CN1257877A - 聚合物氧化物及其应用 - Google Patents
聚合物氧化物及其应用 Download PDFInfo
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- CN1257877A CN1257877A CN99126482A CN99126482A CN1257877A CN 1257877 A CN1257877 A CN 1257877A CN 99126482 A CN99126482 A CN 99126482A CN 99126482 A CN99126482 A CN 99126482A CN 1257877 A CN1257877 A CN 1257877A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
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- RQDMEYLMEMRZME-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 RQDMEYLMEMRZME-UHFFFAOYSA-N 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- DDDRMZMSFMQPPC-UHFFFAOYSA-L [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 Chemical compound [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 DDDRMZMSFMQPPC-UHFFFAOYSA-L 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- HRGXHRPMGDCKQM-UHFFFAOYSA-L dichlorocobalt;pyridine Chemical compound Cl[Co]Cl.C1=CC=NC=C1 HRGXHRPMGDCKQM-UHFFFAOYSA-L 0.000 description 1
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
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- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical class CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
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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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
本发明涉及用茂金属催化剂制备的重均分子量在40,000g/mol以上的聚乙烯与氧气或含氧气的混合气体反应制备的聚合物氧化物。这些聚合物氧化物很适于制备水分散体。作为在母炼胶中分散颜料时加入的一种材料,或用于聚烯烃的表面改性或极性改性。另一个适宜的应用领域是用作添加剂例如作塑料加工的润滑剂。
Description
本发明涉及了在水介质中分散性改善了的聚合物氧化物，通过用聚乙烯塑料氧化降解制备它们的方法，以及涉及它们的应用。
本发明特别涉及了用茂金属催化体系制备的重均分子量Mw＞40,000g/mol的高分子量聚乙烯氧化得到的在水介质中分散性改善了的聚合物氧化合物及其这些聚合物氧化物的应用。
具有塑料性质的乙烯均聚和共聚物可通过受控氧化降解转变为极性产物。这类聚合物氧化物具有含氧官能团，如羧基、酯基和酮基，并且由于这些氧化物具有由此产生的极性而适合于制备例如用于擦光剂或工业领域的水分散体。聚乙烯氧化物也用作加工成型塑料的助剂(参看：乌尔曼工业化学百科全书，第五版，卷A28，155-156页，Weinheim1996)。
聚乙烯塑料的氧化降解工艺已为人熟知，可通过在软化点以下，用氧气或含氧混合气体处理精细分散的原料来完成(DE-A-1520 008)。这种加工方法的变体是在惰性分散介质，如水中进行此反应(DE-A-3 238 652)。在软化点以上温度下，乙烯均聚和共聚物在惰性分散介质中的氧化降解也有报道(DE-A-2 035 706，EP-A-28 384)。用于氧化的聚乙烯是在钛和/或铬过渡金属催化剂作用下，由低压工艺或自由基高压工艺进行乙烯聚合制备的。
