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    • 专利摘要:
    The present invention provides at least one member selected from the group consisting of hindered phenols, hindered amines, lactones, sulfides, phosphites, benzotriazoles, benzophenones and 2- (2-hydroxyphenyl) -1,3,5-triazines. A method of stabilizing plastics and plastic compositions and simultaneously phase compatibilizing by incorporating a polymerizable compound obtainable by reacting a compound having a functional group with a compatibilizer.
    公开号:KR20000049270A
    申请号:KR1019990703379
    申请日:1997-10-20
    公开日:2000-07-25
    发明作者:루돌프 파엔드너；하인즈 허프스트；쿠르트 호프만；사무엘 에반스；알프레드 스타인만
    申请人:시바 스폐셜티 케미칼스 홀딩 인코포레이티드；
    IPC主号:
    专利说明:

    Functionalized polymers
    The present invention relates to the stabilization of plastics and plastic compositions (renews mixed with unused materials or optionally unused materials) by incorporating certain compatibilizers, while at the same time improving their mechanical properties.
    The process for the preparation of the polymer mixture is a confirmed process for producing plastics with novel properties. However, as is known, polymers with different structures cannot usually be mixed with each other: the processing of two different plastics will result in a macroscopic mixture with insufficient mechanical properties. So-called compatibiliser is used commercially to improve the compatibility and properties of the plastic mixture. Such compatibilizers are polymers that can prevent or reduce the separation of two or multicomponent systems or improve dispersion to produce homogeneous mixtures of different plastics with good mechanical properties.
    Known compatibilizers are mainly based on polymers of polar and nonpolar structure which can be prepared by conventional polymerization reactions.
    Compatibilizers are used in unused plastic compositions and reclaimed materials. In this case, the manufacturing process, or the plastic collection used, results in a plastic composition having mechanical properties suitable for new applications only when a compatibilizer is added to the plastic composition.
    In Kunststoffe 83 (1993), 10, 820 to 822 and Kunstsoffe 85 (1995) 4, 446 to 450, K. Hausmann is known as polyethylene / polyethylene terephthalate (PE / PET) and polyamide / polyethylene (PA / PE Discusses the problem of recycling incompatible plastics such as Compatibilizers are used for regeneration. R.-E. in Kunststoffe 83 (1993) 5, 369-372. Grutzner. R.Gartner and H.-G. Hock published a study on a similar system (PE / PA composite foil). R. Muhlhaupt and J. Rosch report on phase compatibilizers for polypropylene / polyamide (PP / PA) mixtures in Kunststoffe 84 (1994) 9, 1153-1158. G. Obieglo and K. Romer also describe the use of compatibilizers in plastic recycling in Kunststoffe 83 (1993) 11, 926-929. In Recylc'91, 8 / 5-1 and Recyle'95, 6 / 4-3, S. Fuzessery describes compatibilizers and polymer modifiers for unused and regenerated thermoplastics. It is known to bind a stabilizer to a polymerizer to obtain a better mixture in the product to be stabilized, thereby preventing the stabilizer from moving. This is described by Polymer Degradation and Stability 25 (1989) by M. Minagawa, 121-141 or by J.M.S.-Pure Appl. By H. Yamaguchi, M.Itoh, H. Ishikawa and K. Kusuda. Chem, A30 (4) (1993), 287-292. Die Angewandte Makromolekulare Chemie 158/159 (1998), 221-231, Advances in Polmer Science 101, pages 65-167, Springer-Verlag Berlin Heidelberg, 1991 and Jan Pospisil, Peter P. Klemchuck, Oxidation inhibition in Organic Materals, No. 1 (1989), 193-224, Jan Pospisil reported an investigation of "functionalized" polymers, ie polymers comprising effective antioxidants, anti-ozone agents, metal deactivators, photostabilizers or biostabilizers. . EP-A 306 729 includes anhydride-functionalized polymers containing hydrazide-functionalized antioxidants or cyclic α, β-unsaturated dicarboxylic anhydrides (with antioxidant functionality) of N-substituted imides and ethylenic or An antioxidant is bound to a polymer obtained by reacting with a copolymer of vinyl aromatic monomers.
    The stabilization of the plastic composition against heat and light is a particular problem since it depends on the polarity of the components and the heterogeneous distribution of the stabilizer compounds results in a polyphase polymer system (stabilizer splitting). This is D.M. Kulich, M.D. Wolkowicz and J.C. Makromol by Wozny. Chem., Macromol. Symp. 70/71, 407-418 (1993). The distribution balance of the stabilizer is additionally influenced by the compatibilizer used, which is a less stable component of the composition. Thermal or photooxidative damage of the compatibilizer quickly destroys the entire composition because the compatibilizing component is damaged.
    Therefore, it is desirable to provide compounds that can enhance not only the compatibility of components in the polymer mixture, but also mechanical properties, and also protect against oxidation and photooxidation damage.
    It has recently been discovered that certain polymers with corresponding stabilizer side chains have the properties described above.
    The present invention comprises one or more functional reactors, including hindered phenols, particle hindered amines, lactones, sulfides, phosphites, benzotriazoles, benzophenones and 2- (2-hydroxyphenyl) -1,3,5- A method for stabilizing and simultaneously phase compatibilizing a plastic or plastic composition by incorporating a polymerizable compound obtainable by reacting a compound selected from the group consisting of triazine with a compatibilizer.
    Suitable sterically hindered phenols comprising at least one reactor and reacting with a compatibilizer compound are compounds of formula (1):
    Where
    R 1 and R 2 are each independently a hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 unsubstituted or substituted on the aromatic ring with OH and / or C 1 -C 4 alkyl on the aromatic ring -C 3 alkyl, unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, or phenyl;
    n is 1, 2 or 3;
    E is OH, SH, NHR 3 , SO 3 H, COOH, -CH = CH 2 , or ego;
    m is 0 or 1;
    R 3 is hydrogen or C 1 -C 9 alkyl;
    R 4 is C 1 -C 12 alkyl, or phenyl unsubstituted or substituted with one or several C 1 -C 4 alkyl, halogen and / or C 1 -C 18 alkoxy;
    When E is OH, SH or -CH = CH 2 , A is -C x H 2x- , -CH 2 -S-CH 2 CH 2- , -C q H 2q- (CO) -OC p H 2p , -C q H 2q- (CO) -NH-C p H 2p -or C q H 2q- (CO) -OC p H 2p -SC q H 2q- ;
    x is 0 to 8;
    p is 2 to 8;
    q is 0 to 3;
    R 1 and n are as defined above; or
    When E is -NHR 3 , A is -C x H 2x -or -C q H 2q- (CO) -NH-C p H 2p -and x, p and q are as defined above;
    When E is COOH or SO 3 H, A is -C x H 2x- , -CH 2 -S-CH 2 -or -CH 2 -S-CH 2 CH 2 -and x is as defined above;
    E is When A is a direct bond, -C q H 2q- (CO) m -O-CH 2 -or -C x H 2x -S-CH 2 and q, m, x, R 1 and R 2 are defined above As;
    E is When A is -CH 2- ;
    C 1 -C 25 alkyl is linear or branched, typically C 1 -C 20- , C 1 -C 18- , C 1 -C 12- , C 1 -C 9- , C 1 -C 6 -or C 1- C 4 alkyl. Typical examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, 1,1-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl or pentacosyl.
    C 1 -C 9 alkyl and C 1 -C 4 alkyl have the meanings defined above up to the number of carbon atoms in question, for example.
    C 2 -C 6 alkenyl radicals may be single or polyunsaturated and are typically allyl, metaallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-penta Dienyl or 5-hexenyl. Allyl is preferred. R 3 , defined as C 2 -C 6 alkenyl, is for example C 2 -C 4 alkenyl.
