Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/06—Oxidation

Definitions

• the present invention relates to oxidized polyolefin waxes with a molecular weight M w in the range from 1000 to 40,000 g / mol, which are obtained by oxidation of polyolefins by means of catalysis with a single-site catalyst based on a complex of a transition metal from groups 5 to 8 of the Periodic table of the elements with no more than one cyclopentadienyl system per metal atom were obtained.
• the present invention also relates to a process for the preparation of oxidized polyolefin waxes by oxidation of polyolefins having a molecular weight M w in the range from 1000 to 40,000 g / mol with oxygen-containing agents at a temperature in the range from 140 to 350 ° C., and to the use of oxidized Waxes as or in coating compositions, as or in floor care products or leather care products, and the use of oxidized polyolefin waxes as or in coating compositions for citrus fruits.
• Oxidized polyolefin waxes are known as such. They are generally obtained by oxidation of generally low molecular weight Ziegler polyethylene, Phillips polyethylene (PE-HD) or also high pressure polyethylene (PE-LD) with air or pure oxygen, see. for example, Kunststoff-Handbuch, Vol.4, p.161 ff. Carl-Hanser-Verlag, 1969.
• PE-HD Phillips polyethylene
• PE-LD high pressure polyethylene
• Such oxidized waxes are used as coating compositions for various fields of application, for example in the surface treatment of floors or citrus fruits.
• carboxyl groups are formed in or on the polymer chains of the starting polyolefin, the number of which can be determined via the so-called acid number.
• a high acid number of the waxes is generally advantageous because the waxes are more dispersible and usable.
• DE-A 196 17 230 discloses oxidized polyethylene waxes which are obtained by oxidation of waxes produced by means of metallocene catalysis.
• EP-A 0 890 583 a process for the oxidation of polyethylene waxes is known, in which inorganic or organic acids are added to the polyethylene melt.
• the waxes obtainable according to DE-A 19617 230 and EP-A 0 890 583 have significantly lower melt viscosities than the starting materials. This is due to the degradation of the polymer chains. A strong degradation of the polymer chains is disadvantageous, however, because this reduces the performance properties. In particular, the hardness in applications of the oxidized waxes known from the prior art in or as floor care products or coating compositions, for example for citrus fruits, can still be improved.
• reaction times for the oxidation are in the range of several hours and are therefore disadvantageously long, which leads to a lower capacity of the plant.
• the object of the present invention was therefore to remedy the disadvantages mentioned and in particular to provide oxidized polyolefin waxes with a relatively high molecular weight and at the same time a large acid number, a large saponification number and a comparatively high hardness and with a high melting point.
• oxidized waxes have been found which have been prepared by oxidation of polyolefin waxes which have been obtained by catalysis of selected complexes of transition metals from groups 5 to 8 of the Periodic Table of the Elements.
• the oxidized waxes according to the invention have a molecular weight M w in the range from 1000 to 40,000 g / mol.
• a process for the production of the oxidized polyolefin waxes according to the invention by oxidation of polyolefins having a molecular weight M w in the range from 1000 to 40,000 g / mol with oxygen-containing agents at a temperature in the range from 140 to 350 ° C. was found.
• the use of oxidized waxes as or in coating compositions the use of oxidized waxes as or in floor care products and the use of oxidized waxes as or in coating compositions for citrus fruits have been found.
• the polyolefins on which the oxidized waxes are based have a weight-average molecular weight M w , determined using the gel permeation chromatography (GPC) method in 1, 2,4-trichlorobenzene at 135 ° C. with a polyethylene or polypropylene standard, in the range from 1000 to 40,000 g / mol, preferably in the range of
• the polydispersity M w / M n of the polyolefins on which the oxidized waxes are based, measured using the GPC method as described, is generally in the range from 1.5 to 3.0, preferably in the range from 1.8 to 2.5.
• the polyolefins on which the oxidized waxes are based can be obtained by polymerizing the corresponding monomers in the presence of complexes of the general formulas Ia to c.
