CN103403012B - 用于制备聚合反应催化剂的低粘性的镁配合物浓缩溶液及其制备方法 - Google Patents
用于制备聚合反应催化剂的低粘性的镁配合物浓缩溶液及其制备方法 Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 53
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 31
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 title description 5
- 239000012141 concentrate Substances 0.000 title description 4
- -1 magnesium alkoxide Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000004820 halides Chemical class 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000004703 alkoxides Chemical class 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 230000011218 segmentation Effects 0.000 claims description 3
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical class CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 claims description 2
- TVBQWTDYXVGWJL-UHFFFAOYSA-N 2-methyl-4-methylidenehexane Chemical class CCC(=C)CC(C)C TVBQWTDYXVGWJL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical group 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 159000000003 magnesium salts Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical class CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- TVSPOLBJUVJVCV-UHFFFAOYSA-N benzene;heptane Chemical compound C1=CC=CC=C1.CCCCCCC TVSPOLBJUVJVCV-UHFFFAOYSA-N 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6548—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof magnesium or compounds thereof, not provided for in C08F4/6543 or C08F4/6546
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Abstract
本发明涉及通过镁醇盐与羧酰卤在基于烃的溶剂中反应制备的低粘性的浓缩含镁配合物溶液以及其制备方法。
Description
本发明涉及碱性镁配合物在基于烃的溶剂中的低粘性的浓缩溶液及其制备方法。
镁醇盐主要是用于制备加载的齐格勒-纳塔-型烯烃聚合反应催化剂。为此,例如以球形颗粒的形式使用不溶性的醇盐(例如乙醇镁),其中该醇盐通过与氯化钛或其它含有钛-卤素键合的化合物(例如双(环戊二烯基)二氯化钛(Cp2TiCl2))的反应转化成活性形式,例如在文件EP 1031580中描述的:
另一种制备加载的齐格勒-纳塔催化剂的可能是基于可溶性的镁醇盐。大部分的镁醇盐(例如甲醇、乙醇、丙醇、异丙醇、叔丁醇等的镁盐)在非质子溶剂中是不溶的,而在2-位支化的伯醇的Mg化合物被证明在烃中是可溶的(WO 85/02176)。因此,例如2-甲基-1-庚醇或2-乙基-1-己醇的镁盐溶于环己烷中的浓度应该是1.3mol/l。混合的Mg醇盐,即具有两种不同的醇盐残基Mg(OR1)(OR2)可以是溶于烃的,如果相对应的醇R1OH是在2-位支化的伯醇而相对应的醇R2OH是仲醇的话(WO 85/02176)。
