 -C-alkyl, C-C8 -alkoxy, halogen or one phenyl, C1-C18 alkyl, C-C 16-cycloalkyl, C 7-C 13-aralkyl, C 2-C 1 -alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom; when YP, Y'and Ym represent a covalent bond, RP represents one of subformulae II-p,ll-o orI-m, R'° represents one of subformulae II-o orI-m, R" represents subformula l-m, or RP, R"°and Rare C6 -C 1o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 -cycloalkyl,C 7-C 13-aralkyl, C 2-C 1 -alkenyl, C2-Co alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 1 -alkyl, which is interrupted by one sulfur atom, R 2p, R2° and R 2m are C-C1o-aryl, which is unsubstituted or substituted by Cl-C 8-alkyl, C-C -alkoxy, 8 halogen or one phenyl, or halogen.
In certain embodiments, the benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I-m2, wherein YP, Y'and Ym are oxygen. In some embodiments, the benzofuranones are of formula I-p or I-o, wherein YP and Y'are oxygen and RP, R2 p, R'°or R 2°does not represent subformula ll-m. In other embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-m1 or I-m2, wherein YP, Y'and Y'm are oxygen, RPtogether with R 2p, R"°together with R2° and R 'together with R2m represent one of subformulae Ill, IV or V and R together with R1P, R 2°together with R"°and R 2m together with R" represent one of subformulae Ill, IV or V.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol or I-o2, wherein YP and Y'are oxygen, RPtogether with R2Pand R"°together with R 2° represent one of subformulae Ill, IV or V and R together with RPand R 2°together with R° represent one of subformulae Ill, IV or V. In certain embodiments, benzofuranones are of formula 1-p1 or I p2, wherein Yp is oxygen and RPtogether with R 2Prepresent one of subformulae Ill, IV or V. In some embodiments, benzofuranones are of formula l-p, wherein Yp is oxygen and R 1P together with R 2Prepresent subformula IV.
The above cited embodiments for compounds of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I-m2 refer individually to the structural units of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I-m2.
These structural units comprise the benzofuran-2-one unit including R4 , R , R and R , the linking phenylene unit including Rp 2, Rp3 , Rp5 , R6 ,pR° 1 , R0 2 , R0 5,R°, R", R"3 , RMand Rm6 and the other-close-to-phosphorus atom unit including RP, R 2 , R°, R 20 , Rlm"and R 2"'with 2 substituents for subformulae Ill, IV or V, i.e. Ra, Ra, R', Ra4 , Rbl, Rb , RW, Rb 4 , Rb 5 , Rb6 , R°1, RC2 , RC3 and RC 4. The above cited embodiments for the three structural units can be combined. Examples thereof are provided below.
In some embodiments, benzofuranones are formula 1-p1, 1-p2, 1-ol, 1-o2, I-mi or I m2, wherein YP, Yoand Y"'are oxygen or represent a covalent bond; when YP, Yoand Y"'are oxygen, R'P represents one of subformulae II-p, ll-o or Il-m, Rl° represents one of subformulae II-o or II-m, R"' represents subformula l-m, or RP together with R2 p, R'° together with R 2 0and Rl'together with R 2' represent one of subformulae Ill, IV or V, or R'P, Rl° and R"' areC 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, CrC8 alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C16 -cycloalkyl, C 7-C1 3-aralkyl, C 2-Cis-alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, orC 2-C1 6 -alkyl, which is interrupted by one sulfur atom, R 2Prepresents one of subformulae II-p, ll-o orI-m, R 20 represents one of subformulae II-o or I-m, R 2 ' represents subformula ll-m, or RP t ogether with RP, R20 together with Rl° and R 2
" together with Rl'represent one of subformulaeIll, IV or V, or R2p, R02 and R2"'areC6-C1O aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, C-C 18 -alkyl, C3 -C 16 -cycloalkyl, C 7-C 13 -aralkyl, C 2-C 18-alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, orC 2-C1 6 -alkyl, which is interrupted by one sulfur atom; when YP, Yoand Y' represent a covalent bond, R'P represents one of subformulae II p, ll-o or Il-m, Rl° represents one of subformulae II-o or I-m, R"' represents subformula l-m, or R1 P, R1°and R''areC 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C C 8-alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 6 -cycloalkyl, C 7-C 1 3-aralkyl, C2-C1
alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, orC 2-C1 6 -alkyl, which is interrupted by one sulfur atom, R 2p, R20 and R 2 ' areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 8-alkoxy, halogen or one phenyl, or halogen; R 4 and R6 are hydrogen, R 5 and R7 are each independently hydrogen or C-C8 -alkyl, Rp2 and R are each independently hydrogen or C-alkyl, Rp3 and Rp5 are each independently hydrogen orC-C 4-alkyl, R° 1and R0 6 are each independently hydrogen or C-C8 -alkyl, R0 2 is hydrogen or C-alkyl, R0 5 is hydrogen orC-C 4-alkyl, R"" is hydrogen or C-alkyl, R"3 and R" 5 2 3 are each independently hydrogen orCrC 4-alkyl, R 6 is hydrogen or C-C 8 -alkyl, Ra, R , Ra 2 and Ra 4 are each independently hydrogen orCrC 4-alkyl, R , Rb , RW, Rb 4 , R sand Rb6 are each independently hydrogen orC-C 4-alkyl and R°1, R 2 , Rand R 4 are each independently hydrogen orC-C 4-alkyl.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mI or I m2, wherein YP, Y'and Y"'are oxygen or represent a covalent bond; when YP, Y'and Y"'are oxygen, R 1P represents one of subformulae II-p, ll-o or Il-m, R° represents one of subformulae II-o or Il-m, R represent subformula l-m, or R'Ptogether with R2 p, R"°together with R2°and Rltogether with R2 ' represent one of subformulae Ill, IV or V, or RP, R°and Rare C6 -C 1o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, C-C 1 -alkyl, or C C 1 -cycloalkyl and R 2Prepresents one of subformulae II-p, ll-o or Il-m, R 2° represents one of subformulae II-o or I-m, R 2"'represents subformula l-m, or R together with RP, R 2° together with R"°and R 2 together with R" represent one of subformulae Ill, IV or V, or R R 2° and R 2 ' are C6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 1 -alkyl or C3 -C 1 -cycloalkyl; when YP, Y'and Y' represent a covalent bond, R1P represents one of subformulae II-p, ll-o or Il-m, R° represents one of subformulae II-o or Il-m, R represents subformula ll-m, or R1P, R° and R" are C6 -C 1 -aryl, which is unsubstituted or substituted by Cl-C 8-alkyl, C-C 1 -alkyl or C-C 1 -cycloakyl and R 2p, R 2°and R 2 ' are C6-C 1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or fluoro; R4 , R 5, R 6 and R 7 are each independently hydrogen or C-C8 -alkyl, Rp2 , Rp3, R p 5and Rp 6are each independently hydrogen or C-C8 -alkyl, R° 1, R° 2, R°5 and R° 6 are each independently hydrogen or CrC8 alkyl, R"1, R- 3 , R"'5and Rm 6 are each independently hydrogen or C-C8 -alkyl, Ra, R2, Ra3 and Ra 4 are each independently hydrogen or C-C8 -alkyl, Rb, Rb 2 , R 3 , Rb 4 , Rb 5 and Rb6 are each independently hydrogen or C-C8 -alkyl and R 1 , R 2 , R 3 and R 4 are each independently hydrogen or C-C8 -alkyl.
In certain embodiments, benzofuranones are of formula1-p1, 1-p2, 1-ol or I-o2, wherein YPand Y'are oxygen or represent a covalent bond; when YPand Y'are oxygen, R'P represents one of subformulae I-p or 11-0, R"°represents subformulae II-o, or R'Ptogether with R2Pand R"°together with R 2°represent one of subformulae Ill, IV or V, or R1 Pand R°are C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, C-C 1 -alkyl, C-C 16 -cycloalkyl, C 7-C 13-aralkyl, C 2-C18 -alkenyl, C 2-C30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom, R2P represents one of subformulae Il-p or 11-0, R 2° represents subformulae II-o, or R22togetherwith R'Pand R 2°together with R° represent one of subformulae Ill, IV or V, or R 2P and R 2°are C6 -C 1o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CrC8 alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 -cycloalkyl, C 7-C 13-aralkyl, C 2-C18 -alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom; when YP and Y° represent a covalent bond, RP represents one of subformulae I-p or 11-0, R° represents subformulall-o, or RP and R° are C-C1 aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, C-C 18 -alkyl, C3 -C 16 -cycloalkyl, C 7-C 13 -aralkyl, C 2-C 18-alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, orC 2-C 16 -alkyl, which is interrupted by one sulfur atom, R 2Pand R2°areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, CC6 4 5 6 7 alkoxy, halogen or one phenyl, or halogen; R , R , R and R are each independently hydrogen orC 1-C 6-alkyl, Rp2 , Rp 3, Rp 5and Rp 6 are each independently hydrogen or CrC8 alkyl, R°1, R° 2, R°5 and R° 6are each independently hydrogen or C-C8 -alkyl, Ra1 , Ra2 , Ra3 and are each independently hydrogen or C-C8 -alkyl, R, R 2 , R, R 4 , R and R are each independently hydrogen or C-C8-alkyl and R°, R 2, RC3 and R4 are each independently hydrogen or C-C8 -alkyl.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol or I-o2, wherein YPand Y'are oxygen or represent a covalent bond; when YPand Y'are oxygen, R'P represents one of subformulae I-p or 11-0, R"°represents subformula ll-o, or R'Ptogether with R2Pand R"°together with R 2°represent subformula Ill, or RPand R"°areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or C-C 18 -alkyl, R2P represents one of subformulae Il-p or II-o, R 2° represents subformula ll-o, or Rtogether with RP and R 2° together with R° represent subformula Ill, or R 2Pand R2° areC6 -C1 o-aryl, which is unsubstituted or substituted by CrC8 alkyl, or C-C 1 -alkyl; when YP and Y'represent a covalent bond, R 1P represents one of subformulae Il-p or 11-0, R° represents subformulall-o, or RP and R'°areC6 -C1 o-aryl, which is unsubstituted or substituted by C-C 2 2 8 -alkyl, or CC 1 -alkyl, R Pand R °areC 6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, or fluoro; R 4 and R6 are hydrogen, R 5 and R7 are each independently hydrogen or C-C8 -alkyl, Rp2 and Rp6 are hydrogen, Rp3 and R are each independently hydrogen orC-C 4-alkyl, wherein one of Rp3 and Rp5 is notCa alkyl, R 1 is hydrogen or C-C8 -alkyl, R°2 is hydrogen, R°5 is hydrogen orC-C 3 -alkyl, R°6 is hydrogen orC1 -C 4-alkyl, Ra 1, Rae, Ra 3 and Ra4 are each independently hydrogen orCr-C4 alkyl, Rb, Rb2, Rb',3 Rb4 , Rband Rb6are each independently hydrogen orC-C 4-alkyl and R°, R 2 , R 3and R4 are each independently hydrogen orC-C 4-alkyl.