也已经知道低分子量聚乙烯蜡可以被氧化得到蜡氧化物。它们是通过将含氧气体接触原料的熔体得到的。这里的初始材料具有低粘度，因而不必加入分散介质。重均分子量低于40,000g/mol，一般低于10,000g/mol的聚乙烯蜡的氧化所得产物不同于具有塑料性质的高分子量聚乙烯所得到的产物。此蜡氧化物分子量相对较低，比聚合物氧化物软。例如用作地板涂覆抛光制剂时，则在硬度和耐脚摩擦方面不及聚合物氧化物。蜡氧化物例如在DE-A-1 227 654中被公开。
用上述聚合物氧化物制备的水分散体，在实际应用中经常有缺陷，例如透明性不够，粘度过高，成膜后光泽降低或贮存稳定性不令人满意。
因此，本发明目的是提供分散性和使用性能有改善并且不具有现有聚合物氧化物不足的聚合物氧化物。
现在已惊喜地发现，如果使用茂金属催化剂制备的高分子量聚合物作初始材料，可获得性能改善的聚合物氧化物。
因此，本发明提供聚合物氧化物，其中初始聚合物是一种用茂金属制备并且重均分子量＞40,000g/mol的聚乙烯，该初始聚合物与氧气或含氧气体混合物反应进行氧化。
初始聚合物：
茂金属催化剂体系制备聚乙烯的聚合工艺是已知的。悬浮工艺在EP-A-578 838中有描述，气相工艺例如在EP-A-323716中有详细描述，高压工艺例如在EP-A-361 866中有详述。
合适的初始聚合物是用茂金属催化剂制备的聚乙烯。对本发明来说，有重均分子量Mw＞40,000g/mol，优选50,000-40,000,000g/mol的乙烯均聚、二元或三元共聚物。此种聚合物的熔体粘度在140℃测量为50,000mPa.s以上，通常在100Pa.s以上。在聚合物中经常作为粘度量度的熔融指数MFR190/5小于100g/10min，通常小于或等于50g/10min。
除乙烯外，该初始聚合物可能还含有占整体聚合物0.1-20wt％的链长为3-30的α-烯烃，优选3～8，例如丙烯，1-丁烯，1-己烯或1-辛烯，特别优选含丙烯或1-丁烯直达10wt％的乙烯共聚物。
优选的初始聚合物，分子量分布MwMn窄，低于5，优选低于4，特别是小于或等于3.5。
初始聚合物的制备：
用于制备初始聚合物的催化剂体系由一种或多种茂金属化合物(I)和一种共催化剂(II)组成，如果需要，也包括另一种催化剂组分(III)和一种清除剂(IV)。此催化体系经常固定在一载体上后进行使用，在这种情况下，对聚合反应有活性的物质可以在施用到载体之前，之间，或之后产生，这取决于组份(I)～(IV)和载体使用顺序的变化。
典型的茂金属化合物(I)具有分子式I，并且包括例如分子式(Ia)、(Ib)或(Ic)的结构：
分子式中的M1是周期表IVB，VB，VIB或VIIIB族的金属，例如钛、锆、铁、铬、钴或镍。
R1和R2可以相同或不同，可为氢原子，C1-C10-烷基，C1-C10-烷氧基，C6-C10-芳基，C6-C10-芳氧基，C2-C10-链烯基，C7-C40-芳烷基，C7-C40-烷芳基，C8-C40-芳链烯基或卤原子。
R3和R4可以相同或不同，在分子式(Ia)～(Ic)的实施方案中被描述，或者是烷基，吡啶基，芳烷基，烷芳基，或单、二烷基吡啶基取代的亚氨基，它们可通过烷基、二烷基芳基或二烷基吡啶基彼此桥接。此外，基团R3和R4两者之一可以是一个取代的氮原子，在这种情况下R28的定义同R21，优选甲基，叔丁基或环己基。
R5～R4可以相同或不同，并且彼此独立，可以是氢原子，卤原子，C1-C18-芳基，C1-C10-烷氧基，或NR2 20-，-SR20-，OSiR3 20-，-SiR3 20-，或-PR2 20-基团，其中R20是C1-C10烷基或C6-C10-芳基，或就含Si或P的基团而言也可以是卤原子，或每两个相邻基团R5，R6，R7，R8，R9，R10，R11，R12，R13或R14，与连接它们的碳原子一起可能形成一个环体系。例如，2-甲基-4-萘基茚基或取代苯并茚基或芴基。这些配体的优选取代基已在R1的描述中给出。
R17是：
＝BR21，＝AlR21，-Ge-，-Sn-,-O-，-S-，＝SO，＝SO2，＝NR19，＝CO，＝PR19或＝P(O)R19，
此处R21，R22和R23可相同或不同，可以是氢原子，卤原子，C1-C30-烷基，C1-C10-氟烷基，C6-C10-氟代芳基，C6-C10-芳基，C1-C10-烷氧基，C2-C10-烯基，C7-C40-芳烷基，C8-C40-芳烯基或C7-C40-烷芳基，或R21和R22或R21和R23在任何一种情况，与连接它们的原子一起可以形成一个有2-8个环碳原子的环。
M2是硅、锗或锡，最好是硅。R17优选＝CR21R22，＝SiR21R22，＝GeR21R22，-O-，-S-，＝SO，＝PR21或＝P(O)R21。R15和R16可以相同或不同，定义同R21。m和n可以相同或不同，为0，1或2。R18和R19定义同R21和R22。
茂金属阐述性实例：