    C 1 -C 4 alkoxy is a linear or branched radical and methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, s-butyloxy, iso-butyloxy or t-butyloxy.
    Phenyl-C 1 -C 3 alkyl is typically benzyl, phenylethyl, α-methylbenzyl or α, α-dimethyl-benzyl. Benzyl is preferred.
    C 5 -C 12 cycloalkyl is typically cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl. C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl is typically 1-methylcyclohexyl.
    Halogen is fluoro, chloro, bromo and iodo, in particular chloro and bromo, preferably chloro.
    The mono or polysubstituted phenyl is preferably substituted 1 to 5 times, eg 1, 2 or 3 times, preferably 1 or 2 times on the phenyl ring.
    Substituted phenyl is substituted or linear or substituted by, for example, linear or branched C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl Branched C 1 -C 4 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy or t-butoxy or fluoro, It is substituted by halogen such as chloro, bromo or iodo.
    Phenyl is particularly preferably substituted by methyl, t-butyl, methoxy and chloro.
    Suitable compounds are compounds of formula (1), wherein R 1 and R 2 are C 1 -C 4 alkyl.
    Other compounds mentioned above are compounds of formula (1), wherein R 1 and R 2 are in the ortho-position relative to the OH group.
    Particularly preferred compounds are those in which A is -C x H 2x- , typically 6-t-butyl-2,4-dimethyl-3-hydroxymethylphenol, 2,6-di-t-butyl-4- (3-hydrate Hydroxypropyl) phenol or 2,6-di-t-butyl-4- (2,2-dimethyl-3-hydroxypropyl) phenol.
    x is typically 0-6, preferably 0-4.
    A is -CH 2 -S-CH 2 -or -CH 2 -S-CH 2 CH 2- , typically 2,6-di-t-butyl-4- (4-hydroxy-2-thiabut- Of note are compounds of formula (1) which are 1-yl) phenol or 6-t-butyl-2,4-dimethyl-3- (4-hydroxy-2-thiabut-1-yl) phenol group.
    Other important compounds of formula (1) are compounds wherein A is -C q H 2q- (CO) -OC p H 2p , p is 2 to 5 and q is 1 to 2 or to be.
    Other suitable compounds are , , , , , 2,6-di-t-butyl-4- (3-aminopropyl) phenol, 2,6-di-t-butyl-4- (2,2-dimethyl-2-amino-ethyl) phenol or 2, 4,6-trimethyl-3-aminomethylphenol.
    If E is COOH, x is preferably 2 or 3.
    Preferred compounds are, for example, 2,6-di-t-butyl-4- (2-carboxyethyl) phenol, 2-t-butyl-6-methyl-4- (2-carboxyethyl) phenol and 2,6-di -t-butyl-4- (3-carboxy-2-thiaprop-1-yl) phenol.
    E is If R 4 is for example C 1 -C 4 alkyl, preferably methyl or ethyl, the compound of formula (1) is for example to be.
    Particularly preferred compounds of formula (1) having epoxy functionality are , And And x is as defined above.
    Particularly preferred compounds of formula (1) having OH-, SH- or NHR 3 functionality are as follows:

    Wherein x is 1 to 8.
    Processes for the preparation of sterically hindered phenols are known to those skilled in the art and include DE-A-42 13 750, DE-A-25 12 895, EP-A-463 835, US 5 189 088, DE-A-24 14 417, US 4 919 684, DE-A-42 42 916, DE-A-20 37 965 and numerous other documents.
    Suitable sterically hindered amines having at least one reactor and reacting with a compatibilizer compound are compounds of formula (2), (2a) or (2b):
    Where
    R 8 is a hydrogen atom, C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, phenyl-C 1 -C 3 alkyl, C 5 -C 12 Cycloalkyl, C 5 -C 8 cycloalkoxy, phenyl, naphthyl, hydroxyethyl, CO-C 1 -C 25 alkyl, CO-phenyl, CO-naphthyl, CO-phenyl-C 1 -C 3 alkyl, O -CO-C 1 -C 20 alkyl or C 1 -C 6 alkyl-SC 1 -C 6 alkyl, C 1 -C 6 alkyl-OC 1 -C 6 alkyl, C 1 -C 6 alkyl- (CO) -C 1 -C 6 alkyl, or ego;
    w is 1 to 10;
    Y is a single bond, C 1 -C 25 alkylene, phenylene, biphenylene, naphthylene, -OC 1 -C 25 alkylene, -NR 9- , -O- or ego;
    Z is a hydrogen atom, -COOR 9- , -NH 2- , -OR 9- , hydroxyethyl, or ego;
    R 9 is hydrogen or C 1 -C 12 alkyl;
    R 10 is as defined for R 8 .
    C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl and C 5 -C 12 cycloalkyl have the meaning given for example in formula (1). C 1 -C 12 alkyl also has the same meaning up to the corresponding number of carbon atoms.
    C 1 -C 25 alkylene is linear or branched such as methylene, ethylene, propylene, isopropylene, n-butylene, s-butylene, iso-butylene, t-butylene, pentylene, hexylene, heptylene , Octylene, nonylene, decylene, dodecylene, tetradecylene, heptadecylene or octadecylene. Y is especially C 1 -C 12 alkylene, such as C 1 -C 8 alkylene, preferably C 1 -C 4 alkylene.
    Particularly preferred examples of formula (2) having epoxy functionality are as follows:
    , And ;
    Wherein R 9 is C 1 -C 12 alkyl.
    Preferred examples of formula (2) having OH- or NH 2 functionality are as follows:
    , , ,
    And ;
    In which x is 1 to 8;
    R 9 is C 1 -C 12 alkyl.
    Those skilled in the art are familiar with the preparation of suitable sterically hindered amine compounds, which are described in EP-A-634 450, EP-A-634 449, EP-A-434-608, EP-A-389 419, EP-A-0 634 399, EP-A-0 001 835 or Makromolekulare Chemie by Luston and Vass, Macromol. Symp. 27, 231 (1989) and other documents.
    Suitable lactones having at least one reactor and reacting with a compatibilizer compound are compounds of formula (3):
    Where
    R 11 , R 12 , R 12a and R 13 are each independently hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl, C 5 -C 12 cycloalkyl or phenyl; And
    G is OH, , -OCH 2 CH 2 OH or -OCH 2 COOH.
    C 1 -C 25 alkyl, C 1 -C 12 alkyl, phenyl-C 1 -C 3 alkyl, C 5 -C 12 cycloalkyl and C 1 -C 25 alkylene are represented by the formulas (1), (2) and (2a) Corresponds to
    Preferred compounds are those of the formula (3), wherein G is a radical OH.
    Particularly suitable compounds of formula (3) are those in which R 11 , R 12 , R 12a and R 13 are hydrogen atoms, C 1 -C 10 alkyl, phenyl-C 1 -C 3 alkyl or cyclohexyl.
    R 11 , R 12 , R 12a and R 13 are preferably C 1 -C 4 alkyl, in particular methyl and t-butyl.
    Preferred compounds of formula (3) are for example:
    , or
    .
    Mixtures of positional isomer compounds can also be used.
    Methods for preparing suitable lactones are known to those skilled in the art and are described in EP-A-591 102 and other documents.
    Suitable sulfides having at least one functional group and reacting with a compatibilizer compound are compounds of formula (4):
    R 15 -SR 16
    Where
    R 15 is C 1 -C 18 alkyl, benzyl, phenyl or ego;
    R 16 is —CH 2 CH 2 OH, , -CH 2 COOH or -CH 2 CH 2 COOH; And
    R 17 is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl.