In other embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mI or I m2, wherein YP, Y'and Ymare oxygen or represent a covalent bond; when YP, Y'and Ym are oxygen, R 1Prepresents one of subformulae II-p, ll-o or Il-m R° represents one of subformulae II-o or Il-m, R" represents subformula l-m, or R'P, R°and R" areC 6 -C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, C-C 1 -alkyl, C-C 1 -cycloalkyl, C 7-C 13-aralkyl, C 2-C 1 -alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, orC 2-C 16 -alkyl, which is interrupted by one sulfur atom, R2P represents one of subformulae II-p,Il-o or I-m, R 2°represents one of subformulae II-o or Il-m, R2"'represents subformula ll-m, or R 2p, R 2°and R2 ' are C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, CrC8 alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 6 -cycloalkyl, C 7-C1 3-aralkyl, C 2-C1 8 -alkenyl,
C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom; when YP, Y'and Y"'represent a covalent bond, RP represents one of subformulae II-p, ll-o or I-m, R'°represents one of subformulae II-o or II m, Ri represents subformula ll-m, or RP, R"°and R" are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, CC 1 -alkyl, C3-C16 cycloalkyl, C 7-C 13-aralkyl, C 2-C 1-alkenyl, C 2-C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16-alkyl, which is interrupted by one sulfur atom, R2 p, R 2°and R2 ' are C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, or halogen; R 4, R5 , R6 and R7 are each independently hydrogen or C-C8 -alkyl, Rp 2 , Rp3 , Rp 5 and Rp 6are each independently hydrogen or C-C8 -alkyl, R1 , R0 2, R0 5 and R0 6 are each independently hydrogen or C-C8 -alkyl and R", R"3 , R"5and Rm6 are each independently hydrogen or C-C8 -alkyl.
In some embodiments, benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-mI or I m2, wherein YP, Yoand Y"'are oxygen, RPtogether with R 2p, R1 °together with R 20 and Rm together with R 2"'represent one of subformulae Ill, IV or V, R2 ptogether with RP, R2°together with R'°and R 2"'together with R" represent one of subformulae Ill, IV or V, R 4, R5 , R6 and Rare each independently hydrogen or C-C8 -alkyl, Rp2 , Rp3 , Rp5 and Rp 6 are each independently hydrogen or C-C8 -alkyl, R° 1, R02, R05 and R0 6are each independently hydrogen or C-C8-alkyl, R", R" 3 , R"'5and Rm6 are each independently hydrogen or CrC8 2 alkyl, R , R, Ra3 and Ra4 are each independently hydrogen or C-C 8 -alkyl, R, R ,Rb, R 4 ,
Rb 5and Rb 6are each independently hydrogen or C-C8 -alkyl and R°, R 2 , R 3 and R4 are each independently hydrogen or C-C8 -alkyl.
In certain embodiments, benzofuranones are of formula1-p1, 1-p2, 1-ol or I-o2, wherein YP and Yoare oxygen, RPtogether with R2Pand R1 °together with R 20 represent one of subformulae Ill, IV or V, R 2p together with R'P and R 2° together with R'° represent one of subformulae Ill, IV or V, R4 , R5 , R6 and R7 are each independently hydrogen or C-C8 -alkyl, Rp 2 , Rp3 , Rp5and Rp 6are each independently hydrogen or C-C8 -alkyl, R1 , R0 2, R0 5 and R0 6 are each independently hydrogen or C-C8 -alkyl, Ra, R, Ra 3 and Ra4 are each independently hydrogen or C-C8 -alkyl, Rb, Rb2, RbW, Rb4 , Rb and Rb6are each independently hydrogen or C-C8-alkyl and R°, R 2 , Rc3 and Rc4 are each independently hydrogen or CrC8 alkyl.
In some embodiments, benzofuranones are of formula 1-p1 or I-p2, wherein YP is oxygen, R1Ptogether with R 2P represent one of subformulae Ill, IV or V, R 4 , R5 , R6 and R7 are each independently hydrogen or C1 -C-alkyl, Rp 2, Rp3 , Rp 5 and Rp 6 are each independently hydrogen or C1 -C 8-alkyl, Ra 1, Raz, Ra 3 and Ra4 are each independently hydrogen or C1-C alkyl, Rbl, Rb2, Rb',3 Rb4 , R and Rb6are each independently hydrogen or C-C8 -alkyl and R°, R 2 , R 3and R4 are each independently hydrogen or C-C8 -alkyl.
In some embodiments in benzofuranone compounds of formulaI-p1 or I-p 2 , YP is oxygen, R1Ptogether with R 2P represent subformula IV, R 4, R5 , R6 and R7 are each independently hydrogen or C-C8 -alkyl, Rp2 , Rp3, Rp 5and Rp 6are each independently hydrogen or C-C8-alkyl and Rbl, Rb2, R 3, Rb4 , Rb5and R b 6are each independently hydrogen or C-C8 -alkyl.
In some embodiments, benzofuranones are selected from compounds of formula (101)-(133).
H 3C CH 3 CH 3 CH 3
H3C H 3C H 101 00 0
H3C H00 0 O \ H 3C H / CH 3 CH 3 H CH 3
H 3C H 3C CH 3 H3 C OH3 CH 3 H 3C
H 3C H H 3C H 2 C-LKj H3- CH 3 H3C CH 3 H
H 2C CH 3
H3 C H 7 102 0 00 0 0 H3C I 0 HCH2 C H0\ICH 3CH HCCH 3 /\ / H C3 H3 H3H 3C H CCH 3
H3C CH 3 CH 3 H2C CH2 HC H H 3C CH 3 HC -H H3C H 3C CH 3
H 3C 0 H3 H3 OH 3
0 H3C H 0 H H3
HCH o3 3~oH I /H CH 3
H 3C H3 10
H 3C OH 3
HH 3 C
H3H
H3 0 0 PO 3 H HCOH
( CH 3 H3
/H 1H4
H C
0 H 3OC4 H3
H3 0 OH3
OH3 H 30
H318
H3 C CH 3 H 3C CH 3
H3C OH 3C
H \0 CH3 106
CH3 CHC H3C CH3H 3C CH 3 H3C H
CHH3H0 H
H3 0 0 0 3 H H 3C OH 3
H3 C o-P H 3C 0 107
3CH
H3C OH0 3 H HCH 3 0 H3
KOH 3
H3C- OH 3
C3 H3 OH3 H3
H 3C CH 3 H 3C CH 3
\/ hH 0-P \ O H-OH 3 109
H3CH 3
OH 3 H3C ------ H 3C CH 3 H 3C H3 O.... OH3 H O1 -3 OH
CH3 H3 C CH 3
3C CH3 CH 3
0 \0 110
OH H3 C CH3 SH3 C CH H 3 3 CH3
O O---- CH -CH H3CH3C
OHHOH
HH 3 7 3 C H3
H3C0 H 3C 03 CH3 OH H3H3 CH3H CH3 CHCH CH3C H3CC H3 H3 OH PH
H3CC CH CH3H3C
CH 3 H 3C
H 3C OH 3 H 30 H2 0LI H3 0- CH 3 CH 3 H H 2C OH 3
H 3C H 7 112 0 H00 0 0 0 H3C 0 00 H 2C H3 O0
H3 C H OH 3 /\/ H 3C H2 H H 3
H 30 OH 3 H 3O OH 3 O3 H2 H2O CH H3 CH3 H 3CH O 3
OH 3 OH 3 H
H30 0 H3 H3 0 OH 3 H 30 0- OH
0 OH3 H
/ OH3 3 H3 0 H3 3 H
H0 OH3
HH 3 C
H3H
0
" H 3C P-0H3 H H0OH CH3 114 HH3
H3 CH C 0
3 C 0
0 0OH H3 C 0H OH3
H3C OH3 /\H 3 OH
HH3C. H
0 OH3 H H 33 H3 0
22 3CH
H3 C CH 3 H 3C CH 3
0H3C 11 CH 3
H3 H30H 3 C CH H0
3 H 00 HH3 11 ,~H OHHH0 H H3 0 H 3 0 3C H3 O3 H3
CH 3C
H3C 0 H3 C CH O3 H3 HOH 3
HH 3C OH3 HH H3
H3C OH3
H C 118 H3C H3 KOH 3 H3 H 3 O H3 H3 O
23C H 3 H
H 3C CH 3 H 3C CH 3 H3CH 3
H3C CH3 O CH3 O
H-C H3OH 3 H 3C ---- O......p\0 11 9 CH3 H3 C CH 3 H3CHCH3 H"0 OH H 30 CH 3 CH3 H3C CH3 H3C OH
H3 HH H3C H 3 3
H CH3 H 3C CH 3
3C CH3 H3 CH3H P12 3 H0 /\ C3H 0 00 3
CH3 H3C ..-- H3C ._~P 121 H3 O
H3H 3 H3 CHH 3
121- CH3 H3C CH3
H3C CH3 H3C CH3
H3C OH 3 00 H3 C /H H3 Op -- P P-0 0 \ 0 0 3 0
H 3 C0 0 H OH 3 H H 3C H3 H 3C OH 3 CH 3 122 H 3C - H3
H3C CH 3 H3 0 CH 3
0 H3 0 0 / x \pCH 3 H 3O O\H3 OH3 H \ 0 0 / H H3C
HC 3C OH 3 H3O OH 3 OH 3 123 H 3O
H3C HC lp\ P-CH 3
CH 3 H3 C -I
~0 0 H 3C o-LO CH 3 0 /\ 0 H 3C 0 H0 H 0 H3 O H3 ~ /H 3 C CH 3 H 3C C 3 15H H 3
H3 0 OH 3 HC CH 3
H 3C OH 3 00C 00
H 3C CH3
3O H3 0H 3DO0 0 \ 0 3 0 H0H 3 0 H3 OH 3 H3 CC
OH 3 OH 3 126 H 3O - H3
H3C OH 3 H3C CH 3
0 0
H 3O 0 00 0 0 0 OH 3 H 3C -p \p N /\ CH 3 CH 3 H \ 0 0/H H30
H3 O OH 3 H3C OH3 OH 3 127 H 3C
H3C 0 0\\ 0 0CH 3
HH 3C CH
C3C3 H HC 0P0 0OH H 0~H 3 H3 C~ C\O
, H3 C OH 3 19H 3 0 - OH C H H3 OH 3 HI OH3
H3 CH3 03- 0 0 H3 C C-o OH 3
OH3 0H0 /\Ppy 0 0 3 0 H O 3 HOH 3
0 H OH 3 OH3 13C 3 H3
H 30 O<H 3 H3 0 OH 3
H3C CH3 27
H 3C 0 0 00 0 CH 3 H 3C \/ CH 3 CH 3 H O O H H 3C
H 3C CH 3 H 3C CH 3 CH 3 131 H3 C
H3C O S0% O O CH 3 H3C -p P
H3C C3 H O O 0 H H3
H3 CH3C I CH3 H 3C CH3 H 3 H3C CH3 CH3 3 CH3 CH 3 132 H3C CH3 H3C OH CH3
H3C CH3 H3C
H3C
H3C CH3 H CH3 H3C CH3 CH3
H3C P-O0CH O CH3 CH3 CH3 CH3 H3C FCH3H3C13 H3C
The present benzofuranones may be prepared as disclosed in US2017/0226323, US2017/0066905 and U.S. app. No. 15/751497, published as W02017/025431.