二(1-正丁基-3-甲基-环戊二烯基)二氯化锆，
二(四氢茚基)(二甲基)锆，
二甲基甲硅烷基-二[1-(2-甲基-4，5-苯并茚基)](二苄基)锆，
二甲基甲硅烷基-二[1-(2-甲基四氢茚基)]二氯化锆，
亚乙基-二-[1-(2-甲基-4-苯基茚基)]二氯化锆，
亚乙基-二-[1-(四氢茚基)]二氯化锆，
亚异丙基(1-茚基)(环戊二烯基)二氯化锆，
亚异丙基(9-芴基)(环戊二烯基)二氯化锆，
(叔丁基酰胺基)[二甲基(四甲基环戊二烯基)甲硅烷基](二甲基)-钛，
2，6-二[1-(2-叔丁基苯亚胺基)乙基]吡啶二氯化铁，
2，6-二[(2，6-二异丙基苯基亚胺基)甲基]吡啶二氯化钴。
合适的共催化剂(II)是有机铝合物，特别是铝氧烷，或也可以为无铝体系，如Rx 26NH4-xBR4 27，Rx 26PH4-xBR4 27，R3 26CBR4 27，BR3 27，这些分子式中，x是1-4中的一个数，基团R26可以相同或不同，为C1-C20-烷基或C6-C12-芳基，或两个R26基团同连接它们的原子一起可形成一个有2-8个环碳原子的环。基团R27可以相同或不同，为芳基，可带烷基、卤代烷基或卤原子取代基。R26的例子是乙基，或苯基，R27的例子是五氟苯基。三烷基铝或其混合物的控制水解制备的铝氧烷，特别是甲基铝氧烷，一般可成功用于活化。
组分(III)是环硼氧烷，分子式为(R21BO)3，如三甲基环硼氧烷，其中基团R21也可以彼此不同。类型(II)其它化合物也可用于代替此化合物以增加此催化体系的活性。
此外，可使用清除剂(IV)以防止聚合体系出现极性催化剂中毒。任何有机铝化合物，如三乙基铝或三异丁基铝或它们的混合物都适用于此。
初始聚合物的氧化：
该氧化过程按下述方法进行，得到的聚合物氧化物，酸度为0.5-200mgKOH/g，140℃时熔体粘度为50-20,000mPa.s，最优选为100-20,000mPa.s。
高分子量的初始聚合物，其氧化降解是通过暴露于氧气或含氧气体中，优选空气，至少在大气压下进行的。这里所用的温度可低于或高于聚合物的软化点。就后一种情况来说，惰性分散介质，如水的存在通常是必要的，以保证聚合物熔体和氧化剂间的相界面足够大，使反应迅速。如果氧化在低于软化点下进行，反应速度降低，但可免去分散介质的加入和随后的再分离。反应的进程用酸度跟踪，可以加入少量以前氧化的聚乙烯作为反应的“初始助剂”。
另外，该制备聚合物氧化物的氧化降解过程，可用过氧化物或偶氮化合物，如2，2′-偶氮二(2-甲基丙腈)；对聚合物预处理或等离子体氧化处理另外加以促进。选择原料时应当优选不稳定聚合物或那些抗氧剂比例低的聚合物。
控制酸、碱或缓冲物质的加入能缩短反应时间，避免交联反应，此聚合物氧化反应可连续或间歇进行。
聚合物氧化物的应用：
本发明进一步提供了该新聚合物氧化物的应用，用于制备水分散体，作为例如在母炼胶中分散颜料时加入的一种材料，或用于聚烯烃的表面改性或极性改性。另一个有利的应用领域是作为塑料加工的润滑剂。
该聚合物氧化物使用助剂如离子或非离子乳化剂，碱如碱金属氢氧化物或氨及胺，和其它添加剂可加工得到水分散体。此类分散体的质量标准有粘度、高温储存稳定性，透明度及当分散体应用于光滑表面时所成薄膜的光泽。
聚合物氧化物中的功能团也可通过羧基、酯和酮基的反应进行衍生。由此得到的添加剂适宜用作表面改性或颜料分散或聚合物共混物的相容剂。
实施例：
本发明用下面的实施例进行更详细地说明：
熔融指数按ISO1133，使用Gttfert公司设备测定。重均分子量Mw、数均分子量Mn和它们的商Mw/Mn用凝胶色谱法在135℃于1，2-二氯苯中测定。熔体粘度依照DIN51562用旋转粘度计测定。滴点按DIN51801/2，酸度按DIN53402，密度按DIN53479在20℃测定，水分散体的粘度，按DIN53211，用流动杯测定。膜的光泽测量用Byk GardnerGmbH的Micro-TRI-gloss型设备进行。
Synperonic 91/4和Synperonic 91/5是ICI公司的乳化剂，GenapolUD 080是Clariant GmbH公司的乳化剂。
高分子量初始聚合物的制备和表征：
原则上，任何用茂金属催化剂制备的乙烯均聚物或共聚物都适用。进行聚合反应的技术并不重要。下列原料用于制备聚合物氧化物：
表1a：茂金属聚乙烯
| 原料 | 茂金属 | Mw | Mw/Mn | MFR190/5 | 密度 | 共单体 |
| No.1 | 二(正丁基-3-甲基环戊二烯基)二氯化锆 | 54,000 | 2.8 | 19 | 0.958 | - |
| No.2 | 二甲基甲硅烷基二(四氢茚基)二氯化锆 | 71,000 | 3.4 | 12 | 0.949 | 丙烯 |
| g/mol | g/10min | G/cm3 |
表1b：Ziegler聚乙烯(作为对比实例)