    The meaning of C 1 -C 18 alkyl and C 1 -C 4 alkyl-substituted phenyl is as defined in formula (1).
    R 15 is preferably C 8 -C 12 alkyl, benzyl or phenyl, in particular C 8 -C 12 alkyl. R 16 is preferably -CH 2 CH 2 OH or to be. Typical examples are Or C 12 H 25 -S-CH 2 CH 2 OH.
    Further suitable compounds of the formula (4) R 15 is , Preferably And to be.
    Methods for preparing suitable sulfides are known to those skilled in the art and described in Abh. Akad. Wiss. DDR Abt. Math., Naturwiss., Tech. (1987), Vol. Oct. 1986 (IN), 511-5; EP-A-166 695, EP-A-413 562 and other documents.
    Suitable phosphites which contain at least one functional group and react with the compatibilizer compound are compounds of formula (5):
    Where
    R 16a is —CH 2 CH 2 OH or —CH 2 CH 2 COOH;
    R 17a is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl.
    The definition of C 1 -C 18 alkyl and C 1 -C 4 alkyl-substituted phenyl is as given in formula (1).
    Particularly suitable phosphites are , And to be.
    The skilled person in this field is Khim. -Famy. Zh. (1998), 22 (2), 170-4 and other documents are familiar with the preparation of suitable phosphites.
    Suitable benzotriazoles, benzophenones and 2- (2-hydroxyphenyl) -1,3,5-triazines comprising at least one functional group and reacting with a compatibilizer compound are formulas (6), (6a), (6b). Or a compound of (6c):

    Where
    R 18 is — (CH 2 ) t —R 20 , Or NH 2 ;
    R 19 is C 1 -C 12 alkyl, α, α-dimethylbenzyl or radical ego;
    R 20 is —OH, —SH, —NHR 30 , —SO 3 H, —COOR 21 , —CH = CH 2 , Or-(CO) -NH- (CH 2 ) u -NCO;
    R 21 is a hydrogen atom, Or -CH 2 -CH (OH) -CH 2 -O- (CO) -R 22 ;
    R 22 is C 1 -C 4 alkyl or phenyl;
    R 23 and R 24 are each independently hydrogen or C 1 -C 4 alkyl;
    R 25 is a hydrogen atom,-(CH 2 ) u -OH, ,-(CH 2 ) u COOH or-(CO) -NH- (CH 2 ) u -NCO;
    R 26 is a hydrogen atom, OH or C 1 -C 12 alkoxy;
    R 27 is hydrogen or OH;
    R 28 is a hydrogen atom or ego;
    R 29 is hydrogen or halogen;
    R 30 is hydrogen or C 1 -C 9 alkyl;
    m is 0 or 1;
    t is 0 to 6;
    u is 2 to 12.
    C 1 -C 4 alkyl is typically straight or branched and is methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, iso-butyl or t-butyl. Methyl is preferred.
    Particularly preferred compounds are for example , Such as hydroxy-substituted benzophenones. These compounds may be further substituted on the aromatic ring, for example by additional hydroxyl groups or alkoxy.
    Chemical formula Benzotriazole is also suitable. In addition to the epoxy-functionalized radicals, hydroxyphenyl groups may also contain alkyl substituents.
    Particularly suitable triazine compounds are for example In the above formula, the phenyl group may be additionally substituted by a methyl group.
    Suitable processes for preparing benztriazole are known to those skilled in the art and are described in EP-A-693 483; Polymer (1995), 36 (17), 3401-8 and other documents. Methods for preparing suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are known to those skilled in the art and described in EP-A-434-608; CA-A-2062217 and other documents. Suitable methods of preparing benzophenones are known to those skilled in the art and are described in EP-A-693 483; EP-A-538 839; Zh. Prikl. Khim. (Leningrad) (1976), 49 (5), 1129-34; JP-A-Hei 3 31235 (Chemical Abstract No. 115: 49102) and other documents.
    The invention also relates to sterically hindered phenols of formula (1), sterically hindered amines of formula (2), (2a) or (2b), lactones of formula (3), sulfides of formula (4), forces of formula (5) Fighting or reacting a benzotriazole, benzophenone or 2,4,6-triaryl-1,3,5-triazine of formula (6), (6a), (6b) or (6c) with a compatibilizer compound Regarding the compounds obtainable:
    (One);
    (2), (2a), (2b);
    (3); R 15 -SR 16 (4);
    (5);
    (6), 6a,
    (6b), (6c);
    In the above formula;
    R 1 and R 2 are each independently a hydrogen atom; C 1 -C 25 alkyl; Phenyl-C 1 -C 3 alkyl unsubstituted or substituted once or multiple times on the aromatic ring by OH and / or C 1 -C 4 alkyl; Unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl; Or phenyl;
    n is 1,2 or 3;
    E is OH, SH, NHR 3 , SO 3 H, COOH, -CH = CH 2 , or ego;
    m is 0 or 1;
    R 3 is hydrogen or C 1 -C 9 alkyl;
    R 4 is C 1 -C 12 alkyl, phenyl unsubstituted or substituted by 1 or several C 1 -C 4 alkyl, halogen and / or C 1 -C 18 alkoxy;
    When E is OH, SH or -CH = CH 2 , A is -C x H 2x- , -CH 2 -S-CH 2 CH 2- , C q H 2q- (CO) -OC p H 2p- , C q H 2q- (CO) -NH-C p H 2p -or -C q H 2q- (CO) -OC p H 2p -SC q H 2q- ;
    x is 0 to 8;
    p is 2 to 8;
    q is 0 to 3;
    R 1 and n are as defined above; or
    When E is -NHR 3 , A is -C x H 2x -or -C q H 2q- (CO) -NH-C p H 2p -and x, p and q are as defined above; or
    When E is COOH or SO 3 H, A is -C x H 2x- , -CH 2 -S-CH 2 -or -CH 2 -S-CH 2 CH 2 -and x is as defined above; or
    E is When A is a direct bond, -C q H 2q- (CO) -O-CH 2 -or -C x H 2x -S-CH 2 -and q, m, x, R 1 and R 2 are defined above As;
    E is When A is -CH 2- ;
    R 8 is a hydrogen atom, C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, phenyl-C 1 -C 3 alkyl, C 5 -C 12 Cycloalkyl, C 5 -C 8 cycloalkoxy, phenyl, naphthyl, hydroxyethyl, CO-C 1 -C 25 alkyl, CO-phenyl, CO-naphthyl, CO-phenyl-C 1 -C 3 alkyl, O -CO-C 1 -C 20 alkyl or C 1 -C 6 alkyl-SC 1 -C 6 alkyl, C 1 -C 6 alkyl-OC 1 -C 6 alkyl, C 1 -C 6 alkyl- (CO) -C 1 -C 6 alkyl, or ego;
    w is 1 to 10;
    Y is a single bond, C 1 -C 25 alkylene, phenylene, biphenylene, naphthylene, -OC 1 -C 25 alkylene, -NR 9- , -O- or ego;
    Z is a hydrogen atom, -COOR 9 , -NH 2 , -OR 9 , hydroxyethyl, or ego;
    R 9 is hydrogen or C 1 -C 12 alkyl;
    R 10 has the same meaning as R 8 ;
    R 11 , R 12 , R 12a and R 13 are each independently hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl, C 5 -C 12 cycloalkyl or phenyl; And
    G is OH, -OCH 2 CH 2 OH, Or -OCH 2 COOH;
    R 15 is C 1 -C 18 alkyl, benzyl, phenyl or ego;
    R 16 is —CH 2 CH 2 OH, , -CH 2 COOH or -CH 2 CH 2 COOH; And
    R 17 is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl;
    R 16a is —CH 2 CH 2 OH or —CH 2 CH 2 COOH;
    R 17a is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl;
    R 18 is — (CH 2 ) t —R 20 , Or NH 2 ;
    R 19 is C 1 -C 12 alkyl, α, α-dimethylbenzyl or radical ego;
    R 20 is —OH, —SH, —NHR 30 , —SO 3 H, —COOR 21 , —CH = CH 2 , Or-(CO) -NH- (CH 2 ) u -NCO;
    R 21 is a hydrogen atom, Or -CH 2 -CH (OH) -CH 2 -O- (CO) -R 22 ;
    R 22 is C 1 -C 4 alkyl or phenyl;
    R 23 and R 24 are each independently hydrogen or C 1 -C 4 alkyl;
    R 25 is a hydrogen atom,-(CH 2 ) u -OH, ,-(CH 2 ) u COOH or-(CO) -NH- (CH 2 ) u -NCO;
    R 26 is a hydrogen atom, OH or C 1 -C 12 alkoxy;
    R 27 is hydrogen or OH;
    R 28 is a hydrogen atom or ego;
    R 29 is hydrogen or halogen;
    R 30 is hydrogen or C 1 -C 9 alkyl;
    m is 0 or 1;
    t is 0 to 6;
    u is 2 to 12.