在制备基于MgCl2的催化剂载体的第一个步骤中,可以由这些含有镁醇盐的溶液通过与羧酰卤的反应制备可溶性的配合化合物。作为羧酰卤优选使用二羧酰卤,特别优选α,β-不饱和二羧酰卤,特别是邻苯二甲酰氯(EP 1229054B1)。在EP 1862480A1中描述了制备这样优选的配合物溶液,其中在合成该溶液时除了羧酰卤外没有使用其它的含卤化合物。然后,首先通过20%的丁基辛基镁在甲苯中的溶液与2当量的乙基己醇反应来制备可溶性的双(乙基己醇)镁盐,该镁盐接下来与邻苯二甲酰氯在60℃反应。在100%产率时,该产物溶液的镁浓度为0.83mmol/g,而使用的邻苯二甲酰氯与双(乙基己醇)镁盐的摩尔比为0.40:1。
该产物的缺点在于,当镁浓度>0.9mmol/g时相对低的产物浓度以及高粘度的产物溶液。
本发明的目的在于,提供可以避免现有技术的这些缺点的产物,即
- 其中溶解形式的镁的浓度为至少0.9mmol/g,
- 是低粘性的(粘度<500mPas)和
- 在最多30℃经过最多4周的时间是存储稳定的。
该目的通过将含有镁醇盐的溶液在基于烃的溶剂或溶剂混合物中与一种或多种羧酰卤反应而实现,其中在以这种方式形成的配合物中溶解的镁的浓度为至少0.9mmol/g,特别优选至少1mmolg和特别优选至少1.1mmolg。羧酰卤官能与镁之间的摩尔比为至少0.84:1,特别优选至少0.9:1和最高1.8:1。作为羧酰卤特别优选使用二羧酰氯,例如邻苯二甲酰氯。对于这些双官能的酰氯,二羧酰氯与镁醇盐的摩尔比为至少0.42:1,优选至少0.45:1,特别优选至少0.50:1和最高0.9:1。令人惊奇地发现,当羧酰氯当量与镁醇盐当量的摩尔比超过约0.9:1时,溶液的粘度急剧下降。这种不可预见的现象造成了镁醇盐和羧酰卤之间的配合物的产物浓度可以明显上升,而其粘度没有增加从而阻止了产物的处理。这些本发明的低粘性的产物溶液特别是可以非常好泵送的和存储稳定的。
作为镁醇盐使用通式为Mg(OCH2R1)2的化合物,该化合物由在2-位支化的伯醇(HOCH2R1)衍生而来。该醇HOCH2R1特别优选选自:异丁醇、2-甲基-1-戊醇、2-乙基-1-丁醇、2-乙基-1-戊醇、2-乙基-4-甲基-1-戊醇、2-丙基-1-庚醇、2-甲基-1-己醇、2-乙基己醇和2-乙基-5-甲基-1-辛醇或所列出的醇的至少两种的任何混合物。
基于烃的溶剂是或含有一种或多种具有5-20个碳原子的脂族化合物,其中可以是环状或开链的化合物。优选的是:环己烷、甲基环己烷、己烷、庚烷、辛烷、壬烷、癸烷、十二烷、十氢萘以及市售的分段馏分(Siedefraktion)(汽油馏分)。
此外,非质子溶剂可以含有芳族化合物或由其组成。优选的是:苯、甲苯、乙苯、二甲苯以及异丙基苯。
在本发明的另一实施方式中,所述本发明的含镁配合物溶液还可以含有极性、非质子溶剂,例如醚类或叔胺类。
本发明的浓缩的由镁醇盐和羧酰氯形成的反应产物在室温通常具有最大500mPas,优选最大100mPas和特别优选最大50mPas的动态溶液粘度,用(例如公司Brookfield的)旋转粘度计测量。
本发明的浓缩的配合物溶液的制备是通过将在2-位支化的镁醇盐(例如双(乙基己醇)镁盐)的溶液与羧酰卤在基于烃的溶剂中在0-120℃,优选20-100℃的温度反应来进行。反应容器和使用的投料必须是干燥的和无空气的,即惰性化的。该反应在保护气体氛围,例如在氮气或氩气下进行。优选先放入所述醇盐溶液和计量添加所述羧酰卤。为了能够跟踪粘度的变化,进行在线粘度测量。例如公司F5(Wunstorf,Niedersachen)提供这样的仪器。
将低粘性的33.7%的双(乙基己醇)镁盐溶液(1.19mmol/g的Mg,粘度约11mPas)放入到90%甲苯和10%庚烷的溶剂混合物中,并加热到60℃。然后首先添加0.40当量的邻苯二甲酰氯(相应剂量=100%)。其中粘度非常剧烈地上升到约180mPas,用公司F5的仪器测量。该粘度相应于用旋转粘度计(例如公司Brookfield的)测量的动态粘度值为几千mPas。在60℃约40分钟的搅拌之后继续加入邻苯二甲酰氯(“PDC”)。在加入另外0.07当量,即总共0.47当量的PDC之后,用公司F5的仪器测量的粘度实际上突然从约115减少到20mPas。
本发明的产物用于制备聚合反应催化剂,特别是多相化的齐格勒-纳塔型的聚烯烃催化剂。
图1显示了在这样的反应过程中粘度的典型变化。
借助下面两个实施例和两个对比例进一步阐述本发明。
实施例:所有反应在干燥的用氩气惰性化的玻璃装置中进行。粘度的测量在室温用公司Brookfield的旋转粘度计在充满氩气的手套箱中进行。
比较例1:
在带有沿着壁转动(wandgängig)的搅拌元件的0.5L双层外套反应器中加入544g双(乙基己醇)镁盐在甲苯中的溶液并加热到60℃,其中该溶液的Mg浓度为1.23mmol/g(ICP-分析)和粘度为560mPas。然后在1小时内滴加54.3g(相应于0.40当量,基于加入的Mg醇盐的量计)。这时的溶液非常粘稠。
在60℃下20分钟的搅拌之后将该溶液冷却到室温。
称重:583g的溶液
Mg浓度:1.12mmol/g
粘度:3200mPas。
比较例2
在带有沿着壁转动的搅拌元件的0.5L双层外套反应器中加入532g 双(乙基己醇)镁盐在70%甲苯和30%庚烷的溶液混合物中的溶液并加热到60℃,其中该溶液的浓度为1.24mmol/g(ICP-分析)和粘度为500mPas。然后在1小时内滴加53.5g(相应于0.40当量,基于加入的Mg醇盐的量计)。这时的溶液极其粘稠。