Organophosphorus stabilizers include organic phosphite and organic phosphonite stabilizers and include for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris-(2-sec-butylphenyl) phosphite (0), distearyl pentaerythritol diphosphite (F), bis(2,4-di-a-cumylphenyl) pentaerythrtitol diphosphite (K), diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (D), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (E), bisisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite (H), 6-isooctyloxy-2,4,8,10 tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin (C), 6-fluoro-2,4,8,10-tetra-tert-butyl-12 methyl-dibenzo[d,g][1,3,2]dioxaphosphocin (A), bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (G), 2,2',2" nitrilo[triethyltris(3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] (B), bis(2,4-di-t butylphenyl) octylphosphite, poly(4,4'-{2,2'-dimethyl-5,5'-di-t-butylphenylsulfide }octylphosphite), poly(4,4'{-isopropylidenediphenol}-octylphosphite), poly(4,4' {isopropylidenebis[2,6-dibromophenol]}-octylphosphite), poly(4,4'- {2,2'-dimethyl-5,5'-di-t butylphenylsulfide}-pentaerythrityl diphosphite), phosphorous acid, mixed 2,4-bis(1,1 dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS No. 939402-02-5), phosphorous acid, triphenyl ester, polymer with alpha-hydro-omega-hydroxypoly[oxy(methyl 1,2-ethanediyl)], C 10-1 alkyl esters (CAS No. 1227937-46-3),
(CH3) 3 C C(CH 3)3 (CH 3) 3C C(CH 3)3
0 0 (A) H C-CH P-F P-0-CH 2CH2 - -N o - 0
C(OH 3 3) (CH 3)30C (H 3 )3 C (CH3) C(CH 3)3 3 (B)
(CH 3)3c O(0H 3)3
~0 (C) P-O-0H 2 C( 4H9)0H 20CH 3 - 0
O(0H 3)3
(CH ) 30 / 0 / P-0-- OC(H 3)3 (D) 3-Q 0 )c0
O(0H 3)3 (C0 3C
O(0H 3)3 (C0 3C 0 \0 HO /-P D o-\)~P-o 3 (E) CH O 3-0 0 0 O(0H 3)3 (CH 3)3C
OH 3
H 3 C--P P--C HH 3 0-0-OH 3 H (F 7 18 18 37 0OO 2 0 OH3
(G)
KCH 330 (0 2 3) LO- 7C)- O(OH 3
fO2 (OHJ (H)
O(OH 3)3
(H 3)3C /- :)~KZ(C23 J 0 O 2OH 3 O(OH3)3
0 \-0 O 3 - OH 3 0 O-P\X P-0 0 OH 3 OH 3 (K) O(OH 3)2 (CH 0 2C
(CH 3 C O(OH 3)3
0 OH 2 /P-O- 8 H 17 (L 0
0 (OH3)3 (CH 3)3C
0
nI 0
n= 1-5
P-O OH (N)
and
0
0 0 (0)
In some embodiments, a combination of one or more organophosphorus stabilizers may be employed.
In certain embodiments, the organophosphorus stabilizer is selected from the group consisting of tris-nonylphenyl phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3'5,5'-tetra-tert butyl-1,1'-biphenyl-2,2'-diyl) phosphite], bis(2,4-di-a-cumylphenyl) pentaerythrtitol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite and combinations thereof.
The amount of benzofuranone stabilizers employed may range from any of about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about 80 ppm, about 90 ppm, about 100 ppm, about 110 ppm, about 120 ppm, about 130 ppm, about 140 ppm, about 150 ppm, about 160 ppm, about 170 ppm, about 180 ppm, about 190 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm or about 500 ppm to any of about 550 ppm, about 600 ppm, about 650 ppm, about 700 ppm, about 750 ppm, about 800 ppm, about 850 ppm, about 900 ppm, about 950 ppm, about 1000 ppm, about 1050 ppm, about 1100 ppm, about 1150 ppm, about 1200 ppm, about 1250 ppm, about 1300 ppm, about 1350 ppm or about 1400 ppm, by weight, based on the weight of the polyolefin.
In other embodiments, the amount of present benzofuranone stabilizers employed may range from any of about 0.05 wt% (weight percent), about 0.07 wt%, about 0.09 wt%, about 0.10 wt%, about 0.15 wt%, about 0.20 wt%, about 0.25 wt%, about 0.30 wt%, about 0.35 wt%, about 0.40 wt%, about 0.50 wt%, about 0.60 wt%, about 0.65 wt%, about 0.70 wt%, about 0.75 wt%, about 0.80 wt%, about 0.90 wt%, about 1.0 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt% or about 5.5 wt% to any of about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, about 7.5 wt%, about 8.0 wt%, about 8.5 wt%, about 9.0 wt%, about 9.5 wt% or about 10.0 wt%, based on the weight of the polyolefin.
In other embodiments, the amount of present benzofuranone stabilizers may range from any of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about wt% or about 30 wt% to any of about 35 wt%, about 40 wt%, about 45 wt% or about 50 wt%, based on the weight of the polyolefin.
The amount of organophosphorus stabilizers employed may range from any of about ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about ppm, about 90 ppm, about 100 ppm, about 110 ppm, about 120 ppm, about 130 ppm, about 140 ppm, about 150 ppm, about 160 ppm, about 170 ppm, about 180 ppm, about 190 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm or about 500 ppm to any of about 550 ppm, about 600 ppm, about 650 ppm, about 700 ppm, about 750 ppm, about 800 ppm, about 850 ppm, about 900 ppm, about 950 ppm, about 1000 ppm, about 1050 ppm, about 1100 ppm, about 1150 ppm, about 1200 ppm, about 1250 ppm, about 1300 ppm, about 1350 ppm or about 1400 ppm, by weight, based on the weight of the polyolefin.
In other embodiments, the amount of organophosphorus stabilizers employed may range from any of about 0.05 wt% (weight percent), about 0.07 wt%, about 0.09 wt%, about 0.10 wt%, about 0.15 wt%, about 0.20 wt%, about 0.35 wt%, about 0.50 wt%, about 0.75 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1.0 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt% or about 5.5 wt% to any of about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, about 7.5 wt%, about 8.0 wt%, about 8.5 wt%, about 9.0 wt%, about 9.5 wt% or about 10.0 wt%, based on the weight of the polyolefin.
In some embodiments, one or more benzofuranones and one or more organophosphorus stabilizers may be employed in a weight/weight ratio of from any one of about1/99, about1/90, about1/80, about1/70, about1/60, about1/50, about1/40, about 1/30, about1/20, about1/10, about1/9, about1/8, about1/7, about 1/6, about1/5, about 1/4, about 1/3, about 1/2 or about 1/1 to any one of about 2/1, about 3/1, about 4/1, about /1, about 6/1, about 7/1, about 8/1, about 9/1, about 10/1, about 20/1, about 30/1, about /1, about 50/1, about 60/1, about 70/1, about 80/1, about 90/1 or about 99/1.
In some embodiments, organophosphorus stabilizers are employed at equal or higher weight levels than the one or more benzofuranones. For example, in some embodiments, the weight/weight ratio of the one or more benzofuranones to one or more organophosphorus stabilizers may be from any one of about 0.05, about 0.10, about 0.15, about 0.20, about 0.25, about 0.30, about 0.35, about 0.40, about 0.45 or about 0.50 to any one of about 0.55, about 0.60, about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.90, about 0.95 or about 1.0.
Also disclosed are additive compositions comprising the one or more benzofuranone compounds and the one or more organophosphorus stabilizers. The weight/weight ratio of the benzofuranones to the organophosphorus stabilizers may be as above.
In some embodiments, the compositions may further comprise one more additional additives selected from the group consisting of antioxidants, ultraviolet light absorbers, hindered amine light stabilizers, acid scavengers, metal deactivators, hydroxylamines, nitrones, amine N-oxides, thiosynergists, peroxide scavengers, nucleating agents, fillers, flame retardants and antistatic agents.
In some embodiments, additional additives may include plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow-control agents, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, antistatic agents or clarifiers such as substituted and unsubstituted bisbenzylidene sorbitols.
Additional additives, individually or collectively, may range from any of about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about 80 ppm, about 90 ppm, about 100 ppm, about 110 ppm, about 120 ppm, about 130 ppm, about 140 ppm, about 150 ppm, about 160 ppm, about 170 ppm, about 180 ppm, about 190 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm or about 500 ppm to any of about 550 ppm, about 600 ppm, about 650 ppm, about 700 ppm, about 750 ppm, about 800 ppm, about 850 ppm, about 900 ppm, about 950 ppm, about 1000 ppm, about 1050 ppm, about 1100 ppm, about 1150 ppm, about 1200 ppm, about 1250 ppm, about 1300 ppm, about 1350 ppm or about 1400 ppm, by weight, based on the weight of the polyolefin.
In other embodiments, additional additives, individually or collectively, may be employed from any of about 0.05 wt% (weight percent), about 0.07 wt%, about 0.09 wt%, about 0.10 wt%, about 0.15 wt%, about 0.20 wt%, about 0.35 wt%, about 0.50 wt%, about 0.75 wt%, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1.0 wt%, about 1.3 wt%, about 1.5 wt%, about 1.7 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt% or about 5.5 wt% to any of about 5.5 wt%, about 6.0 wt%, about 6.5 wt%, about 7.0 wt%, about 7.5 wt%, about 8.0 wt%, about 8.5 wt%, about 9.0 wt%, about 9.5 wt% or about 10.0 wt%, based on the weight of the polyolefin.
Hindered amine light stabilizers are, in some embodiments, compounds containing one or more moieties of formula
R1 R2
N-R
R3 R4
wherein R 1, R 2, R 3 and R 4 are independently methyl or ethyl and wherein R is H, methyl, hydroxy, propoxy, octyloxy, cyclohexyloxy, acyloxy or N-(2-hydroxy-2-methylpropoxy).
Suitable hindered amine light stabilizers are for example:
(1) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, (2) bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (3) bis(1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (4) bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, (5) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (6) bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (7) bis(1-acyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (8) bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4 hydroxybenzylmalonate (9) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethyl amino-s-triazine, (10) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, (11) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine, (12) 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, (13) 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, (14) 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, (15) bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (16) bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate, (17) 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butyl amino} 6-(2-hydroxyethylamino)-s-triazine, (18) 4-benzoyl-2,2,6,6-tetramethylpiperidine, (19) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate, (20) 2,2,6,6-tetramethylpiperidin-4-yI octadecanoate, (21) bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, (22) 1,2,2,6,6-pentamethyl-4-aminopiperidine, (23) 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, (24) tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, (25) tris(2-hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidin-4-yl)propyl) nitrilotriacetate, (26) tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (27) tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, (28) 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), (29) 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione, (30) 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, (31) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, (32) 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
(33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, (33a) bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, (34) reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro s triazine with N,N'-bis(3-aminopropyl)ethylenediamine), (35) condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, (36) condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4 tert octylamino-2,6-dichloro-1,3,5-triazine, (37) condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4 cyclohexylamino-2,6-dichloro-1,3,5-triazine, (38) condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4 morpholino-2,6-dichloro-1,3,5-triazine, (39) condensate of N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4 morpholino-2,6-dichloro-1,3,5-triazine, (40) condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5 triazine and 1,2-bis(3-aminopropylamino)ethane, (41) condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5 triazine and 1,2-bis-(3-aminopropylamino)ethane, (42) a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro
[4,5]decane and epichlorohydrin, (43) poly[methyl,(3-oxy-(2,2,6,6-tetramethylpiperidin-4-yl)propyl)] siloxane, CAS#182635 99-0, (44) reaction product of maleic acid anhydride-Cl8 -C 22-a-olefin-copolymer with 2,2,6,6 tetramethyl-4-aminopiperidine, (45) oligomeric condensate of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2 chloro-4,6-bis(dibutylamino)-s-triazine, (46) oligomeric condensate of 4,4'-hexamethylenebis(amino-1,2,2,6,6-pentaamethyl piperidine) and 2,4-dichloro-6-[(1,2,2,6,6-pentaamethylpiperidin-4-yl)butylamino]-s-triazine end capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine, (47) oligomeric condensate of 4,4'-hexamethylenebis(amino-1-propoxy-2,2,6,6-tetramethyl piperidine) and 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino] s triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine, (48) oligomeric condensate of 4,4'-hexamethylenebis(amino-1-acyloxy-2,2,6,6-tetramethyl piperidine) and 2,4-dichloro-6-[(1-acyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino] s triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine, (49) product obtained by reacting (a) with (b) where (a) is product obtained by reacting 1,2 bis(3-aminopropylamino)ethane with cyanuric chloride and (b) is (2,2,6,6-tetramethyl piperidin-4-yl)butylamine, (50) (4-piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy))-, 4,4'-carbonate and (51) 1,3,5-triazine-2,4,6-triamine, N2,N2'-1,6-hexanediylbis[N4,N6-dibutyl-N2,N4,N6 tris(2,2,6,6-tetramethyl-4-piperidinyl)-, N-propoxy.