    Compatibilizers with specific reactors are suitable for preparing new compounds. Such compatibilizers are polymers comprising acid groups, acid anhydride groups, ester groups, epoxy groups or alcohol groups. Also suitable are copolymers or terpolymers of polyethylene, polypropylene, vinyl acetate or styrene with acrylates.
    Typical examples are polymers having acrylic acid (AA) functionality, glycidyl methacrylate (GMA) functionality, methacrylic acid (MAA) functionality, maleic anhydride (MAH) functionality or vinyl alcohol (VA) functionality.
    Preferred compatibilizers are, for example, copolymers of polyethylene acrylic acid (PE-AA), polyethylene glycidyl methacrylate (PE-GMA), polyethylene methacrylic acid (PE-MAA), polyethylene maleic anhydride (PE-MAH) or polyethylene And terpolymers of vinyl acetate and acrylate (such as PE-AA-acrylate).
    Also suitable as compatibilizers are maleic anhydride (MAH-g-PE-vinyl acetate) grafted to polyethylene vinyl acetate, maleic anhydride (MAH-g-LDPE) grafted to low density polyethylene, maleic anhydride (grafted to high density polyethylene) MAH-g-HDPE), maleic anhydride (MAH-g-LLDPE) grafted to low density linear polyethylene, acrylic acid (AA-g-PP) grafted to polypropylene, glycidyl methacrylate (grafted to polypropylene) GMA-g-PP), maleic anhydride (MAH-g-PP) grafted to polypropylene, maleic anhydride (MAH-g-EPDM) grafted to ethylene / propylene terpolymer, male grafted to ethylene / propylene rubber Graft polyethylene or polypropylene copolymer selected from the group consisting of acid anhydride (MAH-g-EPM) and maleic anhydride (MAH-g-PE / PP) grafted to the polyethylene / polypropylene copolymer.
    Other suitable compatibilizer components include styrene / acrylonitrile (SAN-g-MAH) grafted with maleic anhydride, styrene / maleic anhydride / methyl methacrylate, styrene / butadiene styrene block copolymers grafted with maleic anhydride ( SBS-g-MAH), styrene / ethylene / propylene / styrene block copolymer grafted with maleic anhydride (SEPS-g-MAH), styrene / ethylene / butadiene / styrene block copolymer grafted with maleic anhydride (SEPS- g-MAH) and acrylic acid / polyethylene / polystyrene terpolymer (AA-PE-PS-tripolymer).
    Important compatibilizers are those containing anhydride units. Examples of suitable anhydrides are itaconic anhydride, citraconic anhydride, bicyclo [2.2.2] -5-octene-2,3-dicarboxylic anhydride, bicyclo [2.2.1] -5-heptene-2,3- Dicarboxylic acid anhydride or maleic anhydride. Maleic anhydride is preferred.
    Particularly suitable as compatibilizers are copolymers or terpolymers having one anhydride. Typical examples include ethylene / vinyl acetate / maleic anhydride terpolymers, ethylene / ethylacrylate / maleic anhydride terpolymers, ethylene / acrylic acid / maleic anhydride terpolymers, styrene / maleic anhydride copolymers or styrene / maleic anhydride / Methyl methacrylate terpolymer.
    Such polymers and their preparation are known and are described in P.J. Flory in Principles of Polymer Chemistry, 1964, Cornell University Press, Ithaca, NY and Compatibilizers and Polymer Modifiers for Unused and Recycled Thermoplastics Including Multipolymers and Multilayer Materials, Maack Business Services, Study MBS No. 10, 1990 September, described in Zurich.
    Also preferred as compatibilizer components are copolymers or terpolymers comprising grafted anhydrides such as maleic anhydride grafted to polypropylene, maleic anhydride grafted to polyethylene, maleic anhydride grafted to ethylene / vinylacetate copolymers, Styrene / ethylene / propylene / styrene block copolymer (SEPS), styrene / ethylene / butylene / styrene block copolymer (SEBS), maleic anhydride (EPDM) grafted to ethylene / propylene terpolymer, ethylene / propylene copolymer There is grafted maleic anhydride.
    Such graft polymers and their preparation are known and described in H.-G.Elias, Makromolekule 1981, Huthig & Wepf Verlag Heidelberg; Or compatibilizers and polymer modifiers for unused and recycled thermoplastics, including multipolymers and multilayer materials, Maak Business Services, Study MBS No. 10, September 1990, Zurich, as well as M.Xanthos, Reactive Extrusion, 1992, Oxford See University Press, NY.
    The maleic anhydride component is typically from 0.05 to 15%, preferably from 0.1 to 10%.
    Also suitable as compatibilizer components are copolymers or terpolymers comprising unsaturated carboxylic acids, typically acrylic acid, methacrylic acid, crotonic acid, fumaric acid, vinyl acetic acid, maleic acid, itaconic acid. Acrylic acid, methacrylic acid, fumaric acid and maleic acid are preferred, and acrylic acid and methacrylic acid are particularly preferred.
    Examples of such copolymers or terpolymers are ethylene / acrylic acid copolymers, propylene / acrylic acid copolymers or ethylene / propylene / acrylic acid terpolymers. Such polymers and methods for their preparation are described in Compatibilizers and Polymer Modifiers for Unused and Regenerated Thermoplastics, including Multi-Polymers and Multi-Layered Materials, Maak Business Services, Study MBS No. 10, September 1990, Zurich.
    The acrylic acid component is typically 0.1 to 30%, preferably 0.1 to 25%.
    The preparation of polymerizable, copolymerizable and tripolymeric compatibilizers is carried out in conventional polymerization procedures familiar to those skilled in the art. The preparation of carboxyl group-containing polymers is described, for example, in N.G. Published by Gaylord in "Reactive Extrusion; Principles and Practice", Polymer Processing Institute, p. 56, Hanser Verlag, Munchen, Wien, New York (1992). From page 116 of the same document, S. Brown describes a process for preparing other carboxylating compatibilizers.
    Compatibilizer compounds selected from the group consisting of hindered phenols, hindered amines, lactones, sulfides, phosphites, benzotriazoles, benzophenones and 2- (2-hydroxyphenyl) -1,3,5-triazines Reaction with compounds having at least one reactor is carried out in a graft reaction or a polymer-like reaction.