在60℃下20分钟的搅拌之后将该溶液冷却到室温。
称重:552g的溶液
Mg浓度:1.15mmol/g
粘度:6200mPas。
实施例1
在比较例1中描述的装置中加入432g 双(乙基己醇)镁盐在70%甲苯和30%庚烷的溶液混合物中的溶液并加热到60℃,其中Mg浓度为1.24mmol/g(ICP-分析)和粘度为500mPas。然后在1小时内滴加57.6g PDC(相应于0.53当量,基于加入的Mg醇盐的量计)。一直到加入约0.5当量的剂量时,该溶液变得明显比较粘稠,在计量加入结束前不久粘度却明显下降。
在60℃下20分钟的搅拌之后将该溶液冷却到室温。
称重:462g的溶液
Mg浓度:1.15mmol/g
粘度:18mPas
存储稳定性:在0℃、10℃和约25℃的温度经过4周时间没有变化。
实施例2
在比较例1中描述的装置中加入432g 双(乙基己醇)镁盐在90%甲苯和10%庚烷的溶液混合物中的溶液并加热到60℃,其中Mg浓度为1.49mmol/g(ICP-分析)和粘度为1500mPas。然后在1小时内滴加61.5g PDC(相应于0.47当量,基于加入的Mg醇盐的量计)。一直到加入约0.4当量的剂量时,该溶液变得明显比较粘稠,在计量加入结束前不久粘度却明显下降。
在60℃下20分钟的搅拌之后将该溶液冷却到室温。
称重:415g的溶液
Mg浓度:1.31mmol/g
粘度:30mPas
存储稳定性:在0℃、10℃和约25℃的温度经过4周时间没有变化。
比较例1显示了,当对于每摩尔Mg醇盐使用0.40当量的PDC时,Mg配合物在纯甲苯中的浓缩溶液具有非常高的粘度为3200mPas。当选择70%甲苯和30%庚烷的混合物来替代甲苯,则在使用同样0.40当量的PDC时观察到更高的粘度为6200mPas(对比例2)。
与此相反,当使用与在对比例2中相同的Mg醇盐,但PDC化学计量提高到0.53当量,却产生了稀液态的Mg配合物溶液(18mPas,实施例1)。实施例2显示了,当对于每当量使用的Mg醇盐使用0.47当量的PDC时,甚至更高的Mg配合物浓度(1.31mmol/g)却是低粘性的。
Claims (20)
1.在基于烃的溶剂中含有镁醇盐与羧酰卤的反应产物的溶液,其特征在于,所溶解的镁浓度为至少0.9mmol/g,而且羧酰卤官能和镁的摩尔比例为至少0.9:1和最高1.8:1,且用旋转粘度计测量,所述溶液在室温具有最大100mPas的动态溶液粘度。
2.根据权利要求1的溶液,其特征在于,所溶解的镁浓度为至少1mmol/g。
3.根据权利要求1或2的溶液,其特征在于,所溶解的镁浓度为至少1.1mmol/g。
4.根据权利要求1或2的溶液,其特征在于,用旋转粘度计测量,它在室温具有最大50mPas的动态溶液粘度。
5.根据权利要求1或2的溶液,其特征在于,它由镁醇盐来制备,该醇盐由在2-位支化的伯醇衍生而来,其中所述醇选自:异丁醇、2-甲基-1-戊醇、2-乙基-1-丁醇、2-乙基-1-戊醇、2-乙基-4-甲基-1-戊醇、2-丙基-1-庚醇、2-甲基-1-己醇、2-乙基己醇和2-乙基-5-甲基-1-辛醇或所列出的醇的至少两种的任何混合物。
6.根据权利要求1或2的溶液,其特征在于,作为羧酰卤选用二羧酰氯。
7.根据权利要求1或2的溶液,其特征在于,作为羧酰卤选用邻苯二甲酰氯。
8.根据权利要求1或2的溶液,其特征在于,在使用二羧酰氯时二羧酰氯与镁醇盐的摩尔比为至少0.50:1和最高0.9:1。
9.根据权利要求1或2的溶液,其特征在于,基于烃的溶剂含有一种或多种具有5-20个碳原子的脂族化合物或由其组成。
10.根据权利要求9的溶液,其特征在于,所述脂族化合物是环状或开链的化合物。
11.根据权利要求9的溶液,其特征在于,所述脂族化合物是环己烷、甲基环己烷、己烷、庚烷、辛烷、壬烷、癸烷、十二烷、十氢萘或市售的分段馏分。
12.根据权利要求11的溶液,其特征在于,所述分段馏分为汽油馏分。
13.根据权利要求1或2的溶液,其特征在于,基于烃的溶剂含有芳族化合物或由其组成。
14.根据权利要求13的溶液,其特征在于,所述芳族化合物是苯、甲苯、乙苯、二甲苯或异丙基苯。
15.根据权利要求1或2的溶液,其特征在于,所述溶液还含有极性非质子溶剂。
16.根据权利要求15的溶液,其特征在于,所述极性非质子溶剂为醚类或叔胺类。
17.制备权利要求1的溶液的方法,其特征在于,一元羧酰卤与镁醇盐以至少0.9:1和最多1.8:1的摩尔比例反应。
18.制备权利要求1的溶液的方法,其特征在于,二羧酰氯与镁醇盐以至少0.50:1和最多0.9:1的摩尔比例反应。
19.根据权利要求17或18的方法,其特征在于,所述反应在0-120℃的温度下进行。
20.根据权利要求17或18的方法,其特征在于,所述反应在20-100℃的温度下进行。
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