• Waxes which can be produced with the aid of single-site catalysts of a transition metal from groups 5 to 8 of the periodic table which contain at most one cyclopentadienyl system per transition metal atom are known as such.
• the chromium complexes required for this are compounds of the general formulas I a to c.
• M is an element from the series V, Nb, Ta, Cr, Mo, W, Mn, Fe in the oxidation state +3; preferably V, Cr or Mo and particularly preferably Cr;
• X 1 , X 2 are selected from
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being particularly preferred; trifluoroacetate, BF 4 -, PF 6 ⁇ or SbF 5 _ ,
• C ⁇ -C 8 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethyl propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-Cg-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pent
• C 3 -Ci 2 ⁇ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohe tyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• C 7 - to C 2 o-aralkyl preferably C 7 - to C 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1- Phenylbutyl, 2-phenylbuyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl,
• C 6 -C ! 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-A thryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phena.nthryl, preferably phenyl, 1-waphthyl and 2-naphthyl, particularly preferably phenyl; - C 12 -C alkoxy, preferably Ci-Cg-alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso -Pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy or - NR 8 R 9 , where R 8
• amino groups with saturated rings are the .W-piperidyl group and the N-pyrrolidinyl group;
• amino groups with unsaturated Ririgen are the N-pyrryl group, the -indolyl group and the N-carbazolyl group;
• X is preferably 1 and X 2, most preferably equal to X 1 and X 2 is chlorine.
• R 1 to R 6 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -C-Ci 8 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethyl propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-Cg-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-
• C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C - to C 2 o-aralkyl preferably C to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl- butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• C 5 -Ci 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, silyl, SiR 10 R 11 R 12 , where R 10 to R 12 independently of one another from hydrogen, C 1 -C 2 alkyl, C 1 -C aralkyl and C 6 -C ⁇ 4 aryl are selected; trimethylsilyl-, triethylsilyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethyl-thexylsilyl-, tert.
• Siloxy OSiR 10 R 1 L R 12 , where R 10 to R 12 are independently selected from hydrogen, C 1 -C 2 alkyl, C 1 -C 5 aralkyl and C 6 -C 4 arl; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert.
• C 1 -C 2 -alkoxy preferably C 1 -C 6 -alkoxy such as methoxy, ethoxy, n-
• C 6 -Ci 4 aryl which in turn is substituted with one or more C 1 -C 12 alkyl, C 1 -C 2 alkenyl, C 3 -Ci 2 cycloalkyl, C e -Ci 4 aryl, silyl SiR 10th R 1: L R 12 , Siloxy OSiR ⁇ ⁇ 12 or
• two adjacent residues can form a 5- to 10-membered ring with the inclusion of the parent aromatic.
• Z 1 to Z 4 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -Ci 8 _ Al yl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,
• C 2 -C 2 alkenyl preferably C 2 - to ⁇ -Cs-alkenyl such as vinyl, allyl, but-3-en-1-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
• C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C to C 2 o-aralkyl preferably C to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-prop
• C 6 -Ci 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, - silyl SiR 10 R 11 R 12 , where R 10 to R 12 independently of one another from hydrogen, -CC 2 -alkyl, C-Ci 5 ⁇ aralkyl and Cg-C ⁇ aryl are selected; Preference is given to trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl-thexylsilyl, tert-butyldimethylsilyl, tert.
• C 1 -C 2 alkoxy preferably C 1 -C 6 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso Pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
• C 6 -Ci 4 aryl which in turn is substituted with one or more C 1 -C 2 alkyl, C 1 -C alkenyl, C 3 -C 2 ⁇ cycloalkyl, C 6 -Ci 4 aryl, silyl SiR ⁇ R ⁇ R, siloxy OSiR ⁇ R H Rl or -C-Ci 2 ⁇ alkoxy, these groups being specified as above;
• a 2 selected from oxygen, sulfur, NR 13 or PR 13 , preferably NR 13 or PR 13 , where R 13 is as specified above.
• two adjacent radicals can form a 5- to 10-membered ring with the inclusion of the stamaromat.