Also included are the sterically hindered N-H, N-methyl, N-methoxy,N-hydroxy, N propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N-(2-hydroxy-2-methylpropoxy) analogues of any of the above mentioned compounds. For example, replacing an N-H hindered amine with an N-methyl hindered amine would be employing the N-methyl analogue in place of the N-H.
For illustrative purposes, some of the structures for the above-named compounds are shown below.
CH CH3 HO 3 0 0 CH 3
(6) H00sO-N 0-C-(CH 2 )8-O-O N-OC8H1
H C CH 3 CH 3 CH3
( 3) 3C n-0 4H9 0 OH 3 HO 0 (8) HO -O N-OH 3 (C\3 H2 OH 3
HN-0H 2 20
NJI N n-O4H N N -N n-O4H9
H30 OH3 HOC O;H3 ()H 30 I OH 3 H3 0 I OH 3 0 0
HO3c
(12) HO s 0 -N OH
O HC CH3 O N-CH3
H3 0 CH (19) CH30 __ HC
N OH O0 HO
0 NH (23) HN 0
O HC CH 3
(25) NR NR R= NH
O "NR O N N3COH )
OH H 3C
(26) R R RNH
0 OH 3 H 3C
(28) HN N N H
0
(29) HN N H O
0
(31) HN N
0
0 0 H N- (CH 2)6 N H
(33)
N N H H
(34)
R R N N HN N N 4 HA-N N NCH
I I H KR
0
-0N
N N -(CH 2)6 N
-N (36) NN-H IN
H H
N-(CH 2 )6 N N .N (38)
N N H H0 n
(41) R
RH Ny~ N II
N N H kR
N NOH
HO 0
N (42) N
n
CH3
(43) 0
N H n
(44)
N 0
H
(45) H
N II H
N N fN
N >- N- N N ~ N -( N N NN
N 4N INN N HH
H nl
(49)
R' N (CH 2)2 -N N C4 Hq
(CH 2)3 II N (CH 2)3 N N
NHR' HR' -C, H9 4 9 N H 4N
H n
where R= R" or H N n = 2or 3 H9C4 I CAH N N N and where R" =A NN
H H o N (CH2) 10 CH 3
0 0 (50)
N
(CH2)10CH3
(51) N1OC3H7
N N N
C3H-70*1N N NNr
N NNN N N N NN
OC 3 H 7 C 3 H70N
In certain embodiments, the compositions may further comprise hindered phenolic antioxidants such as -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters, for instance esters of mono- or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i octanol, a mixture of linear and branched C-C9 -alkanol, octadecanol, a mixture of linear and branched C 13-C 1 -alkanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, glycerol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxylethyl)isocyanurate, N,N'-bis-(hydroxyl-ethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
In other embodiments, hindered phenolic antioxidants include tris(3,5-di-tert-butyl-4 hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6 trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4 hydroxybenzylphosphonic acid, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di tert-butyl-4-hydroxyphenyl) propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4 hydroxyhydrocinnamamide), 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5 triazine-2,4,6-(1H,3H,5H)-trione, 2,2'-methylenebis(4-methyl-6-tert-butylphenol)monoacrylate or alpha-tocopherol.
In some embodiments, the compositions comprise essentially no or no hindered phenolic antioxidants. Essentially no means not purposefully added and wherein only inadvertent or trace amounts may be present, for instance s 500 ppm (parts per million), s 400ppm,5300ppm,5200ppm,5150ppm,5100ppm,575ppm,550ppm,525ppms ppm, s 15 ppm, s 10 ppm, 5 5 ppm, s 4 ppm, s 3 ppm, s 2 ppm or s 1 ppm, by weight, based on the weight of the polyolefin.
Thiosynergists include for example dilauryl thiodipropionate or distearyl thiodipropionate.
Acid scavengers include hydrotalcites and amorphous basic aluminum magnesium carbonates, such as those described in U.S. Pat. Nos. 4,427,816, 5,106,898 and 5,234,981. Hydrotalcite is also known as hycite, DHT4A, DHT4V, DHT4Z, DHT4A2 or DHT4C. Hydrotalcites are natural or synthetic and may include a coating. Natural hydrotalcite is held to possess a structure Mg 6 AI 2(OH) 1 6CO 3 .4 H 20. A typical empirical formula of a synthetic hydrotalcite is A1 2Mg 4 . 3 5OH 11 . 3CO 6 3(1 . 6 7 ).x H20. Examples of the synthetic product include Mg o0 7Alo.3(OH) 2(CO 3) 0 15.0.54 H 20, Mg 45 Al 2(OH)13CO3.3.5 H 20 andMg 42Al(OH)12.4CO3.
In some embodiments, acid scavengers include metal salts of fatty acids, for example alkali or alkali earth metal salts of fatty acids. In some embodiments, acid scavengers include calcium, magnesium, zinc, sodium, potassium or aluminum salts of fatty acids. In some embodiments, acid scavengers include calcium, magnesium, zinc, sodium, potassium or aluminum stearate, behenate, ricinoleate or palmitate. In certain embodiments, acid scavengers include calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate. In other embodiments, acid scavengers include zinc oxide.
In some embodiments, a combination of one or more acid scavengers may be employed.
Ultraviolet (UV) light absorbers may be selected from the group consisting of hydroxyphenylbenzotriazole, tris-aryl-s-triazine, hydroxybenzoate, 2-hydroxybenzophenone and cyanoacrylate ultraviolet light absorbers (UVAs).
Hydroxyphenylbenzotriazole UVAs may include those disclosed in U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586;4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905,4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; ,410,071; 5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987, ,977,219 and 6,166,218, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl) 2H-benzotriazole, 5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3 sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)-2H benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3,5-bis-a-cumyl-2 hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-(o-hydroxy-octa (ethyleneoxy)carbonyl-ethyl)-, phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5 methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl) 2H-benzotriazole, dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl 2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2 (2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2 hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-t-butyl-2 hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-t-buty-5-(2-(2 ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-(2 isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2'-methylene-bis(4-t-octyl-(6-2H benzotriazol-2-yl)phenol), 2-(2-hydroxy-3-a-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(2 hydroxy-3-t-octyl-5-a-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-a-cumyl phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole, 5 chloro-2-(2-hydroxy-3-a-cumyl-5-t-octylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5
(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2 hydroxy-3-a-cumyl-5-t-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-t octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzo triazole, methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxy hydrocinnamate, 5-butylsulfonyl-2-(2-hydroxy-3-a-cumyl-5-t-octylphenyl)-2H-benzotriazole, -trifluoromethyl-2-(2-hydroxy-3-a-cumyl-5-t-butylphenyl)-2H-benzotriazole, 5 trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2 hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butyl phenyl)-2H-benzotriazole and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H benzotriazole.
Tris-aryl-s-triazine UVAs may include those disclosed in U. S. Pat. Nos. 3,843,371; 4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414; 5,354,794; ,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973; 5,597,854; 5,681,955; ,726,309; 5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704; 6,060,543; 6,242,598 and 6,255,483, and US published application nos. 2015/329684 and 2017/327475, for example 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, dodecanedioic acid, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl] ester, 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine, CYASORB 1164, 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4 dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy) phenyl]-6-(4-bromophenyl)-s-triazine, 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4 chlorophenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine, 2,4 bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine, 2-phenyl 4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy 2-hydroxypropyloxy)phenyl]-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3 benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine, 2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6 (2,4-di-n-butyloxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy* 2-hydroxypropyloxy)-5-a-cumylphenyl]-s-triazine (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups), methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy 2-hydroxypropoxy)phenyl]-s-triazine}, methylene bridged dimer mixture bridged in the 3:5', :5' and 3:3' positions in a 5:4:1 ratio, 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso propylideneoxyphenyl)-s-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-a cumylphenyl)-s-triazine, 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxy propyloxy)phenyl]-s-triazine, 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy) phenyl]-s-triazine, mixture of 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2 hydroxypropoxy)-phenyl)-s-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3 tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine, TINUVIN 400, 4,6-bis-(2,4-dimethyl phenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine and 4,6 diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.
Hydroxybenzoate UV absorbers may include for instance esters of substituted and unsubstituted benzoic acids, as for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2-Hydroxybenzophenone UV absorbers include for example the 4-hydroxy, 4 methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2' hydroxy-4,4'-dimethoxy derivatives.
Cyanoacrylate UV absorbers include for instance pentaerythritol tetrakis(2-cyano-3,3 diphenylacrylate), a-cyano-P,P-diphenylacrylic acid ethyl ester or isooctyl ester and a-cyano P-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester.
In some embodiments, the UVA may include 5-chloro-2-(3-t-butyl-2-hydroxy-5 methylphenyl)-2H-benzotriazole, 2-(3,5-bis-a-cumyl-2-hydroxyphenyl)-2H-benzotriazole, 4,6 diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine, 4,6-bis-(2,4-dimethylphenyl)-2-(2 hydroxy-4-octyloxyphenyl)-s-triazine, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or 4 octyloxy-2-hydroxybenzophenone.
Many of the UVAs are commercial, for example TINUVIN 326, TINUVIN 234, TINUVIN 1577, TINUVIN 1600, CYASORB UV 1164, CYASORB THT, CYASORB UV 2908, CHIMASSORB 81, UVINUL 3030, ADK LA-F70, ADK LA-1000, TINUVIN 400, etc.
Hydroxylamine stabilizers may include for example N,N-dibenzylhydroxylamine, N,N diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N heptadecyhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N octadecyihydroxylamine, N-methyl-N-octadecylhydroxylamine or, in certain embodiments, N,N-di(C16-C 18alkyl)hydroxylamine.
In certain embodiments, the polyolefin comprises polyethylene (PE) homopolymers, polyethylene random or block copolymers, polypropylene (PP) homopolymers, polypropylene random or block copolymers, ethylene/propylene copolymers, a mixture of polypropylene and polyethylene or a mixture of different types of polyethylene. In certain embodiments, the polyolefin is polypropylene. In some embodiments, polyethylene is linear low density (LLDPE), low density (LDPE), medium density (MDPE) or high density (HDPE). Mixtures mentioned above are for example PP/HDPE, PP/LDPE and LDPE/HDPE. Also included are ternary mixtures such as PP/HDPE/LLDPE. The polyolefins may be formulated with or without crosslinking.
The polyolefin composition contains for instance 2 about 10 weight percent (wt%) polyolefin, for instance 2 about 15 wt%, 2 about 20 wt%, 2 about 25 wt%, 2 about 30 wt%, 2 about 35 wt%, 2 about 40 wt%, 2 about 45 wt%, 2 about 50 wt%, 2 about 55 wt%, 2 about wt%, 2 about 65 wt%, 2 about 70 wt%, 2 about 75 wt%, 2 about 80 wt% or 2 about 85 wt% polyolefin, based on the weight of the composition.
Polypropylene may be a polypropylene homopolymer, a polypropylene random copolymer, alternating or segmented copolymer or block copolymer containing one or more comonomers selected from the group consisting of ethylene, C 4-C30 -a-olefins, vinylcyclohexane, vinylcyclohexene, C 4-C20alkandienes, C5 -C 12 cycloalkandienes and norbornene derivatives; the total mol amount of propylene and the comonomer(s) being 100%.
Polypropylene copolymer also covers long chain branched polypropylene copolymer.
Examples of suitableC 4-C 30o-olefins are 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1-eicosene, 4-methyl-1-pentene, 1-eicosene, 1-docosene, 1-tetracosene, 1 hexacosene, 1-octacosene and 1-triacontene.