    The reaction can be carried out in solution or in the melt, depending on the reactants.
    In this case, different reactors can be used, such as tanks, extruders, mixers and the like. Extrusion is preferred.
    Reaction extrusion is described in Reactive Extrusion, Principle and Practice by M. Xanthos, Polymer Processing Institute, Hanser Verlag, Munchen 1992.
    The reactants may be premixed or separated, that is, introduced into the extruder through a separate dosing mechanism and reacted in the extruder. Liquid components or low-melt components can also be introduced into the extruder via an input pump (side channel balance). Degassing of the melt in the extruder is also useful and is particularly preferably removed when a low molecular weight product is obtained in the reaction. For this purpose the extruder needs to be equipped with a corresponding degassing apparatus. The production reaction is carried out on a commercially available single- or twin screw extruder. Preferred are twin-screw extruders. Mixing is carried out by conventional techniques such as granulation. It is also possible to produce and use masterbatches (concentrates) from compatibilizers / stabilizers by known methods.
    The ratio of compatibilizer component to stabilizer component in the polymer-like reaction is of course limited by the number of reactors present on the compatibilizer component. Suitable compatibilizer / stabilizer weight ratios are 100: 0.05 to 100: 50, in particular 100: 0.1 to 100: 25, preferably 100: 1 to 100: 20.
    The novel compatibilizer / stabilizer compounds can be used, for example, to stabilize the following polymers and in particular mixtures of these polymers.
    1. Polymers of monoolefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also cyclopentene or Polymers of cycloolefins such as norborene, such as (optionally crosslinkable) polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and branched low density polyethylene (VLDPE).
    2. 1) As mentioned below, for example, mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g. PP / HDPE, PP / LDPE, PP / HDPE / LDPE, PP / HDPE / LLDPE / Mixtures of polymers such as LDPE) and mixtures of other forms of polyethylene (eg, LDPE / HDPE, LLDPE / LDPE, HDPE / LLDPE / LDPE).
    3. For example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but- 1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / alkyl acrylate aerial Copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), as well as ethylene and propylene and hexadiene, dicyclopenta Copolymers of diolefins with monoolefins such as dienes or terpolymers of dienes such as ethylidene-norbornene; And, for example, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene acrylic acid copolymers and alternating or random poly Mixtures of the copolymers described above in 1), such as alkylene / carbon monoxide copolymers, with another, and mixtures of these with polymers such as polyamides.
    4. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).
    5. For example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / Styrene, such as methyl acrylate, or copolymers of α-methyl styrene with dienes or acrylic derivatives; Mixtures of styrene copolymers with high impact strength with other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; And styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.
    6. Graft copolymers of styrene or α-methylstyrene, such as styrene to polybutadiene, styrene to polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; Polybutadiene with styrene, acrylonitrile and methyl methacrylate; Styrene and maleic anhydride in polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; Styrene and maleimide in polybutadiene; Styrene and alkyl acrylates or methacrylates to polybutadiene; Styrene and acrylonitrile in ethylene / propylene / diene terpolymers; Graft copolymers in which styrene and acrylonitrile are grafted to polyalkyl acrylate or polyalkyl methacrylate and styrene and acrylonitrile to acrylate / butadiene copolymer, as well as the copolymers described below 5). Mixtures, such as copolymer mixtures known as ABS, MBS, ASA or AES polymers.
    7. Halogen-containing polymers such as polychloroprene, rubber, copolymers of chlorinated or sulfochloride polyethylene, ethylene and ethylene chloride, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride , Polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymer.
    8. polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; Impact-modified polymethyl methacrylate, polyacrylamide and polyacrylonitrile, modified with butyl acrylate
    9. 8) Copolymers of monomers mentioned below or between other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylics Ronitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.
    10. Unsaturated alcohols and polymers derived from amines, acyl derivatives or their acetals such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl malate, polyvinyl butyral, polyallyl phthalate Or polyallyl melamine; As well as copolymers with the olefins described above in 1).
    11. Polyamides and hybrid polyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / Aromatic polyamides starting from 12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Polyamides prepared with or without elastomers as modifiers from hexamethylenediamine and isophthalic acid and / or terephthalic acid, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly m-phenylene isoph Deamide; And also block copolymers, olefin copolymers, ionomers or chemically bonded or grafted elastomers of the polyamides with polyolefins; Or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as polyamides or hybrid polyamides modified with EPDM or ABS; And polyamides that are condensed during the reaction (RIM polyamide system).
    12. Polyesters derived from dicarboxylic acids and diols and / or hydroxide carboxylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoate As well as block mixed ether esters derived from hydroxyl-terminated polyethers; And also polyesters modified with polycarbonates or MBS.
    13. Polycarbonates and polyester carbonates.
    14. Blends of the above polymers (polyblends), such as PP / EPDM, poly-amide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PA / LDPE, PE / PET, PS / PE, PS / PP, PS / PE / PP, PE / PP / PET / PS.
    The new compatibilizer / stabilizer compound is added to the polymer to be stabilized in an amount of 0.5 to 30%, such as 1 to 20%, preferably 2 to 15% (based on the amount of polymer to be stabilized).
    The amount added depends on the one hand on the number of active stabilizing groups in the compound and on the other hand on the requirements of the polymer or polymer mixture to be stabilized.
    The novel compatibilizer / stabilizer compounds can also be used for phase compatibilization in plastic compositions in which the compounds simultaneously act as stabilizers. Such plastic compositions may be unused plastic compositions (described above) or may be recycled.
    The novel compatibilizer / stabilizer compounds can in principle be used in incompatible plastic compositions, unused or reclaimed or mixtures of unused and recycled. The plastic composition consists of two or more components. The new compound is preferably added to a mixture of polar and nonpolar plastics.
    Nonpolar components of the plastic composition are, for example, polyolefins, typically polyethylene (PE) and polypropylene (PP). Of particular interest are low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) and copolymers such as ULDPE and MDPE as well as ethylene / propylene (EPM) and ethylene / propylene / diene copolymers (EDPM). These nonpolar plastics also incorporate copolymers with polystyrene (PS, EPS) and styrene components (such as ABS, ASA, HIPS, IPS) and polyvinyl chloride (PVC) as well as predominant vinyl chloride components (such as CPE). Include.
    The polar component is, for example, polyester, polyamide or polycarbonate, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).
    Particular preference is given to mixtures of polyethylene and polypropylene or mixtures with polyethylene and polyamides.
    The novel compatibilizer / stabilizer compound is for example 25 to 100% by weight, preferably 35 to 95% by weight, such as 40 to 85% by weight of polyolefin, 0 to 25% by weight of polystyrene, 0 to 25% by weight of polyvinyl chloride And 0 to 25% by weight of other thermoplastics. Non-thermoplastics can also be obtained in small amounts in the mixture.
    Usually low density polyethylene is predominant in polyolefins and polyethylenes (PE). Polystyrene (PS) can also be a copolymer with a predominant styrene component (eg ABS, HIPS) and polyvinyl chloride (PVC) can also be a copolymer with a predominant vinyl chloride component (eg CPE). Other thermoplastics present in the materials used are in particular polyethylene terephthalate (PET) and polyamides, polycarbonates, cellulose acetates and polyvinylidene chlorides. Non-thermoplastics can typically be present in minor amounts of up to 5% in the form of polyurethanes, formaldehyde resins and phenolic resins or aminoplastics as well as natural rubbers or elastomers such as rubber. In addition, small amounts of foreign matter that are difficult to remove, such as paper, pigments, paint systems, printing inks, adhesives, may be present in the plastics used. Small amounts of cellulose or fiber material do not interfere with recycling.