• X 3 , X 4 and X 5 are independently of one another - halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being particularly preferred;
• Ci-Cis-Al yl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-
• Nonyl, n-decyl, and n-dodecyl preferably Ci-Cg-alkyl such as
• C 3 -Ci 2 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,
• C 7 - to C 2 o-aralkyl preferably C 7 - to C 12 -phenylalkyl such as
• C 6 -C 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,
• 1-naphthyl and 2-naphthyl particularly preferably phenyl; -C-Ci 2 _ lkoxy, preferably -C-C 6 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso Pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy or
• R 8 and R 9 are independently selected from hydrogen, -CC 2 alkyl, C 2 -C 2 alkenyl and C 6 -C 4 aryl, which are a saturated or unsaturated 5- to Can form 10-membered ring; the dimethylamino, the diethylamino, the diisopropylamino, the methylphenyla ino group and the diphenylamino group are preferred.
• Examples of amino groups with saturated rings are the N-piperidyl group and the N-pyrrolidinyl group;
• amino groups with unsaturated rings are the N-pyrryl group, the N-indolyl group and the W-carbazolyl group;
• X 3 to X 5 are preferably the same, very particularly preferably X 3 to X 5 are chlorine.
• u 1 to Nu 3 are selected independently of one another from N or P, Nu 1 and Nu 2 are preferably each N and particularly preferably Nu 1 to Nu 3 are each N.
• R 14 to R 15 are independently of one another hydrogen, halogen such as fluorine , Chlorine, bromine or iodine, with chlorine and bromine being preferred;
• Ci-Cis-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo -Pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-p
• Butyl, C 1 -C 12 alkyl substituted one or more times with donor atoms for example non-cyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example methoxymethyl, ethoxymethyl, ethoxyethyl, ⁇ -hydroxyethyl, ⁇ -ethoxypropyl, (2-ethylhexyloxy) propylidene, methoxyethoxypropylidene or ⁇ -dimethylaminopropyl; one or more halogenated -CC 2 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromethyl, tribromo- methyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl and perflu
• C 2 ⁇ -C 2 alkenyl preferably C 2 - to ⁇ -Cs-alkenyl such as vinyl, allyl, but-3-en-l-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and
• C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C 7 to C ⁇ 2 o _ aralkyl preferably C 7 - to C 2 phenylalkyl such as benzyl, 1-Pheriethyl, 2-phenethyl, 1-phenyl propyl, 2-propyl phenyl, 3 -phenyl -propyl, 1- Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• C 6 -Ci 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, silyl SiR 10 R 1: ⁇ -R 12 , where R 10 to R 12 independently of one another from hydrogen, C ⁇ -C ⁇ 2 alkyl, C 7 -C ⁇ s -Aralkyl and C 6 -Ci 4 -aryl are selected; the trimethylsilyl-, triethylsilyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethyl-thexylsilyl-, tert-butyldimethylsilyl-,
• silyloxy OSiR 10 R 1 L R 12 , where R 10 to R 12 are independently selected from hydrogen, C 1 -C 2 alkyl, C 7 -Ci 5 aralkyl and C 6 -Ci 4 ⁇ Ar 1; preferred are the tri ethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert. the trimethyl silyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred;
• C ⁇ -Ci 2 alkoxy preferably -CC 6 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec. -Butoxy, tert. -Butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-
• Cg-Ci 4 -aryl which in turn is substituted with one or more -CC 12 alkyl, -CC 2 alkenyl, C 3 -Ci 2 cycloalkyl, C 5 -C 4 aryl, silyl Si l ⁇ R ll R l2 f süo y OSiR 10 R 1: 1 -R 12 or -CC 2 alkoxy, these groups being specified as above; R 14 to R 15 are preferably the same.