Examples of suitableC 4-C 20alkandienes include hexadiene and octadiene. Examples of suitable C-C1 2cycloalkandienes include cyclopentadiene, cyclohexadiene and cyclooctadiene. Examples of suitable norbornene derivatives include 5-ethylidene-2 norbornene (ENB), dicyclopentadiene (DCP) and methylene-domethylene hexahydronaphthaline (MEN).
A propylene/ethylene copolymer contains for example about 50% to about 99.9%, in some embodiments about 80% to about 99.9% and in other embodiments about 90% to about 99.9% by weight of propylene.
A propylene copolymer wherein the comonomer is aC9 -C 20o-olefin such as e.g. 1 nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene; C-C20 alkandiene, C 9-Cl 2 cycloalkandiene or a norbornene derivative such as e.g. 5-ethylidene-2-norbornene (ENB) or methylene-domethylene-hexahydronaphthaline (MEN) may contain more than about 90 mol%, from about 90 mol% to about 99.9 mol% or from about 90 mol% to about 99 mol% propylene.
A propylene copolymer wherein the comonomer is aC 4 -C 8a-olefin such as e.g. 1 butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or 4-methyl-1-pentene; vinylcyclohexane, vinylcyclohexene, C 4-Calkandiene orC 5-Ccycloalkandiene may contain more than 80 mol%, from about 80 to about 99.9 mol% or from about 80 mol% to about 99 mol% propylene.
Further examples of polypropylene are propylene/isobutylene copolymer, propylene/butadiene copolymer, propylene/cycloolefin copolymer, terpolymers of propylene with ethylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; propylene/1-olefin copolymers where the 1-olefin is generated in situ; and propylene/carbon monoxide copolymers.
Allyl or vinyl terminated oligomers of ethylene or propylene may be employed as branches in polymerization reactions with propylene to prepare branched polypropylenes of high melt strength as disclosed in U.S. Pat. No. 8,399,725 and U.S. Pub. Nos. 2013/0274425, 2013/0274425, 2013/0030135 and 2013/0137829.
Polypropylene's linear chain structure results in the polymer exhibiting low melt strength and a lack of strain hardening. This can result in processing issues where polymer extensibility is needed. In contrast, polypropylenes exhibiting high melt strength are valued in industrial converting operations such as blow molding, thermoforming or foaming of polypropylene sheet. Polypropylene based compositions of this invention exhibit acceptable melt strength, extensibility and strain hardening to produce extruded profiles and siding.
Advantageously, the polyolefin comprises a polypropylene homopolymer or copolymer of a suitably high melt strength, optionally blended with a polyethylene homopolymer or copolymer. The blend may further contain a third polymer suitable to facilitate compatibility, partial miscibility or miscibility of the different polyolefins. Such materials are referred to as interfacial tension reducing agents or compatibilizers.
Suitable compatibilizers are typically polymers that contain two or more different segments each of which are miscible or compatible with the individual components to be blended. A compatibilized polymer blend need not be fully miscible nor satisfy all thermodynamics of mixing (e.g. resulting in a single phase, or single glass transition temperature), yet such a blend of different polymer structures will exhibit improved resultant properties over the individual components.
One type of compatibilizer for blending of PP and PE are segmented "olefin block copolymers" or "OBC", containing propylene, ethylene and optionally additional alpha-olefin sequences such as those produced by Dow Global Technologies and taught in U.S. Pub. Nos. 2011/032621, 2011/060103, 2010/298515, 2011/054121 and 2011/015354. Included are Dow products under the trade name INFUSE and ExxonMobil VISTAMAXX products. These block copolymers are produced with an overall molecular weight distribution and segment molecular weight distribution such that Mw/Mn > 1.4, with two or more ethylene and alpha-olefin blocks per chain and low molecular weights (Mw < 200,000 g/mol). These alternating block copolymers are characterized by crystallizable, rigid 'hard block' segments and an amorphous, elastomeric 'soft block' content. The hard block content ranges from 12-84 wt.% in these OBCs and total 1-octene content (i.e. conferring long chain branches) range from 3 to 14 wt.%. OBCs may compatibilize a blend of PP and HDPE where an increase in elongation to break and tensile strength can be achieved compared to a non compatibilized blend of HDPE and PP.
The polypropylene homopolymer or copolymer or blend with polyethylene optionally compatibilized may be chemically crosslinked to introduce long chain branches (LCB) off of the polypropylene main chain resulting in higher melt strength and extensibility and lower melt flow than is generally commercially available.
Chemical crosslinking of a polypropylene homopolymer or copolymer with another polypropylene or with a polyethylene homo- or copolymer and/or with a compatibilizing material is advantageous. Such crosslinking processes may impart a valuable increase in polyolefin blend melt strength, melt extensibility, mechanical and tensile strength useful in the present extrusion processes. Such crosslinking processes onto polypropylene may produce long chain branching (LCB) on the polypropylene main chain and create an enhanced amount of polymer chain entanglements that results in higher polymer melt strength.
Crosslinking may be accomplished with agents such as organic peroxides or by treatment with a radiation source such as ultraviolet light, electron beam or gamma irradiation. Radiation may be accomplished in a reduced oxygen or zero oxygen environment. For instance, a polypropylene of high melt strength and melt extensibility is obtainable by the blending of a linear polypropylene with a branched polypropylene (b-PP) in an extruder. The b-PP is prepared by reacting a peroxide with an unmodified polypropylene and optionally a bifunctional unsaturated monomer capable of grafting onto the unmodified polypropylene to produce long chain branches, US2015175789. In another example, U.S. Pat. Nos. 5,508,318, 5,731,362, 5,591,785, 5,554,668 and 4,916,198 disclose compounding of blends of irradiated and non-irradiated olefin polymer materials suitable for extrusion.
In contrast to downstream extrusion or polymer chemical modification to form crosslinks or long chain branches to improve melt strength, the formation of long chain branching on polyolefins may be conducted upstream during polymer manufacture. In an example, polyethylene may be modified in a polymerization unit via exposure to a low level of oxygen, called 'oxygen tailoring', resulting in formation of long chain branching and enhanced melt strength, as taught in U.S. Pub. No. 2012/100357.
The polyolefin may contain an additive that promotes a higher level of crystallinity upon melt converting the polymer into shaped articles. Such additives are referred to as nucleating agents.
The degree of crystallinity in polypropylene is an important parameter influencing properties such as modulus, yield stress, strength, etc. Within the scope of this invention is the use of nucleating agents which influence the favorable formation of a degree of crystallinity that improves polymer melt strength during extrusion processing and improvement of mechanical properties in the end use article. Suitable nucleating agents are for instance sodium benzoate, 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate, zinc glycerolate, calcium salt of 1,2-dicarboxylic acid cyclohexane, aromatic trisamide compounds, cis-endo-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium salt, aluminum hydroxy-bis[4-(tert-butyl)benzoate] and sorbitols such as 1,3:2,4-bis(3,4-dimethyl benzylidene)sorbitol 1,3:2,4-bis(4-methylbenzylidene)sorbitol or 1,3:2,4-bis(3,4 dimethylbenzylidene)sorbitol, as taught in U.S. Pat. Nos. 7,423,088, 7,790,793 and 8,183,312 and U.S. Pub. No. 2012/0190797.
Nucleating agents may be present for instance from about 10 parts per million (ppm) to about 10,000 ppm, from about 12 ppm to about 1,000 ppm, from about 12 ppm to about 500 ppm or from about 12 ppm to about 300 ppm or about 400 ppm, by weight based on the weight of the polyolefin.
The polyolefin advantageously contains an inorganic (mineral) filler to balance melt strength and extensibility or drawability to allow extrusion production of profiles and siding. Fillers are described in more detail below.
The polyolefin comprising a polypropylene homopolymer or copolymer optionally blended with a polyethylene homopolymer or copolymer, where the blend may further contain a compatibilizer may exhibit a high melt strength. Melt strength for the polyolefin may be at least about 4 centiNewtons (cN) at 210°C. For instance, the melt strength of the polyolefin is about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about13, about14, about15, about16, about17, about18, about19, about 20, about 21, about 22, about 23 about 24 or about 25 centiNewtons at 210°C. For instance the melt strength is 2 about 5, 2 about 7, 2 about 9, 2 about 11, 2 about 13, 2 about 15, 2 about 17, 2 about 19, 2 about 21 or 2 about 23 centiNewtons at 210°C.
Polyolefins can be prepared by the following methods:
a) radical polymerization (normally under high pressure and at elevated temperature) or
b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups lVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either - or a-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(Ill) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or IlIla of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
Polypropylenes are produced by processes as described in literature including Kissin, Y. V. (2008), Alkene Polymerization Reactions with Transition Metal Catalysts, Elsevier, pp. 207-. ISBN 978-0-444-53215-2; Hoff, Ray and Mathers, Robert T. (2010), Handbook of Transition Metal Polymerization Catalysts, John Wiley & Sons, pp. 158- ISBN 978-0-470-13798-7; Moore, E. P. (1996) Polypropylene Handbook, Polymerization, Characterization, Properties, Processing, Applications, Hanser Publishers: New York, ISBN 1569902089; Benedikt, G. M. and Goodall, B. L. (eds.) (1998) Metallocene Catalyzed Polymers, ChemTech Publishing: Toronto, ISBN 978-1-884207-59-4; Malpass, D.B., Introduction to Industrial Polyethylene, Properties, Catalysts, Processes, Wiley Publ., (2010); and Malpass, D.B., Introduction to Industrial Polypropylene, Properties, Catalysts, Processes, Wiley Publ., (2012).
In some embodiments, polyolefins include virgin polyolefin, polyolefin recyclates or mixtures thereof. Polyolefin recyclates may be obtained from domestic, commercial or industrial waste or from useful material collections. Recyclates may originate from packaging materials, for example, films, bags, bottles and other containers or foams. It is also possible for polyolefins which have been previously damaged by use, storage or processing to be stabilized. These materials originate, for example, from useful material collections or return obligations, for example from the automobile industry, electrical/electronic industry, construction, agriculture or the textile industry.
The incorporation of the present benzofuranones and organophosphorus stabilizers into a polyolefin is carried out by known methods, for example before or after molding or also by applying a dissolved or dispersed additive mixture to the polyolefin, with or without subsequent evaporation of the solvent. Present benzofuranones and organophosphorus stabilizers can also be added to a polyolefin in the form of a masterbatch which contains the additives in a concentration of, for example, about 2% to about 40% by weight, based on the total weight of the masterbatch. In the form of a masterbatch, the polymer of the masterbatch need not be the same as the polyolefin. Molding may be carried out with known mixing machines, for instance mixers, kneaders or extruders.
Present benzofuranones and organophosphorus stabilizers can be premixed or added individually. Present benzofuranones and organophosphorus stabilizers can also be added before or during the polymerization or before crosslinking. Present benzofuranones and organophosphorus stabilizers can be incorporated into a polyolefin in pure form or encapsulated in waxes, oils or polymers.
Present benzofuranones and organophosphorus stabilizers can also be sprayed onto a polyolefin. They are able to dilute other additives or their melts so that they may be sprayed also together with these additives onto a polyolefin.
In certain embodiments, the present benzofuranone additives and organophosphorus stabilizers are incorporated into a polyolefin by melt blending in an extruder. The present benzofuranones and organophosphorus stabilizers may be added together or separately.
In some embodiments, a process of preparing a polyolefin composition includes measurement of raw materials by weight followed by the dry blending of raw ingredients. The mixture may be fed to a screw extruder at a constant feed rate to extrude the material into a desired form, followed by water cooling and drying.
Also subject of the invention are articles, e.g. shaped articles, comprising the present polyolefin compositions. Examples of shaped articles include and are not limited to those listed in items 1-1) through IIV-8).