| 原料 | 型号 | Mw | Mw/Mn | MFR190/5 | 密度 | 共单体 |
| No.3 | Hostalen GA 7260 | 56,000 | 4.7 | 53 | 0.957 | - |
| No.4 | Hostalen GB 7250 | 68,100 | 5.2 | 24 | 0.950 | 丙烯 |
| g/mol | g/10min | g/cm3 |
聚合物氧化物的制备：
实施例1-3；对比实施例1-3。
5.0kg表1a/b中所列的初始聚合物，20l水，300g酸度为60mgKOH/g的氧化聚乙烯在高压反应器中加热。一旦内部温度达到140℃，2000l/h的预热空气计量加入到搅拌着且保持15bar恒压的混合物中。氧化度由抽样跟踪。一旦达到所要求的酸度，停止进空气，并停搅拌。相分离后，由底阀排出分散水，保留在反应器中的蜡熔体由蒸馏除去残留水份而干燥。熔体排出到盘中。测定了产物的下列性能：
表2：聚合物氧化物的性能
| 实施例 | 原料(从表1a/b) | 酸度mgKOH/g | 熔体粘度/140℃[mPa.s] | 滴点[℃] |
| 1 | No.1 | 16 | 2380 | 124 |
| 2 | No.1 | 23 | 810 | 122 |
| 3 | No.2 | 17 | 3800 | 125 |
| 对比实施例1 | No.3 | 17 | 1820 | 123 |
| 对比实施例2 | No.3 | 27 | 835 | 120 |
| 对比实施例3 | No.4 | 16 | 2450 | 122 |
水分散体的制备：
实施例4和5；对比实施例4和5。
一种混合物，含有280g聚合物氧化物，644g去离子水，45.0gSynperonic 91/4，20.0g Synperonic 91/5，7.0g二乙基氨基乙醇，2.0g氢氧化钾(86％浓度)和2.0g亚硫酸钠，在11配有搅拌器、温度计和加热套的压力反应器中加热。一旦内温达到90℃，开搅拌器(150rpm)。继续加热至143℃，恒温进一步搅拌20分钟，然后在40分钟内冷却反应器内容物至约30℃。得到的分散体(固含量35％)的性能列于表3中。可以看出，由茂金属聚乙烯制备的分散体具有更好的透明度、粘度和储存稳定性等。
表3
| 实施例 | 聚合物氧化物 | 分散体的透明度(0.1％1cm测定池)％ | 涂膜的光泽/％(测量角20/60°)％ | 分散体粘度(从4mmDIN杯中排出时间)秒 | 50℃储存一周后分散体的稠度 | |
| 未稀释(固含量35％) | 稀释至固含量30％ | |||||
| 4 | 实施例1 | 63 | 82/90 | 56 | 17 | 液体 |
| 5 | 实施例3 | 65 | 83/91 | 38 | 13 | 液体 |
| 对比实施例4 | 对比实施例1 | 55 | 80/89 | 210 | 23 | 不再为易流动液体 |
| 对比实施例5 | 对比实施例3 | 53 | 79/90 | 190 | 22 | 不再为易流动液体 |
实施例6和对比实施例6
混合物，由276g聚合物氧化物，644g去离子水，69g Genapol UD080，7.0g二乙基氨基乙醇，2.0g氢氧化钾(86％强度)和2.0g亚硫酸钠组成，在1l压力反应器中加热。当内温达到90℃时，开搅拌器(150rpm)。继续加热至143℃，恒温搅拌20分钟，然后在40分钟内将反应器内容物冷却至约30℃。所得分散体的性能列于表4中。
| 实施例 | 聚合物氧化物 | 分散体的透明度(0.1％，1cm测定池)％ | 涂膜的光泽(测量角20/60°)％ | 分散体的粘度(从4mmDINS杯中排出时间)秒 |
| 6 | 实施例2 | 63 | 80/89 | 23 |
| 对比实施例6 | 对比实施例2 | 48 | 78/80 | 30 |
Claims (6)
1.一种聚合物氧化物，其中初始聚合物是用茂金属催化剂制备的，重均分子量在40,000g/mol以上的聚乙烯，该初始聚合物与氧气或含氧气的气体混合物反应进行氧化。
2.权利要求1的聚合物氧化物，由乙烯均聚物或含有0.1-20wt％的C3-C8-α-烯烃的共聚物或三元共聚物制备。
3.权利要求1或2的聚合物氧化物，其中初始聚合物含有可达10wt％的丙烯或1-丁烯。
4.权利要求1至3中任何一项的聚合物氧化物，酸度为0.5-200mgKOH/g，140℃时熔体粘度为50-20,000mPa.s。
5.权利要求1至4中任何一项的聚合物氧化物的制备工艺，其特征为用空气氧化初始聚合物。
6.权利要求1至4中任何一项聚合物氧化物在制备水分散体或作为塑料加工的润滑剂的用途。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100700463B1 (ko) * | 1999-12-13 | 2007-03-29 | 바스프 악티엔게젤샤프트 | 안료 농축물 및 그의 생산 방법 |