• R 17 to R 22 are independent of one another
• ⁇ C ⁇ -Ci 8 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dirnethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl
• C ⁇ C 2 alkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl perifluoromethyl, difluoromethyl, C 1 -C 2 alkyl substituted one or more times with donor atoms *, for example non-cyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example methoxymethyl, ethoxymethyl, ethoxyethyl, ⁇ -hydroxyethyl, ⁇ -ethoxypropyl, (2-ethylhexyloxy) propylidene, methoxyethoxypropylidene or ⁇ -d
• C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C 7 - to C 2 o-aralkyl preferably C 7 - to C ⁇ 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1- Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
• C 6 -Ci aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, - silyl SiR 10 R 11 R 12 , where Rio to R 12 independently of one another from hydrogen, C 1 -C 2 -alkyl, C 7 -C 5 aralkyl and Cs -C ⁇ -Ar l are selected; the trimethylsilyl, triethylsi- lyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethyl-thexylsilyl-, tert-butyldimethylsilyl-,
• R 10 to R 12 are independently selected from hydrogen, C 1 -C 2 alkyl, C 7 -C 5 aralkyl and C 6 -Ci 4 aryl; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert-butyldimethylsilyloxy, tert.
• n-pentoxy iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n ⁇ propoxy and n-butoxy;
• - C 6 -C-aryl which in turn are substituted by one or more C ⁇ -Ci 2 -alkyl, C 2 alkenyl, C 3 -C 2 cycloalkyl, C 6 -C 4 aryl, silyl SiR 10 R 11 R 12 , siloxy OSiR 10 R H R i2 or C ⁇ -Ci 2 alkoxy, these groups "as specified above;
• R 17 , R 19 and R 2X are each the same, and preferably R x8 , R 20 and R 22 are each hydrogen.
• R 17 to R 22 are very particularly preferably hydrogen.
• the triazacyclohexane ligands necessary for the synthesis of these very particularly preferred compounds can be synthesized particularly well.
• the metal complexes in particular the chromium complexes, can be obtained in a simple manner if the corresponding metal salts such as e.g. Reacts metal chlorides or metal carbonyls with the ligand, e.g. B. in P. Chaudhuri, K. "Wieghardt, Prog. Inorg. Chem. 1987, 35, 329 or G. P. Stahley et al., Acta Crystall.
• the corresponding metal salts such as e.g. Reacts metal chlorides or metal carbonyls with the ligand, e.g. B. in P. Chaudhuri, K. "Wieghardt, Prog. Inorg. Chem. 1987, 35, 329 or G. P. Stahley et al., Acta Crystall.
• aluminum or boron compounds with electron-withdrawing radicals for example trispentafluorophenylborane, trispentafluorophenylaluminium, N, N-dimethylanilinium tetrakis-pentafluorophenylborate, tri-n-butylammonium tetrakis-pentafluorophenylborate, N, N-di-diamine - (3,5-bisperfluoromethyl) phenylborate,
• electron-withdrawing radicals for example trispentafluorophenylborane, trispentafluorophenylaluminium, N, N-dimethylanilinium tetrakis-pentafluorophenylborate, tri-n-butylammonium tetrakis-pentafluorophenylborate, N, N-di-diamine - (3,5-bisperfluoro
• Dirnethyl 0 anilinium tetrakis pentafluorophenyl borate, tritylium tetrakis pentafluorophenyl borate and trispentafluorophenyl borane are preferred.
• boron or aluminum compounds are used as active gates for the complexes of the general formulas la to c, they are generally used in a molar ratio of 1:10 to 10: 1, based on M, a; preferably 1: 2 to 5: 1 and particularly preferably 1: 1.5 to 1.5: 1.
• Another suitable class of cation-forming compounds are the aluminoxanes of the general formula II a to b.
• aluminoxanes are products which are obtained by careful partial hydrolysis of aluminum alkylene (see DE-A 30 07 725). These products are not purely available, but as mixtures of open-chain and cyclic structures of type II a and b. These mixtures are probably in dynamic equilibrium with one another.
• radicals R 23 * 1 are independent of one another
• Ci-Cia-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably -C ⁇ C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n
• C 7 - to C 2 o-aralkyl preferably C 7 - to -C -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1st -Phenyl-butyl, 2-phenyl-butyl, f-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl, or
• C 3 -Ci 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; and n is an integer from 0 to 40, preferably from 1 to 25 and particularly preferably from 2 to 22.