1-1) Floating devices, marine applications, pontoons, buoys, plastic or composite lumber for decks or piers, boats, kayaks, oars and beach reinforcements.
1-2) Automotive applications, interior applications, exterior applications, for example bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank, body side moldings, convertible tops, exterior mirrors, exterior trim, fasteners/fixings, front end module, glass, hinges, lock systems, luggage/roof racks, pressed/stamped parts, seals, side impact protection, sound deadener/insulator and sunroof.
1-3) Road traffic devices, for instance sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
1-4) Devices for plane, railway, motor car (car, motorbike, trucks) including furnishings.
1-5) Devices for space applications, for example rockets and satellites, e.g. reentry shields.
1-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges and shelters.
I-1) Appliances, cases and coverings in general and electric/electronic devices (personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl and panel devices.
11-2) Jacketing for other materials such as steel or textiles.
11-3) Devices for the electronic industry, for example insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards and materials for electronic data storage such as chips, check cards or credit cards.
11-4) Electric appliances, for example washing machines, tumblers, ovens (microwave oven), dish-washers, mixers and irons.
11-5) Covers for lights (e.g. street-lights, lamp-shades).
11-6) Applications in wire and cable (semi-conductor, insulation and cable-jacketing).
11-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines and vacuum cleaners.
Ill-1) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles and knobs.
111-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swimming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves and conveyor belts.
111-3) Sanitary articles, for instance shower cubicles, lavatory seats, covers and sinks.
111-4) Hygienic articles, for example diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes and bed pans.
111-5) Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes and drainage systems.
111-6) Profiles of any geometry (window panes) and siding.
111-7) Glass substitutes, for example extruded or co-extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles and greenhouse.
Ill-8) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards and tiles.
111-9) Intake and outlet manifolds.
111-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles and tarpaulins.
IV-1) Plates (walls and cutting board), trays, artificial grass, synthetic (such as Astro-Turf@), artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics) and tapes.
IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic articles/geotextiles/monofilaments; filters; wipes/curtains (shades)/medical applications), bulk fibers (applications such as gown/protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, "balloon-silk", camping articles, tents, airbeds, sun beds, bulk bags and bags. Non woven fabrics such as medical fabrics and related apparel, industrial apparel, outdoor fabrics, in-home furnishing and construction fabrics.
IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, center console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles and trunk trim.
V) Films (packaging, dump, laminating, agriculture and horticulture (greenhouse covers, tunnel, low walk-in tunnel, high tunnel, mulch, silage, silo-bags, silo-stretch, fumigation, air bubble, keder, solawrap, thermal, bale wrap, nursery, film tubes), greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries and connectors. Films may have a mono-layer structure or a multi-layer structure, for example three, five or seven layers. Examples include film structures represented by A-B-A, A-B-C, A-B-C-B-A, A-B-C-B-D, A-B-C-D-C-B-A, A-A-B-C B-A-A, wherein A, B, C and D represent different polymers or tackifiers. Layers may also be arranged to provide films having an even number of layers, i.e. two, four or six layers such as A-A-B-A, A-A-B-B, A-A-B-A-A, A-B-B-A-A, A-A-B-C-B, A-A-B-C-A-A and the like.
VI-1) Food packing and wrapping (flexible and solid), bottles.
VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs and cans.
VI-3) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices and packing for pharmaceuticals blister.
VII-1) Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle/clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks and snap-closures.
VIl-2) Support devices, articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles and cans.
VII-3) Furniture in general, foamed articles (cushions, impact absorbers), foams, sponges, dish clothes, mats, garden chairs, stadium seats, tables, couches, toys, building kits (boards/figures/balls), playhouses, slides and play vehicles.
VII-4) Materials for optical and magnetic data storage.
VII-5) Kitchen ware (eating, drinking, cooking, storing).
VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes) and adhesive tapes.
VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards and display technologies.
VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO 2, mica, nanocomposites, dolomite, silicates, glass, asbestos).
In certain embodiments, a shaped article is a film, pipe, profile, bottle, tank, container or fiber. The shaped articles may be prepared by molding, for instance injection molding, blow molding, compression molding, rotomolding, slush-molding or extrusion molding.
The methods and compositions of the present invention provide for excellent color performance and enhanced thermal stability of polyolefins during melt processing. Melt processing stability may be exhibited by improved retention of molecular weight and maintenance of polymer molecular architecture.
The articles "a" and "an" herein refer to one or to more than one (e.g. at least one) of the grammatical object. Any ranges cited herein are inclusive. The term "about" used throughout is used to describe and account for small fluctuations. For instance, "about" may mean the numeric value may be modified by ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, +0.3%, ±0.2%, ±0.1% or±0.05%. All numeric values are modified by the term "about" whether or not explicitly indicated. Numeric values modified by the term "about" include the specific identified value. For example "about 5.0" includes 5.0.
U.S. patents, U.S. patent applications and published U.S. patent applications discussed herein are hereby incorporated by reference.
Unless otherwise indicated, all parts and percentages are by weight. Weight percent (wt%), if not otherwise indicated, is based on an entire composition free of any volatiles.
Examples
The following additives are employed in the Examples: A01 is a hindered phenolic antioxidant, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); A02 is a hindered phenolic antioxidant octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate; Phos1 Phos6 are organophosphorus stabilizers; tris(2,4-di-tert-butylphenyl) phosphite (Phos1); tris nonylphenyl phosphite (Phos2); bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (Phos3); bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Phos4); 2,2',2"-nitrilo[triethyltris(3,3'5,5' tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] (Phos5); bis(2,4-di-a-cumylphenyl) pentaerythrtitol diphosphite (Phos6); DOVERPHOS LGP-11, proprietary liquid phosphite stabilizer (Phos7); a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1 dimethylpropyl)phenyl phosphites (Phos8).
Additive loadings are in ppm (parts per million) by weight, based on the weight of the polymer. Where total amount of phosphorus (P) is listed with the formulations, this is also reported in ppm by weight, based on the weight of the polymer.
Polymer plaques are tested for color development according to ASTM-313 with a DCI SF600 spectrophotometer; large area view; spectral component included; 2 degree observer. Color is expressed as yellowness index (Y).
Melt flow rate retentions are determined for polymer samples from the zero pass and fifth passextrudate. Melt flow rate is performed according to ASTM-1238 on a Tinius-Olsen Extrusion Plastometer at 190°C; 2.16 kg; measured in grams of polymer that flow out of a defined orifice in 10 minutes.
Oxidative Induction Time (OIT) is a measure of oxidative stability of the polymer. OIT is measured with a differential scanning calorimeter (DSC). Scans are collected using a heating rate of 10°C/minute under nitrogen from 50°C to 190°C, switching to oxygen and holding at isothermal conditions until catastrophic oxidation. Time to onset of catastrophic oxidation (observed as a strong exotherm) is reported in minutes.
Example 1 m-LLDPE
Cast film grade metallocene linear low density polyethylene (m-LLDPE) is formulated with additives listed below.
1) 500 ppm Phos1; 24 ppm P 2) 1000 ppm Phos1; 48 ppm P 3) 400 ppm Phos1; 100 ppm benzofuranone (109); 23 ppm P 4) 375 ppm Phos1; 125 ppm benzofuranone (109); 23 ppm P 5) 425 ppm Phos1; 125 ppm benzofuranone (109); 25 ppm P 6) 450 ppm Phos2; 100 ppm benzofuranone (109); 23 ppm P 7) 187 ppm Phos3; 100 ppm benzofuranone (109); 23 ppm P 8) 304 ppm Phos4; 100 ppm benzofuranone (109); 23 ppm P 9) 187 ppm Phos5; 100 ppm benzofuranone (109); 23 ppm P 10) 264 ppm Phos6; 100 ppm benzofuranone (109); 23 ppm P
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 250 ppm A02 and 200 ppm A01. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. The compounded formulations are extruded multiple times in a single screw extruder fitted with a Maddock mixing section at 260°C, open to air. Pelletized samples of the third pass extrudate are compression molded into 3.2 mm plaques. Results are below.
formulation YI melt flow (zero pass) melt flow (fifth pass) OIT
1 3.5 3.68 3.07 74 2 2.8 3.70 3.42 110 3 3.2 3.70 3.16 111 4 3.1 3.78 3.45 113 5 2.9 3.86 3.73 122 6 2.2 3.71 3.13 109 7 1.6 3.75 3.09 124 8 2.2 3.70 3.16 108 9 2.0 3.71 3.40 107 10 1.3 3.72 3.31 84
Example 2 Blow Molding Grade HMW Cr-HDPE
Blow molding grade chromium catalyzed high molecular weight high density polyethylene (HMW Cr-HDPE), high load melt index (HLMI) 5.5, is formulated with additives listed below.
1) 620 ppm Phos1 2) 1250 ppm Phos1 3) 375 ppm Phos1; 125 ppm benzofuranone (109) 4) 450 ppm Phos1; 150 ppm benzofuranone (109) 5) 375 ppm of a 1:1 weight mix of Phos/Phos6; 125 ppm benzofuranone (109) 6) 375 ppm of a 1:1 weight mix of Phos/Phos3; 125 ppm benzofuranone (109)
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 500 ppm A01. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. Pelletized samples are compression molded into 3.2 mm plaques. Results are below.
formulation YI OIT 1 6.8 93 2 6.8 146 3 7.9 103 4 8.3 98 5 5.8 94 6 3.8 108
Example 3 m-LLDPE
Blown film grade metallocene linear low density polyethylene (m-LLDPE) is formulated with additives listed below.
1) 500 ppm Phos1; 24 ppm P 2) 1000 ppm Phos1; 48 ppm P 3) 375 ppm Phos1; 125 ppm benzofuranone (109); 23 ppm P 4) 500 ppm Phos2; 21 ppm P 5)1000ppm Phos2;43 ppm P 6) 375 ppm Phos2; 125 ppm benzofuranone (109); 21 ppm P 7) 500 ppm Phos7; 24 ppm P 8)1000ppm Phos7;48 ppm P 9) 375 ppm Phos7; 125 ppm benzofuranone (109); 22 ppm P 10)500ppm Phos8;27ppm P 11)1000ppm Phos8;53ppm P 12) 375 ppm Phos8; 125 pp benzofuranone (109); 25 ppm P
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 500 ppm zinc stearate and 500 ppm A02. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. The compounded formulations are extruded multiple times in a single screw extruder fitted with a Maddock mixing section at 260°C, open to air. Pelletized samples of the third pass extrudate are compression molded into 3.2 mm plaques. Results are below.
formulation YI melt flow (zero pass) melt flow (fifth pass) OIT 1 3.9 0.92 0.58 52 2 3.3 0.94 0.70 67 3 1.1 0.93 0.66 85 4 -0.4 0.94 0.80 59 5 -0.7 0.89 0.89 65 6 1.0 0.89 0.88 92 7 3.3 0.94 0.52 29 8 1.2 0.93 0.62 36 9 1.5 0.93 0.64 57
10 0.9 0.94 0.61 60 11 0.4 0.95 0.80 68 12 0.9 0.92 0.75 81
Example 4 Blown Film Grade m-LLDPE
Blown film grade metallocene linear low density polyethylene (m-LLDPE) is formulated with additives listed below.