    A mixture of novel compatibilizer / stabilizer compounds is also added to the plastic composition to be stabilized to make it compatible. For example, a mixture of compounds having the same compatibilizer backbone and having different functionalities as stabilizers, typically compounds with phenolic antioxidant functions and compounds with benzotriazole functions, compounds with antioxidant functions and HALS functions It is convenient to use mixtures, mixtures of compounds with HALS function and compounds with UV absorbing function or mixtures of compounds with antioxidant function and compounds with HALS function and compounds with UV absorbing function.
    The plastic composition may additionally be mixed with other additives known to the skilled person. Such additional additives are used in combination in conventional amounts and are described in detail in the following literature (“Plastic Additives” Gachter / Muller, Hanser Verlag, Munchen / Wien / New York, 3rd edition).
    Typically the novel compatibilizer / stabilizer compounds can be incorporated into the polymer or polymer mixture to be stabilized according to the following method:
    As an emulsion or dispersion,
    As a dry mixture while mixing additional components or polymer mixtures,
    By directly introducing a manufacturing apparatus (e.g. calender, blender, kneader, extruder, etc.),
    As a solution or melt.
    The plastic composition can be prepared by a known method by mixing the novel compound and optional additives with the plastic composition using a known device, such as the preparation device described above. Additional additives may be added alone or in mixtures in the form of so-called masterbatches.
    The compatibilizer / stabilizer compound and compatible plastic composition are prepared by directly adding a suitable monofunctional functionalizing stabilizer compound and a radical initiator to the plastic composition, i.e., by not preparing the compatibilizer / stabilizer compound in advance. It is possible to manufacture in a one step process. In a similar manner, suitable monofunctional functionalized stabilizer compounds and corresponding compatibilizers can be processed together with the polymer mixture to react with the stabilizer compounds without the need for processing the compatibilizer compounds first, thereby simultaneously obtaining an improved compatibilized polymer mixture.
    The plastic composition obtainable according to the invention can be in the desired shape according to known methods. Such methods are, for example, by grinding, calendering, extrusion, injection molding, sintering or spinning and extrusion blow molding or plastisol processing.
    The novel manufacturing process involves two different aspects which can be achieved using the novel polymerizable compatibilizer / stabilizer compound, two different objectives.
    On the one hand, the polymers are compatible with each other in different polymer mixtures (unused material or rework) that will form multiple phases without compatibilizers, thereby stabilizing the polymers simultaneously.
    On the other hand, since the polymer backbone of the compatibilizer / stabilizer compound is compatible with the polymer to be stabilized, the stabilizer becomes compatible or the solubility in the polymer is improved.
    It also reduces the migration of stabilizers from the polymer, for example in the extraction medium. In such cases, for example, the compounds are used in fuel tanks, geotextiles, dry cleaning fibers (eg fabrics, carpet layers), pipes, food contact articles and the like.
    The following examples illustrate the invention in more detail. Parts and percentages herein are parts by weight and percentages unless otherwise indicated.
    I) Preparation of Functionalized Polymer
    Example A
    On a twin screw-screw extruder (TW 100, Haake, Germany), 2% 2,3-epoxypropyl-3,5-bis (1,1- 2) at 210-230 ° C. (heating zones 1-5) and 45 rpm The SEBS copolymer (styrene / ethylene / butadiene / styrene copolymer) is extruded together with the maleic anhydride group (Kraton R FG 1901, shell product) with the addition of dimethylethyl) -4-hydroxybenzenepropionate. The original form was no longer observed in the analysis by gas chromatography performed continuously; That is, fully chemically bonded to the polymer chain.
    Example B
    Polyethylene / acrylic acid / acrylate (Lucalen R A 3110 MX, manufactured by BASF) in 2% 2,3-epoxypropyl 3,5-bis (1,1-dimethylethyl) -4-hydrate Extruded with oxybenzenepropionate.
    Example C
    The procedure of Example B is repeated but 4% of 2,3-epoxypropyl 3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropionate is used.
    Example D
    In a manner similar to Example A, the SEBS copolymer with maleic anhydride groups is reacted with 2% 1,2,2,6,6-pentamethyl-4- (2,3-epoxypropyloxy) piperidine.
    Example E
    In a manner similar to Example B, polyethylene / acrylic acid / acrylate is reacted with 2% of 1,2,2,6,6-pentamethyl-4- (2,3-epoxypropyloxy) piperidine.
    Example F, G, H
    Similar methods as in Example E use 1,2,2,6,6-pentamethyl-4- (2,3-epoxypropyloxy) piperidine of 4%, 6% and 8%, respectively.
    Ⅱ) Use of Polymeric Stabilizer
    Examples 1 to 3 (impact strength upon oven aging action)
    To test the obtained product, a mixture of 70% LDPE, low density polyethylene (Lupolen R 3026F, manufactured by BASF) and polyamide 6 (Ultramid R B30, pre-dried, manufactured by BASF) was functionalized A test sample is mixed with a compatibilizer at 240 ° C., 75 rpm (double-screw extruder TW 100, Haake, Germany), granulated and injection molded at 240 ° C. The impact strength of this test sample is determined according to DIN 53 448 upon aging at 100 ° C. in a circulating air oven.
    For comparison, compositions comprising the corresponding non-functionalized compounds in place of the functionalized compatibilizers are prepared and tested.
    The compositions tested and the results are shown in Table 1 below. The higher the impact strength value, the more stable the test composition.
    Example5% of each additiveImpact strength [kJ / ㎡] 0 hours500 hours1000 hours2500 hours5000 hours7725 hours-2921581611136053Kraton FG 1901571509458451311241Lucaren A 3110 MX673476361195145112 OneCompound of Example A544503479473448428 2Compound of Example B663581583570538478 3Compound of Example C692580578571538419
    The values obtained indicate that the functionalized compatibilizer stabilizes the polymer more effectively with longer aging times as compared to the non-functionalized compatibilizer.
    Examples 4 to 8: (impact strength at the time of artificial weathering test)
    Test samples are prepared in a similar manner to those described in Examples 1 to 3 to determine the impact strength during artificial weathering tests. The weather resistance test is carried out in a weather tester (type Ci 65A, manufactured by Atlas, BPT (black panel temperature) 63 ° C., RH (relative humidity) 60%, water spray).
    The compositions and test results are shown in Table 2 below.
    Example5% of each additiveImpact strength [kJ / ㎡] 0 hours1000 hours2000 hours5000 hours-2929910493Kraton FG 1901571835245Lucaren A 3110 MX6731229755 4Compound of Example D569456408283 5Compound of Example E702651503249 6Compound of Example F635588485269 7Compound of Example G668670533362 8Compound of Example H596535476416
    The figures obtained indicate that the functionalized compatibilizer stabilizes the polymer more effectively with longer weathering tests than the non-functionalized compatibilizer.
    Examples 9 to 12 (impact strength upon aging after extraction)
    A mixture of 70% low density polyethylene (LDPE) (Lupolen R 3026 F, BASF) and 30% polyamide 6 (Ultramid R B36, pre-dried, BASF) was mixed with a new compatibilizer / stabilizer compound 240 The test is carried out in a twin-screw extruder at 75 rpm. Test samples are injection molded at 240 ° C.
    The test sample is stored in extraction medium:
    A) In a white split for 25 days at room temperature,
    B) in water with 1% Igepal CO630 (nonoxynol 9) for 2 weeks at 40 ° C.
    The dried test sample is aged at 100 ° C. in a circulating air oven. The impact strength during aging is measured in accordance with DIN 53 448.