• Mixtures of different aluminoxanes are particularly preferred activators in which polymerization is carried out in a solution of a paraffin, for example n-heptane or isododecane.
• a particularly preferred mixture is the CoMAO commercially available from Witco GmbH with a formula of [(CH 3 ) 0 , 9 (iso-CH 9 ) o, ⁇ A10] n .
• Useful molar ratios M: Al are in the range from 1:10 to 1:10 to 1: 10,000, preferably 1:50 to 1: 1000 and particularly preferably 1: 100 to 1: 500.
• the selected complex of general formulas I a to c and the cation-forming compound together form a catalyst system.
• the activity of this catalyst system can be increased further by adding one or more further aluminum alkyl compounds of the general formula A1 (R 23 ) 3 .
• the activity of the catalyst system can be increased by adding further aluminum alkyl of the general formula A1 (R 23 ) 3 or aluminoxanes;
• Aluminum alkyls of the general formula A1 (R 23 ) 3 or aluminoxanes can also act as molecular weight regulators.
• Another effective molecular weight regulator is hydrogen.
• the molar mass can be regulated particularly well by the reaction temperature and the residence time.
• Modern large-scale manufacturing processes for polyolefin waxes are solution processes, suspension processes, bulk polymerisation processes in liquid or supercritical monomer as well as gas phase processes, the latter being agitated gas phases or gas phase fluidized bed processes.
• Monomers which are particularly suitable are ethylene and C 3 - to C 1 -C 1 -ene, ie propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene. Ethylene and / or propylene are preferably used as monomers.
• the monomers can be homopolymerized or copolymerized with one another in any ratio.
• Preferred polyolefins on which the oxidized waxes are based are ethylene homopolymers with a density in the range from 0.90 to 0.98 g / cm 3 , preferably in the range from 0.94 to 0.97 g / cm 3 and an M w , determined by the GPC method as described above, in the range from 1000 to 40,000 g / mol, preferably in the range from 2000 to 20,000 g / mol.
• ethylene / C 3 -C 1 -C 1 -en-ene copolymers with a total content of structural units based on the alk-1-ene or the alk-1-ene in the copolymer in the range from 0.1 to 15 ⁇ ttol%, preferably in the range of 1 to 10 mol%, based on the copolymer.
• Preferred ethylene / alk-1-ene copolymers are ethylene-propylene copolymers with a content of structural units based on the propylene in the copolymer in the range from 0.1 to 10 mol%, preferably in the range from 1 to 5 mol -%, based on the copolymer.
• the copolymers generally have an M w , determined using the GPC method as described above, in the range from 1000 to 40,000 g / mol, preferably in the range from 2000 to 20,000 g / mol.
• polyolefins on which the oxidized waxes are based are isotactic propylene homopolymers with a pentad content mmmm of isotactic pentads, determined by the method of X3 C-MR spectroscopy, in the range from 90 to 98% and an Mw with the method of GPC as described above, in the range from 1000 to 40,000 g / mol, preferably in the range from 2000 to 20,000 g / mol.
• copolymers of propylene with ethylene and / or C 4 -C 1 -C 1 -alkenes are also suitable as base polyols.
• These propylene copolymers usually have a total content, based on the ethylene and / or the C 4 -C 1 -C 10 -alk-1-enes, of structural units in the copolymer in the range from 0.1 to 15 mol%, preferably in the range from 1 up to 10 mol% on the copolymer.
• Preferred propylene copolymers are propylene-ethylene copolymers with a content of structural units based on the ethylene in the copolymer in the range from 0.1 to 10 mol%, preferably in the range from 1 to 5 mol%, based on the copolymer.
• the propylene copolymers generally have an M w , determined by the GPC method as described above, in the range from 1000 to 40,000 g / mol, preferably in the range from 1000 to 20,000 g / mol.
• the monomers are homo- or copolymerized in the presence of complexes of the general formulas I a to c.
• Suitable reactors for the preparation of the polymers or copolymers are, inter alia, continuously operated stirred kettles, it also being possible, if appropriate, to use a number of several stirrer kettles connected in series.