1)500ppm A02;0ppm P 2) 500 ppm Phos1; 500 ppm A02; 24 ppm P 3) 1000 ppm Phos1; 500 ppm A02; 48 ppm P 4) 375 ppm Phos1; 500 ppm A02; 125 ppm benzofuranone (109); 23 ppm P 5) 450 ppm Phos1; 500 ppm A02; 150 ppm benzofuranone (109); 27 ppm P 6) 600 ppm Phos1; 150 ppm benzofuranone (109); 34 ppm P 7) 800 ppm Phos1; 200 ppm benzofuranone (109); 46 ppm P
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 500 ppm zinc stearate. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. The compounded formulations are extruded multiple times in a single screw extruder fitted with a Maddock mixing section at 260°C, open to air. Pelletized samples of the third pass extrudate are compression molded into 3.2 mm plaques. Results are below.
formulation YI OIT 1 0.6 22 2 0.6 29 3 0.2 42 4 1.3 85 5 0.7 101 6 -0.6 8 7 -0.5 10
Example 5 zn-LLDPE
Blown film grade Ziegler-Natta linear low density polyethylene (zn-LLDPE) is formulated with additives listed below.
1) ---- ; 0 ppm P 2) 500 ppm Phos1; 24 ppm P 3) 1000 ppm Phos1; 48 ppm P 4) 300 ppm Phos1; 100 ppm benzofuranone (109); 18 ppm P 5) 375 ppm Phos1; 125 ppm benzofuranone (109); 23 ppm P 6) 450 ppm Phos1; 150 ppm benzofuranone (109); 27 ppm P 7) 400 ppm benzofuranone (109); 15 ppm P 8) 500 ppm benzofuranone (109); 19 ppm P 9) 600 ppm benzofuranone (109); 22 ppm P
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 450 ppm of a 4/5 weight mixture of A01/A02 and 800 ppm zinc oxide. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. The compounded formulations are extruded multiple times in a single screw extruder fitted with a Maddock mixing section at 260°C, open to air. Pelletized samples of the third pass extrudate are compression molded into 3.2 mm plaques. Results are below.
formulation YI melt flow (zero pass) melt flow (fifth pass) OIT 1 3.4 1.79 1.32 25 2 1.0 1.94 1.65 40 3 1.3 1.96 1.85 58 4 2.2 2.00 1.70 43 5 2.0 2.01 1.78 64 6 2.9 2.00 1.86 72 7 2.2 1.96 1.79 89 8 2.4 1.96 1.84 109 9 3.2 2.00 1.86 114
Example 6 m-LLDPE
Cast film grade metallocene linear low density polyethylene (m-LLDPE) is formulated with additives listed below.
1) ---- ; 0 ppm P 2) 500 ppm Phos1; 24 ppm P 3) 1000 ppm Phos1; 48 ppm P 4) 300 ppm Phos1; 100 ppm benzofuranone (109); 18 ppm P 5) 375 ppm Phos1; 125 ppm benzofuranone (109); 23 ppm P 6) 450 ppm Phos1; 150 ppm benzofuranone (109); 27 ppm P 7) 400 benzofuranone (109); 15 ppm P 8) 500 benzofuranone (109); 19 ppm P 9) 600 ppm benzofuranone (109); 22 ppm P
Additives are blended with granular polymer free of any stabilization additives. In addition to the additives listed, all formulations are blended with 450 ppm of a 4/5 weight mixture of A01/A02, 300 calcium stearate and 500 ppm hydrotalcite. Thoroughly blended formulations are melt compounded in a twin screw extruder at 210°C under nitrogen. The compounded formulations are extruded multiple times in a single screw extruder fitted with a Maddock mixing section at 260°C, open to air. Pelletized samples of the third pass extrudate are compression molded into 3.2 mm plaques. Results are below.
formulation YI melt flow (zero pass) melt flow (fifth pass) OIT 1 3.7 4.07 2.70 63 2 4.4 4.10 3.43 93 3 4.4 4.06 3.83 111 4 3.5 4.10 3.69 112 5 3.6 4.08 3.76 119 6 4.9 4.09 3.84 129 7 4.4 4.04 3.68 141 8 4.4 4.05 3.75 139 9 5.3 4.08 3.87 150

Claims (24)

Claims
1. A composition comprising
i) a polyolefin,
ii) one or more benzofuranone compounds selected from the group consisting of formula l-pl, I p2, 1-ol, 1-o2, 1-m1 and 1-m2 Rip 0
0 Z 0 Rp 3 P~2P YP-Rp Rp330\D
Rp5 Rp5 Rp2 Rp2
-p1 -p2 H H O R4 O R4 o I R7 R5 R7 R5
R6 R6
Rio RII 7 O/ R10 R RO
00 4 4 R H R H /R \4 /H \ -o2 2 2 Ro Ro5 Ro R°5|-o2
Rol Ro6 -01 R°l R°6
O-Rlm
O--z 0
Rim /R2m 0 /
/ Rm5 Rms
/m3Rm 6 Rm 3 Rm RRm1 Rm1
0 Rml 0 m
H I-m1 H 1-m2 0 R4 0 R4
| | R7 R5 R7 R5
wherein X and Z are independently P or P=O; YP, Y'and Ym are oxygen or represent a covalent bond; when YP, Y'and Ym are oxygen, R1 represents one of subformulae II-p, ll-o or I1-m
Rp3 Ro 5 R° 6
Rp 5 ROi Rp2
O RP0 Ro2
H H |1-o O R4 O R4
RI R RI R
Rms
Rm3 Rme Rm3m
O Rl
0 R
R
R"°represents one of subformulae II-o or Il-m, Rm represents subformula ll-m, or R 1Ptogether with R 2p, R° together with R 2°and Rl together with R 2m represent one of subformulae Ill, IV or V
Ra1 Ra4
Ill
H* H H H
R2 Ra3
Rc1 S Re4
H H H H
Rc 2 Rc 3
or R1 P, R"°and R"are C 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C C 8-alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 6 -cycloalkyl, C 7-C 1 3-aralkyl, C2-C1
alkenyl, C 2-C 3o-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 1 -alkyl, which is interrupted by one sulfur atom, R2 P represents one of subformulae II-p, ll-o orI-m, R 2° represents one of subformulae II-o or Il-m, R2"'represents subformula ll-m, or R2p together with R1 P, R 2°together with R"°and R 2" together with Rl represent one of subformulae Ill, IV or V, or R2p, R 2° and R 2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, CC 1 -alkyl, C3-C16 cycloalkyl, C 7-C 13-aralkyl, C 2-C 1-alkenyl, C 2-C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16-alkyl, which is interrupted by one sulfur atom; when YP, Y'and Y' represent a covalent bond, R'P represents one of subformulae II-p, ll-o orI-m, R° represents one of subformulae II-o orI-m, R represents subformula ll-m, or R 1P, R"°and R" are C 6-C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, CrC8 alkoxy, halogen or one phenyl, CC 1 -alkyl, C-C 1 6 -cycloalkyl, C 7-C1 3-aralkyl, C 2-C1 8 -alkenyl,
C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom, R 2p, R 2° and R2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C-C 8-alkyl, C-C 8-alkoxy, halogen or one phenyl, or halogen; R 4 , R5 , R6 and Rare each independently hydrogen or C-C8 -alkyl, RP2 , RP 3 , RP5 and Rp 6 are each independently hydrogen or C-C8 -alkyl, R° 1, R 02, R 05 and R 06are each independently hydrogen or C-C8 -alkyl, R", R", Rsand Rm are each independently hydrogen or C-C8 -alkyl, R , R, Ra and Ra4 are each independently hydrogen or C-C8 -alkyl, R, R 2 , R, R 4 , R and R are each independently hydrogen or C-C8 -alkyl and R°, R 2, R1 3 and R°4 are each independently hydrogen or C-C8 -alkyl
and
iii) one or more organophosphorus stabilizers.
2. The composition according to claim 1, wherein the polyolefin comprises polypropylene.
3. The composition according to claim 1, wherein the polyolefin comprises polyethylene.
4. The composition according to claim 1, wherein the organophosphorus stabilizers are selected from the group consisting of triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(2,4-di-tert-butylphenyl) phosphite, tris-(sec-butylphenyl) phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-a-cumylphenyl) pentaerythrtitol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxy-pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di tert-butylphenyl)4,4'-biphenylene-diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite,2,2',2"-nitrilo[triethyltris(3,3'5,5'-tetra tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite],bis(2,4-di-t-butylphenyl)octylphosphite, poly(4,4'-{2,2'-dimethyl-5,5'-di-t-butylphenylsulfide-}octylphosphite),poly(4,4'{ isopropylidenediphenoll-octylphosphite),poly(4,4'-{isopropylidenebis[2,6-dibromophenol]} octylphosphite),poly(4,4'-{2,2'-dimethyl-5,5'-di-t-butylphenylsulfide}-pentaerythrityl diphosphite),
(CH 3)3C C(CH 3)3 C(CH 3) 3
0O (CH 2) 3CH 3 O (CH3)3C O-P , OH2 P-O--C8 H17 S- 0 CHCH 2 03 2 C0 2
C(CH 3) 3
C (CH 3)3 (CH 3)3C
O P--o(M) nI
n=1-5 and
0 __
P-0 OH (N) 0 C
5. The composition according to claim 1, wherein the organophosphorus stabilizers are selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, tris-nonylphenyl phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] and bis(2,4-di-a-cumylphenyl) pentaerythrtitol diphosphite.
6. The composition according to claim 1, comprising tris-(2,4-di-tert-butylphenyl) phosphite.
7. The composition according to any of claims 1 to 6, further comprising one or more compounds selected from the group consisting of hindered phenolic antioxidants.
8. The composition according to any of claims 1 to 6, further comprising one or more hindered phenolic antioxidants selected from the group consisting of -(3,5-di-tert-butyl-4 hydroxyphenyl)propionic acid esters.
9. The composition according to any of claims 1 to 6, wherein the composition comprises essentially no hindered phenolic antioxidants.
10. The composition according to any of claims 1 to 6, wherein the one or more benzofuranone compounds are present from about 20 ppm to about 1000 ppm by weight, based on the weight of the polyolefin.
11. The composition according to any of claims 1 to 6, wherein the one or more organophosphorus stabilizers are present from about 20 ppm to about 1000 ppm by weight, based on the weight of the polyolefin.
12. The composition according to any of claims 1 to 6, wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more organophosphorus stabilizers is from about 0.05 to about 1.0.
13. The composition according to any of claims 1 to 6, wherein the benzofuranone compounds are selected from the group consisting of formula l-pl, 1-p2 and |-ol.
14. The composition according to any of claims 1 to 6, wherein in the benzofuranone compounds, X and Z are P and Y is 0.
15. The composition according to any of claims 1 to 6, wherein the benzofuranone compounds are formula 1-p1, 1-p2, 1-ol, 1-o2, I-mI or I-m2, wherein YP, Y° and Ym are oxygen or represent a covalent bond; when YP, Y° and Ym are oxygen, R'P represents one of subformulae II-p, ll-o or Il-m, R° represents one of subformulae II-o or I-m, R represents subformula ll-m, or R'Ptogether with R 2p, R"°together with R2°and R"together with R2m represent one of subformulae Ill, IV or V, or R'P, R"°and R" are C-C1 o-aryl, which is unsubstituted or substituted by C1 -C-alkyl, C-C8 -alkoxy, halogen or one phenyl, C1-C18 alkyl, C-C 1 -cycloalkyl, C 7-C 13-aralkyl, C 2-Cis-alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom, R 2p represents one of subformulae II-p, ll-o or I-m, R 2°represents one of subformulae II-o or II m, R2 represents subformulall-m, or Rtogether with R'P, R2°together with R"°and R2 together with R" represent one of subformulaeIll, IV or V, or 2R p, R 2°and 2R are C-C1 aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C8 -alkoxy, halogen or one phenyl, C-C 18 -alkyl, C-C 16 -cycloalkyl, C 7-C 13 -aralkyl, C 2-C 18-alkenyl, C 2-C 30-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 16 -alkyl, which is interrupted by one sulfur atom; when YP, Y'and Ymrepresent a covalent bond, R1 Prepresents one of subformulae II p, Il-o or I-m, R"°represents one of subformulae II-o orI-m, R" represents subformula l-m, or R'P, R"°and R"are C 6 -C 1o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C C 8-alkoxy, halogen or one phenyl, CC 1 8 -alkyl, C-C 1 -cycloalkyl, C 7-C 13-aralkyl, C2-C18 alkenyl, C 2-C 3o-alkyl, which is interrupted by one or more oxygen atoms, or C 2-C 1 -alkyl, which is interrupted by one sulfur atom, R2 p, R2°and R 2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C1 -C8 -alkyl, C-C 8-alkoxy, halogen or one phenyl, or halogen; R 4 and R 6 are hydrogen, R 5 and R7 are each independently hydrogen or C-C8 -alkyl, Rp2 and Rp6are each independently hydrogen or C-alkyl, Rp 3 and Rp5 are each independently hydrogen or C-C 4-alkyl, R° 1and R° 6 are each independently hydrogen or C-C8 -alkyl, R°2 is hydrogen or C-alkyl, R°5 is hydrogen or C-C 4-alkyl, R" is hydrogen or C-alkyl, R"'3 and R"'5 are each independently hydrogen or C-C 4-alkyl, Rm 6 is hydrogen or C-C8 -alkyl, Ra1 , Ra2 , Ra3 2 and Ra 4 are each independently hydrogen or CC 4-alkyl, Rb, Rb , RW, Rb 4 , Rb 5 and Rb6 are each independently hydrogen or C-C 4-alkyl and R°, R 2 , Rand R 4 are each independently hydrogen or C-C 4-alkyl.