    The higher the impact strength value and the less this value decreases after aging, the more stable the test composition is. The test results for the test compound and the extraction variant A are shown in Table 3, and the test results for the extraction variant B are shown in Table 4.
    LDPE / PA670: 30Impact strength after extraction in white split [kJ / ㎡] Example 0 hours503 hours723 hours1006 hours1990 hours4004 hours 95% of the compound of Example B535554574582595538 105% of the compound of Example C547542557541567515
    LDPE / PA670: 30Impact strength after extraction in water / surfactant [kJ / ㎡] Example 0 hours235 hours498 hours750 hours1241 hours2995 hours 115% of the compound of Example B636579591600591578 125% of the compound of Example C661539575563580555
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] From the group consisting of sterically hindered phenols, sterically hindered amines, lactones, sulfides, phosphites, benzotriazoles, benzophenones and 2- (2-hydroxy-phenyl) -1,3,5-triazines having at least one functional group A method of stabilizing a plastic or plastic composition and simultaneously phase compatibilizing by incorporating a polymerizable compound obtainable by reacting the selected compound with a compatibilizer.
    [2" claim-type="Currently amended] The process of claim 1 wherein the sterically hindered phenol is a compound of formula (1):
    (One)
    Where
    R 1 and R 2 are each independently a hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl unsubstituted or substituted one or more on the aromatic ring with OH and / or C 1 -C 4 alkyl , Unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, or phenyl;
    n is 1, 2 or 3;
    E is OH, SH, NHR 3 , SO 3 H, COOH, -CH = CH 2 , or ego;
    m is 0 or 1;
    R 3 is hydrogen or C 1 -C 9 alkyl;
    R 4 is C 1 -C 12 alkyl, or phenyl unsubstituted or substituted with one or several C 1 -C 4 alkyl, halogen and / or C 1 -C 18 alkoxy;
    When E is OH, SH or -CH = CH 2 , A is -C x H 2x- , -CH 2 -S-CH 2 CH 2- , -C q H 2q- (CO) -OC p H 2p , -C q H 2q- (CO) -NH-C p H 2p -or -C q H 2q- (CO) -OC p H 2p -SC q H 2q- ;
    x is 0 to 8;
    p is 2 to 8;
    q is 0 to 3;
    R 1 and n are as defined above; or
    When E is -NHR 3 , A is -C x H 2x -or -C q H 2q- (CO) -NH-C p H 2p -and x, p and q are as defined above;
    When E is COOH or SO 3 H, A is -C x H 2x- , -CH 2 -S-CH 2 -or -CH 2 -S-CH 2 CH 2 -and x is as defined above;
    E is When A is a direct bond, -C q H 2q- (CO) m -O-CH 2 -or -C x H 2x -S-CH 2 , and q, m, x, R 1 and R 2 are As defined;
    E is When A is -CH 2- .
    [3" claim-type="Currently amended] The process of claim 1 wherein the sterically hindered amine is a compound of formula (2), (2a) or (2b):
    (2) (2a)
    (2b)
    Where
    R 8 is a hydrogen atom, C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, phenyl-C 1 -C 3 alkyl, C 5 -C 12 Cycloalkyl, C 5 -C 8 cycloalkoxy, phenyl, naphthyl, hydroxyethyl, CO-C 1 -C 25 alkyl, CO-phenyl, CO-naphthyl, CO-phenyl-C 1 -C 3 alkyl, O -CO-C 1 -C 20 alkyl or C 1 -C 6 alkyl-SC 1 -C 6 alkyl, C 1 -C 6 alkyl-OC 1 -C 6 alkyl, C 1 -C 6 alkyl- (CO) -C 1 -C 6 alkyl, or ego;
    w is 1 to 10;
    Y is a single bond, C 1 -C 25 alkylene, phenylene, biphenylene, naphthylene, -OC 1 -C 25 alkylene, -NR 9- , -O- or ego;
    Z is a hydrogen atom, -COOR 9 , -NH 2 , -OR 9 , hydroxyethyl, or ego;
    R 9 is hydrogen or C 1 -C 12 alkyl;
    R 10 is as defined for R 8 .
    [4" claim-type="Currently amended] The process of claim 1 wherein the lactone is a compound of formula (3):
    (3)
    Where
    R 11 , R 12 , R 12a and R 13 are each independently hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl, C 5 -C 12 cycloalkyl or phenyl; And
    G is OH, OCH 2 CH 2 OH, Or -OCH 2 COOH.
    [5" claim-type="Currently amended] The process of claim 1 wherein the sulfide is a compound of formula (4):
    R 15 -SR 16 (4)
    Wherein R 15 is C 1 -C 18 alkyl, benzyl, phenyl or ego;
    R 16 is —CH 2 CH 2 OH, , -CH 2 COOH or -CH 2 CH 2 COOH; And
    R 17 is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl.
    [6" claim-type="Currently amended] The process of claim 1 wherein the phosphite is a compound of formula (5):
    (5)
    Where
    R 16a is —CH 2 CH 2 OH or —CH 2 CH 2 COOH;
    R 17a is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl.
    [7" claim-type="Currently amended] The method of claim 1, wherein the benzotriazole, benzophenone and 2,4,6-triaryl-1,3,5-triazine are compounds of formula (6), (6a), (6b) or (6c) :
    (6) (6a)
    (6b) (6c)
    Where
    R 18 is — (CH 2 ) t —R 20 , Or NH 2 ;
    R 19 is C 1 -C 12 alkyl, α, α-dimethylbenzyl or radical ego;
    R 20 is —OH, —SH, —NHR 30 , —SO 3 H, —COOR 21 , —CH = CH 2 , Or-(CO) -NH- (CH 2 ) u -NCO;
    R 21 is a hydrogen atom, Or -CH 2 -CH (OH) -CH 2 -O- (CO) -R 22 ;
    R 22 is C 1 -C 4 alkyl or phenyl;
    R 23 and R 24 are each independently hydrogen or C 1 -C 4 alkyl;
    R 25 is a hydrogen atom,-(CH 2 ) u -OH, ,-(CH 2 ) u COOH or-(CO) -NH- (CH 2 ) u -NCO;
    R 26 is a hydrogen atom, OH or C 1 -C 12 alkoxy;
    R 27 is hydrogen or OH;
    R 28 is a hydrogen atom or ego;
    R 29 is hydrogen or halogen;
    R 30 is hydrogen or C 1 -C 9 alkyl;
    m is 0 or 1;
    t is 0 to 6;
    u is 2 to 12.
    [8" claim-type="Currently amended] The method of claim 1 wherein the compatibilizer compound is a polymer comprising an acid group, an acid anhydride group, an ester group, an epoxy group or an alcohol group or a copolymer or terpolymer of polyethylene, polypropylene, vinyl acetate or styrene with acrylic acid.
    [9" claim-type="Currently amended] The compound according to claim 8, wherein the compatibilizer compound has an acrylic acid (AA) function, a glycidyl methacrylate (GMA) function, a methacrylic acid (MAA) function, a maleic anhydride (MAH) function or a vinyl alcohol (VA) function. Method of polymer.
    [10" claim-type="Currently amended] The compound of claim 8 wherein the compatibilizer compound is polyethylene acrylic acid (PE-AA), polyethylene glycidyl methacrylate (PE-GMA), polyethylene methacrylic acid (PE-MAA) or polyethylene maleic anhydride (PE-MAH). A copolymer or a terpolymer of polyethylene and vinyl acetate and acrylic acid or a terpolymer of polyethylene and acrylate and acrylic acid.