• the polymerization reactions can be carried out in the gas phase, in suspension, in liquid and in supercritical monomers or in inert solvents.
• the oxidation of the polyolefins on which the oxidized waxes are based can be carried out using pure oxygen or gases containing oxygen. Air is preferably used for the oxidation of the polyolefins.
• Organic peroxides e.g. Add di-tert-butyl peroxide; it is also conceivable to add heavy metal salts such as manganese acetate.
• inorganic or organic acids are hydrochloric acid or nitric acid.
• Mono-, di- or tricarboxylic acids can be mentioned as organic acids. Suitable monocarboxylic acids have 1 to 3 carbon atoms, formic acid and acetic acid being preferred.
• Suitable dicarboxylic acids have 2 to 6 carbon atoms.
• Examples of preferred dicarboxylic acids are oxalic acid, malonic acid, maleic acid, tartaric acid, malic acid and adipic acid.
• Particularly preferred dicarboxylic acids are tartaric acid, malic acid and adipic acid; a particularly preferred tricarboxylic acid is citric acid. Since acetic acid and adipic acid are often formed in the course of the oxidation, the addition of additional acid is not absolutely necessary.
• Suitable oxidation processes for polyolefin waxes are known in principle, for example, from DE-A 20 35 706.
• the metalocene polyolefin according to the invention preferably an ethylene homopolymer
• a tubular reactor or a stirred autoclave at a Temperature in the range of 140 to 350 ° C, preferably 150 to 250 ° C and a pressure in the range of 100 to 20,000 kPa, preferably in the range of 500 to 4000 kPa with oxygen-containing gases, preferably air around.
• the amount of oxygen supplied is then generally in the range from 0.1 to 1000 1 oxygen / h-kg wax, preferably in the range from 1 to 50 1 oxygen / h-kg wax.
• the available oxidized polyolefin waxes in particular the oxidized waxes from ethylene homopolymer, have one
• Ratio of acid number to saponification number in the range from 1: 1 to 1: 4, preferably in the range from 1: 1 to 1: 2.
• the acid number is determined by titration according to DIN 53402.
• the saponification number is determined by titration according to DIN 53401.
• Suitable acid numbers are 1 to 150 mg KOH / g, preferably 10 to 50 mg KOH / g and particularly preferably 15 to 30 mg KOH / g.
• the melting point of the oxidized waxes according to the invention determined by the method of differential scanning calorimetry (DSC) according to DIN 51007, is usually in a range from 90 to 125 ° C., preferably in a range from 110 to 125 ° C.
• the hardness of the oxidized waxes according to the invention is determined using the ball indentation method; according to DIN 50133, it is usually in a range from 800 to 2000 N / mm 2 , preferably in a range from 1000 to 1500 N / mm 2 .
• the viscosity of the oxidized waxes according to the invention is usually in the range from 100 to 10,000 cSt, preferably in the range from 200 to 5000 cSt.
• the waxes according to the invention are well suited as coating compositions or as components in coating compositions.
• the coating composition is usually characterized by its high hardness and high gloss.
• the oxidized waxes according to the invention are particularly well suited as a component in floor care products or leather care products, in particular shoe care products.
• the polymerization was terminated by relaxing the autoclave.
• Clariant wax PE 130 produced by Ziegler-Natta catalysis, was used as comparative example VI.
• a polyethylene wax produced by metal locene catalysis according to DE-A 196 17 230 was used as a comparative example V2.
• Oxidations of waxes 1, VI and V2 were carried out in a stirred (impeller stirrer) 1-1 steel autoclave with pressure maintenance.
• the wax to be oxidized was placed in front (800 g) and heated to 160 ° C. After the wax had melted, the stirrer was switched on and air (30 l / h-kg) was passed through. The reaction was stopped when the desired acid number was reached, the oxidized wax was drained and analyzed.
• the acid number was determined in accordance with DIN 53402,

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• 2001
  • 2001-06-15 WO PCT/EP2001/006823 patent/WO2001098377A2/de not_active Ceased
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