16. The composition according to any of claims 1 to 6, wherein the benzofuranones are of formula 1-p1, 1-p2, 1-ol, 1-o2, I-m1 or I-m2, wherein YP, Y'and Y' are oxygen or represent a covalent bond; when YP, Y'and Y"'are oxygen, R1Prepresents one of subformulae II-p, ll-o or Il-m, R° represents one of subformulae II-o or Il-m, R" represents subformula ll-m, or R'P together with R 2p, R"°together with R 2°and R" together with R 2"'represent one of subformulae Ill, IV or V, or R'P, R° and R" are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 1 -alkyl or C-C 1 -cycloalkyl and R 2Prepresents one of subformulae II-p, ll-o or Il-m, R 2° represents one of subformulae II-o or I-m, R 2"'represents subformula ll-m, or R2 ptogether with R'P, R 2°together with R"°and R 2"'together with R" represent one of subformulae Ill, IV or V, or R 2p, R 2°and R 2 ' are C-C1 o-aryl, which is unsubstituted or substituted by C-C8 -alkyl, C-C 18 -alkyl or C-C 16 -cycloalkyl; when YP, Y'and Y"'represent a covalent bond, R1 Prepresents one of subformulae II-p, ll-o orI-m, R'° represents one of subformulae II-o orI-m, R" represents subformula l-m, or R'P, R° and Rare C6 -C 1 o-aryl, which is unsubstituted or substituted by C-C 8 -alkyl, C-C 1 -alkyl or C C 1 -cycloalkyl and R 2p, R 2° and R 2 ' are C-C 1 -aryl, which is unsubstituted or substituted by Cl-C 8-alkyl or fluoro.
17. The composition according to any of claims 1 to 6, wherein the benzofuranones are of formula 1-p1, 1-p2, 1-ol or I-o2, wherein YP and Y° are oxygen or represent a covalent bond; when YP and Y'are oxygen, R'P, R 2p, R1°or R 2 0does not represent subformula Il-m; when YP and YOrepresent a covalent bond, RPor R10 does not represent subformula l-m.
18. The composition according to any of claims 1 to 6, wherein the benzofuranones are of formula 1-p1, 1-p2, 1-ol or -o2,wherein YP and Y° are oxygen, R'P together with RP and R" together with R 2°represent one of subformulae Ill, IV or V, RP t ogether with R'Pand R2 ° togetherwith R°represent one of subformulae Ill, IV or V, R 4 , R5 , R6 and R7 are each independently hydrogen or C-C8 -alkyl, Rp2 , Rp3, Rp 5and Rp 6are each independently hydrogen or C-C8-alkyl, R° 1, R02, R05 and R0 6 are each independently hydrogen or CrC8 alkyl, R 1, R, Ra and Ra4 are each independently hydrogen or C-C8 -alkyl, R, R 2,R 3 ,R 4
, Rb 5 and Rb 6 are each independently hydrogen or C-C8 -alkyl and R°, R 2 , R3 and R4 are each independently hydrogen or C-C8 -alkyl.
19. The composition according to any of claims 1 to 6, wherein the benzofuranones are selected from the group consisting of compounds of formula (101)-(133)
H 3C CH 3
CH 3 CH 3 H3C H 3C H 101 0 H00 00 0
H3 0 H 0C I-POH 3 OH 3 H /\/ H 3 H 3C H3 C OH 3 H3C OH3 CH 3 H 3C
H 3C H H 3C H 2 C-LKj H3- CH 3 H3C CH 3 H
H 2C CH 3
H3 C H 7 102 0 00 0 0 H3C I 0 HCH2 C H0\ICH 3CH HCCH 3 /\ / H C3 H3 H3H 3C H CCH 3
H3C CH 3 CH 3 H2C CH2 HC H H 3C CH 3 HC -H H3C H 3C CH 3
H 3C 0 H3 H3 OH 3
0 H3C H 0 H H3
HCH o3 3~oH I /H CH 3
H 3C H3 10
H 3C OH 3
HH 3 C
H3H
H3 0 0 PO 3 H HCOH
( CH 3 H3
/H 1H4
H C
0 H 3OC4 H3
H3 0 OH3
OH3 H 30
H379
H3 C CH 3 H 3C CH 3
H3C OH 3C
H \0 CH3 106
CH3 CHC H3C CH3H 3C CH 3 H3C H
CHH3H0 H
H3 0 0 0 3 H H 3C OH 3
H3 C o-P H 3C 0 107
3CH
H3C OH0 3 H HCH 3 0 H3
KOH 3
H3C- OH 3
C3 H3 OH3 H3
H 3C CH 3 H 3C CH 3
\/ hH 0-P \ O H-OH 3 109
H3CH 3
OH 3 H3C ------ H 3C CH 3 H 3C H3 O.... OH3 H O1 -3 OH
CH3 H3 C CH 3
3C CH3 CH 3
0 \0 110
OH H3 C CH3 SH3 C C HH 3 3 CH3
O O---- CH -CH H3CH3C
OHHOH
HH 3 7 3 C H3
H3C0 H 3C 03 CH3 OH H3H3 CH3H CH3 CHCH CH3C H3CC H3 H3 OH PH
H3CC CH CH3H3C
CH 3 H 3C
H 3C OH 3 H 30 H2 0LI H3 0- CH 3 CH 3 H H 2C OH 3
H 3C H 7 112 0 H00 0 0 0 H3C 0 00 H 2C H3 O0
H3 C H OH 3 /\/ H 3C H2 H H 3
H 30 OH 3 H 3O OH 3 O3 H2 H2O CH H3 CH3 H 3CH O 3
OH 3 OH 3 H
H30 0 H3 H3 0 OH 3 H 30 0- OH
0 OH3 H
/ OH3 3 H3 0 H3 3 H
H0 OH3
HH 3 C
H3H
0
" H 3C P-0H3 H H0OH CH3 114 HH3
H3 CH C 0
3 C 0
0 0OH H3 C 0H OH3
H3C OH3 /\H 3 OH
HH3C. H
0 OH3 H H 33 H3 0
83 3CH
H3 C CH 3 H 3C CH 3
0H3C 11 CH 3
H3 H30H 3 C CH H0
3 H 00 HH3 11 ,~H OHHH0 H H3 0 H 3 0 3C H3 O3 H3
CH 3C
H3C 0 H3 C CH O3 H3 HOH 3
HH 3C OH3 HH H3
H3C OH3
H C 118 H3C H3 KOH 3 H3 H 3 O H3 H3 O
84 H3HC H
H 3C CH 3 H 3C CH 3 H3CH 3
H3C CH3 O CH3 O
H-C H3OH 3 H 3C ---- O......p\0 11 9 CH3 H3 C CH 3 H3CHCH3 H"0 OH H 30 CH 3 CH3 H3C CH3 H3C OH
H3 HH H3C H 3 3
H CH3 H 3C CH 3
3C CH3 H3 CH3H P12 3 H0 /\ C3H 0 00 3
CH3 H3C ..-- H3C ._~P 121 H3 O
H3H 3 H3 CHH 3
121- CH3 H3C CH3
H3C CH3 H3C CH3
H3C OH 3 0 0 H3 C /H H3 Op -- P P-0 0 \ 00 3 0
H 3 C0 0 H OH 3 H H 3C H3 H 3C OH 3 CH 3 122 H 3C - H3
H3C CH 3 H3 0 CH 3
0 H3 0 0 / x \pCH 3 H 3O O\H3 OH3 H \ 0 0 / HH 3C
HC 3C OH 3 H3O OH 3 OH 3 123 H 3O
H3C HC lp\ P-CH 3
H3 C CH3 CH 3
~0 0 H 3C o-LO CH 3 0 /\ 0 H 3C 0 H0 H 0 H3 O H3 ~ /H 3 C CH 3 H 3C C 3 15H H 3
H3 0 OH 3 HC CH 3
H 3C OH 3 00C 00
H 3C CH3
3O H3 0H 3DO0 0 \ 0 3 0 H0H 3 0 H3 OH 3 H3 CC
OH 3 OH 3 126 H 3O - H3
H3C OH 3 H3C CH 3
0 0
H 3O 0 00 0 0 0 OH 3 H 3C -p \p N /\ CH 3 CH 3 H \ 0 0/H H30
H3 O OH 3 H3C OH3 OH 3 127 H 3C
H3C 0 0\\ 0 0CH 3
HH 3C CH
C3C3 H HC 0P0 0OH H 0~H 3 H3 C~ C\O
, H3 C OH 3 19H 3 0 - OH C H H3 OH 3 HI OH3
H3 CH3 03- 0 0 H3 C C-o OH 3
OH3 0H0 /\Ppy 0 0 3 0 H O 3 HOH 3
0 H OH 3 OH3 13C 3 H3
H 30 O<H 3 H3 0 OH 3
H3C CH3 88
H 3C 0 0 00 0 CH 3 H 3C \/ CH 3 CH 3 H O O H H 3C
H 3C CH 3 H 3C CH 3 CH 3 131 H3C
H3C O S0% O O CH 3 H3C -p P
H3C C3 H O O 0 H H3 H3 CH3-H3C I CH3 H3C CH3 12 H3C CH3 CH3 3 CH3 CH3 132 H3C CH3 H3C CH3
H3C H3COCHH O
H3C
H3C CH3 H CH3 H3C CH3 CH3
H3C p---O-0 CH3 0 CH3
CH3 CH3
'ICH3 H3 CH3 133 H3C
20. A shaped article comprising the composition according to any of claims 1 to 6.
21. A method of preparing the shaped article according to claim 20, the method comprising melt blending the composition.
22. An additive composition comprising ii) one or more benzofuranone compounds selected from the group consisting of formula -pl, 1-p 2 , 1-ol, 1-o2, 1-m1 and 1-m2 of claim 1 and iii) one or more organophosphorus stabilizers.
23. The additive composition according to claim 22, wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more organophosphorus stabilizers is from about 0.05 to about 1.0.
24. A method of stabilizing a polyolefin against deleterious effects of heat, light and oxygen, the method comprising incorporating into the polyolefin ii) one or more benzofuranone compounds selected from the group consisting of formula 1-p1, 1-p2, 1-ol, 1-o2, 1-m1 and 1-m2 of claim 1 and iii) one or more organophosphorus stabilizers.
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