    [11" claim-type="Currently amended] 9. The compatibilizer compound according to claim 8, wherein the compatibilizer compound is maleic anhydride (MAH-g-PE-vinyl acetate) grafted to polyethylene vinyl acetate, maleic anhydride (MAH-g-LDPE) grafted to low density polyethylene, graft to high density polyethylene Maleic anhydride (MAH-g-HDPE), maleic anhydride (MAH-g-LLDPE) grafted to low density linear polyethylene, acrylic acid (AA-g-PP) grafted to polypropylene, glycine grafted to polypropylene Diyl methacrylate (GMA-g-PP), maleic anhydride (MAH-g-PP) grafted to polypropylene, maleic anhydride (MAH-g-EPDM) grafted to ethylene / propylene terpolymer, ethylene / propylene Graft polyethylene or polypropylene copolymers selected from the group consisting of maleic anhydride (MAH-g-EPM) grafted to rubber and maleic anhydride (MAH-g-PE / PP) grafted to polyethylene / polypropylene copolymer Way.
    [12" claim-type="Currently amended] The styrene / acrylonitrile (SAN-g-MAH) grafted with maleic anhydride, styrene / maleic anhydride / methyl methacrylate, styrene / butadiene styrene grafted with maleic anhydride Block copolymer (SBS-g-MAH), styrene / ethylene / propylene / styrene block copolymer grafted with maleic anhydride (SEPS-g-MAH), styrene / ethylene / butadiene / styrene block grafted with maleic anhydride A graft styrene co- or terpolymer selected from the group consisting of copolymer (SEPS-g-MAH) and acrylic acid / polyethylene / polystyrene terpolymer (AA-PE-PS-tripolymer).
    [13" claim-type="Currently amended] The method of claim 8, wherein the compatibilizer compound is a vinyl alcohol copolymer.
    [14" claim-type="Currently amended] The method of claim 1 wherein the polymer to be stabilized is at least two different polymers.
    [15" claim-type="Currently amended] The method of claim 1 wherein the polymer to be stabilized is a recycled material.
    [16" claim-type="Currently amended] Sterically hindered phenols of formula (1), sterically hindered amines of formula (2), (2a) or (2b), lactones of formula (3), sulfides of formula (4), phosphites or formulas (5) 6), (6a), (6b) or (6c) benzotriazole, benzophenone or 2,4,6-triaryl-1,3,5-triazine can be obtained by reaction with a compatibilizer compound compound:
    (One);
    (2), (2a), (2b);
    (3); R 15 -SR 16 (4);
    (5);
    (6), 6a,
    (6b), (6c);
    Where
    R 1 and R 2 are each independently a hydrogen atom; C 1 -C 25 alkyl; Phenyl-C 1 -C 3 alkyl unsubstituted or substituted one or more on the aromatic ring by OH and / or C 1 -C 4 alkyl; Unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl; Or phenyl;
    n is 1, 2 or 3;
    E is OH, SH, NHR 3 , SO 3 H, COOH, -CH = CH 2 , or ego;
    m is 0 or 1;
    R 3 is hydrogen or C 1 -C 9 alkyl;
    R 4 is C 1 -C 12 alkyl, phenyl unsubstituted or substituted by 1 or several C 1 -C 4 alkyl, halogen and / or C 1 -C 18 alkoxy;
    When E is OH, SH or -CH = CH 2 , A is -C x H 2x- , -CH 2 -S-CH 2 CH 2- , -C q H 2q- (CO) -OC p H 2p- , -C q H 2q- (CO) -NH-C p H 2p -or -C q H 2q- (CO) -OC p H 2p -SC q H 2q- ;
    x is 0 to 8;
    p is 2 to 8;
    q is 0 to 3;
    R 1 and n are as defined above; or
    When E is -NHR 3 , A is -C x H 2x -or -C q H 2q- (CO) -NH-C p H 2p -and x, p and q are as defined above; or
    When E is COOH or SO 3 H, A is -C x H 2x- , -CH 2 -S-CH 2 -or -CH 2 -S-CH 2 CH 2 -and x is as defined above; or
    E is When A is a direct bond, -C q H 2q- (CO) -O-CH 2 -or -C x H 2x -S-CH 2 -and q, m, x, R 1 and R 2 are defined above As;
    E is When A is -CH 2- ;
    R 8 is a hydrogen atom, C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, phenyl-C 1 -C 3 alkyl, C 5 -C 12 Cycloalkyl, C 5 -C 8 cycloalkoxy, phenyl, naphthyl, hydroxyethyl, CO-C 1 -C 25 alkyl, CO-phenyl, CO-naphthyl, CO-phenyl-C 1 -C 3 alkyl, O -CO-C 1 -C 20 alkyl or C 1 -C 6 alkyl-SC 1 -C 6 alkyl, C 1 -C 6 alkyl-OC 1 -C 6 alkyl, C 1 -C 6 alkyl- (CO) -C 1 -C 6 alkyl, or ego;
    w is 1 to 10;
    Y is a single bond, C 1 -C 25 alkylene, phenylene, biphenylene, naphthylene, -OC 1 -C 25 alkylene, -NR 9- , -O- or ego;
    Z is a hydrogen atom, -COOR 9 , -NH 2 , -OR 9 , hydroxyethyl, or ego;
    R 9 is hydrogen or C 1 -C 12 alkyl;
    R 10 has the same meaning as R 8 ;
    R 11 , R 12 , R 12a and R 13 are each independently hydrogen atom, C 1 -C 25 alkyl, phenyl-C 1 -C 3 alkyl, C 5 -C 12 cycloalkyl or phenyl; And
    G is OH, OCH 2 CH 2 OH, Or -OCH 2 COOH;
    R 15 is C 1 -C 18 alkyl, benzyl, phenyl or ego;
    R 16 is —CH 2 CH 2 OH, , -CH 2 COOH or -CH 2 CH 2 COOH; And
    R 17 is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl;
    R 16a is —CH 2 CH 2 OH or —CH 2 CH 2 COOH;
    R 17a is C 1 -C 18 alkyl or unsubstituted or C 1 -C 4 alkyl-substituted phenyl;
    R 18 is — (CH 2 ) t —R 20 , Or NH 2 ;
    R 19 is C 1 -C 12 alkyl, α, α-dimethylbenzyl or radical ego;
    R 20 is —OH, —SH, —NHR 30 , —SO 3 H, —COOR 21 , —CH = CH 2 , Or-(CO) -NH- (CH 2 ) u -NCO;
    R 21 is a hydrogen atom, Or -CH 2 -CH (OH) -CH 2 -O- (CO) -R 22 ;
    R 22 is C 1 -C 4 alkyl or phenyl;
    R 23 and R 24 are each independently hydrogen or C 1 -C 4 alkyl;
    R 25 is a hydrogen atom,-(CH 2 ) u -OH, ,-(CH 2 ) u COOH or-(CO) -NH- (CH 2 ) u -NCO;
    R 26 is a hydrogen atom, OH or C 1 -C 12 alkoxy;
    R 27 is hydrogen or OH;
    R 28 is a hydrogen atom or ego;
    R 29 is hydrogen or halogen;
    R 30 is hydrogen or C 1 -C 9 alkyl;
    m is 0 or 1;
    t is 0 to 6;
    u is 2 to 12.
    [17" claim-type="Currently amended] Use of a compound according to claim 16 as a stabilizer and simultaneously a phase compatibilizer in a plastic or plastic composition.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-10-31|Priority to EP96810726
    1996-10-31|Priority to EP96810726.8
    1997-10-20|Application filed by 시바 스폐셜티 케미칼스 홀딩 인코포레이티드
    2000-07-25|Publication of KR20000049270A
    2005-06-17|Application granted
    2005-06-17|Publication of KR100496132B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP96810726|1996-10-31|
    EP96810726.8|1996-10-31|
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