| WO2001064776A1 (de) * | 2000-03-01 | 2001-09-07 | Clariant Gmbh | Verbesserung der dispergierung von pigmenten in polypropylen |
| DE50107834D1 (de) * | 2000-03-01 | 2005-12-01 | Clariant Gmbh | Dispergierung von pigmenten in polyolefinen |
| DE10015593A1 (de) * | 2000-03-29 | 2001-10-11 | Clariant Gmbh | Verwendung von Polyolefinwachsen in der Kunststoffverarbeitung |
| DE10159955A1 (de) | 2001-12-06 | 2003-06-26 | Clariant Gmbh | Verwendung von polar modifizierten Polyolefinwachsen in Fototonern |
| DE10216118A1 (de) * | 2002-04-12 | 2004-04-22 | Clariant Gmbh | Verwendung von Metallocenwachsen in Pulverlacken |
| US6677395B1 (en) | 2002-11-27 | 2004-01-13 | Basell Poliolefine Italia S.P.A. | Irradiated, oxidized olefin polymer dispersing agents |
| DE102004016790A1 (de) * | 2004-04-06 | 2005-11-17 | Clariant Gmbh | Verwendung von Wachsen als Modifizierungsmittel für gefüllte Kunststoffe |
| JP5466501B2 (ja) * | 2007-02-27 | 2014-04-09 | 出光興産株式会社 | 酸化変性プロピレン系重合体及びその製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| NL288516A (zh) | 1962-02-06 | |||
| US3322711A (en) | 1963-10-17 | 1967-05-30 | Allied Chem | Polymer oxidation process and emulsion therefrom |
| US3383338A (en) | 1963-10-17 | 1968-05-14 | Allied Chem | Flame-retardant, non-shrinking ureaformaldehyde foams and process of making same |
| DE2035706C3 (de) | 1970-07-18 | 1975-09-11 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Herstellung von Oxidationsprodukten von Äthylenpolymeren |
| US4132691A (en) * | 1977-04-06 | 1979-01-02 | M&T Chemical Inc. | Lubricant composition for vinyl chloride polymers |
| DE3066715D1 (en) | 1979-11-02 | 1984-03-29 | Hoechst Ag | Oxidation products of ethylene copolymers and their use |
| DE3238652A1 (de) | 1981-10-21 | 1983-05-05 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von oxidierten ethylen(co)polymerisaten |
| DE3427883A1 (de) * | 1984-07-28 | 1986-01-30 | Hüls AG, 4370 Marl | Gleitmittel fuer die kunststoff-verarbeitung |
| US4912075A (en) | 1987-12-17 | 1990-03-27 | Exxon Chemical Patents Inc. | Method for preparing a supported metallocene-alumoxane catalyst for gas phase polymerization |
| US4935397A (en) | 1988-09-28 | 1990-06-19 | Exxon Chemical Patents Inc. | Supported metallocene-alumoxane catalyst for high pressure polymerization of olefins and a method of preparing and using the same |
| TW197978B (zh) * | 1991-02-07 | 1993-01-11 | Hoechst Ag | |
| EP0578838A1 (en) | 1992-04-29 | 1994-01-19 | Hoechst Aktiengesellschaft | Olefin polymerization catalyst, process for its preparation, and its use |
| DE59305691D1 (de) | 1992-05-26 | 1997-04-17 | Hoechst Ag | Verfahren zur Herstellung von Polyolefinwachsen |
| US5750813A (en) | 1992-12-15 | 1998-05-12 | Clarian & Gmbh | Process for the preparation of polyolefin waxes |
| TW322495B (zh) * | 1992-12-15 | 1997-12-11 | Hoechst Ag | |
| DE19617230A1 (de) * | 1996-04-30 | 1997-11-06 | Basf Ag | Oxidierte Metallocen-Polyolefin-Wachse |
-
1998
- 1998-12-24 DE DE19860174A patent/DE19860174A1/de not_active Withdrawn
-
1999
- 1999-10-26 JP JP11303304A patent/JP2000191724A/ja not_active Withdrawn
- 1999-12-11 ES ES99124692T patent/ES2177191T3/es not_active Expired - Lifetime
- 1999-12-11 EP EP99124692A patent/EP1013672B1/de not_active Expired - Lifetime
- 1999-12-11 DE DE59901389T patent/DE59901389D1/de not_active Expired - Fee Related
- 1999-12-21 US US09/469,061 patent/US6384148B1/en not_active Expired - Fee Related
- 1999-12-23 CN CN99126482A patent/CN1257877A/zh active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111201250A (zh) * | 2017-10-10 | 2020-05-26 | 泰国聚乙烯有限公司 | 氧化聚乙烯蜡 |
| CN111201250B (zh) * | 2017-10-10 | 2023-03-14 | 泰国聚乙烯有限公司 | 氧化聚乙烯蜡 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19860174A1 (de) | 2000-06-29 |
| ES2177191T3 (es) | 2002-12-01 |
| DE59901389D1 (de) | 2002-06-13 |
| EP1013672A2 (de) | 2000-06-28 |
| EP1013672B1 (de) | 2002-05-08 |
| US6384148B1 (en) | 2002-05-07 |
| JP2000191724A (ja) | 2000-07-11 |
| EP1013672A3 (de) | 2000-08-09 |
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