CN1330728C - 热熔粘合剂 - Google Patents
热熔粘合剂 Download PDFInfo
- Publication number
- CN1330728C CN1330728C CNB2004800144835A CN200480014483A CN1330728C CN 1330728 C CN1330728 C CN 1330728C CN B2004800144835 A CNB2004800144835 A CN B2004800144835A CN 200480014483 A CN200480014483 A CN 200480014483A CN 1330728 C CN1330728 C CN 1330728C
- Authority
- CN
- China
- Prior art keywords
- wax
- polyolefin
- hotmelt
- melt viscosity
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims abstract description 8
- 239000004831 Hot glue Substances 0.000 title abstract description 3
- 239000001993 wax Substances 0.000 claims abstract description 69
- 239000012943 hotmelt Substances 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 3
- 229920013640 amorphous poly alpha olefin Polymers 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 230000019612 pigmentation Effects 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 2
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- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229920000098 polyolefin Polymers 0.000 abstract description 6
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 20
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- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
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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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920006113 non-polar polymer Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-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
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- XPVIQPQOGTVMSU-UHFFFAOYSA-N (4-acetamidophenyl)arsenic Chemical compound CC(=O)NC1=CC=C([As])C=C1 XPVIQPQOGTVMSU-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- CISVRDKQPCPFQX-UHFFFAOYSA-N C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.C=CC=CC Chemical compound C(C1=CC=CC=C1)[Zr]CC1=CC=CC=C1.C=CC=CC CISVRDKQPCPFQX-UHFFFAOYSA-N 0.000 description 1
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- KPWMGUMUJVLSHH-UHFFFAOYSA-L CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC2=CC=CC=C12 Chemical compound CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC2=CC=CC=C12 KPWMGUMUJVLSHH-UHFFFAOYSA-L 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical compound Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Abstract
本发明涉及含有聚烯烃蜡的热熔粘合剂,其中所述的聚烯烃蜡采用茂金属催化剂制备并具有80-165℃的滴点或环/球软化点和最大为40000mPa.s的熔体粘度,所述熔体粘度在高于滴点或软化点10℃的温度下测量。
Description
本发明涉及包含采用茂金属催化剂制备的聚烯烃蜡的热熔粘合剂。
热熔粘合剂是无溶剂的粘合剂,其以热的、熔融液态施用于待粘合基材,并在凝固后显示它们的粘合效果。由于它们的多方面的优点,它们正越来越广地在尤其包装、家具、纺织品和鞋工业中用作常规溶剂型粘合剂的经济的和环境友好的替代品。普通热熔粘合剂配方的成分是极性或非极性的聚合物(通常为乙烯-醋酸乙烯酯共聚物)树脂和蜡。
极性或非极性聚合物用作骨架物质;它们确保粘合剂的内聚粘牢并同时有助于向基材的粘合作用。树脂的添加改善了粘合作用,并可能向粘合剂各组分施加增进相容性的效果。蜡用于改性,但也可以相应地适合用作骨架物质。它们调节粘合剂的重要物理性能,诸如硬度、熔体粘度和软化点,并且在它们对晾置时间、粘合作用、内聚作用等方面的作用方面,也决定性地影响应用技术特性。
迄今使用的蜡包括粗粒结晶的和微晶的石蜡、费-托合成蜡和聚烯烃蜡。
聚烯烃蜡可以通过支化高聚物聚烯烃塑料的热降解制备,或通过烯烃的直接聚合制备。合适的聚合方法包括例如高压技术,其中烯烃,通常为乙烯,在高压和高温下通过自由基机理反应形成支链蜡,此外还有低压法或齐格勒法,在这些方法中乙烯和/或高级1-烯烃借助有机金属催化剂在比较低的压力和温度下聚合。
新近公开的低压法变型是这样一种操作方式:其中所用的有机金属催化剂为茂金属化合物。所述茂金属化合物含有钛、锆或铪原子作为活性中心,并且通常与助催化剂结合使用,所述助催化剂的例子有有机铝或硼化合物,优选铝氧烷化合物。需要时,聚合反应在用作分子量调节剂的氢的存在下进行。茂金属法的特征在于,与较早期的齐格勒技术相比,可以获得具有更窄分子量分布、更均匀的共单体***、更低熔点和更高催化剂产率的蜡。
现已令人惊奇地发现,使用茂金属催化剂制备的聚烯烃蜡特别有利地适用作热熔粘合剂用的配方组分。特别地,发现含有茂金属蜡的热熔粘合剂,在粘合力(向基材上的粘合作用)和低温柔韧性方面具有突出的性能。
因此,本申请的主题是含有聚烯烃蜡的热熔粘合剂,其中所述聚烯烃蜡采用茂金属催化剂制备并具有80-165℃的滴点或环/球软化点和最大为40000mPa.s的熔体粘度,该熔体粘度在高于滴点或软化点10℃的温度下测量。
聚烯烃蜡优选具有90-160℃的滴点或环/球软化点和最大为30000mPa.s的熔体粘度,该熔体粘度在高于滴点或软化点10℃的温度下测量。
这里,熔体粘度根据DIN53019使用旋转粘度计测定,滴点根据DIN51801/2测定,和环/球软化点根据DIN EN 1427测定。
根据DIN53019的熔体粘度如下测定:
将待测试液体置于在两个同轴圆筒之间的环形间隙中,其中一个圆筒以恒定转数旋转(转子),而另一个静止不动(定子)。测定转数和用以克服液体在环形间隙内的摩擦阻力所需的转矩。从***的几何尺寸和所测得的转矩和转数值,就可计算出在液体中占支配地位的剪切应力,和速度梯度。
通过规定一定的几何情况,上述标准描述了用于测量牛顿和非牛顿流体在具有同轴圆筒的旋转粘度计中的流动行为的标准流型。
滴点表征了固体脂肪、润滑剂、沥青等的可熔融性。滴点是施加在温度计的水银球上-或施加在固定于温度计上的滴点测量仪(例如Ubbelohde型)的螺纹接口上-的测试材料在其自身重量下滴落时的温度点。
根据DIN51801/2,这使用Ubbelohde型接种点仪(Impfpunktgert)如下实施:
将圆筒形的金属套管胶接到温度计下部分,向该套管上可拧上第二个金属套管。在此第二个金属套管的侧面有用于压力补偿的小孔,和在下部分有三个与该套管下缘相距7.5mm的锁定销。将具有向下逐渐变细的圆筒形螺纹接口向该套管配合,其中该螺纹接口由58wt%-63wt%铜含量的铜-锌合金(黄铜)制成。必须将金属套管的上部分胶接到温度计上,使得当下部分紧紧地拧上时,温度计容器的下缘与金属套管的下缘分隔开。在金属套管中的锁定销允许螺纹接口以这样的方式引入套管中,使得温度计容器在任意点上都与螺纹接口内壁等距。将预制的样品以可浇注状态装入到竖立在板上的螺纹接口中,使得产生过量。在正好还能滑动推开的温度下,将螺纹接口小心地推到温度计上的夹具上,使得温度计容器不与螺纹接口壁接触。带有螺纹接口的温度计通过塞子固定于试管中部,其中该塞子中心有通孔和在一侧刻有凹槽。螺纹接口下缘与试管底部的距离应为25mm。将试管以它的最多至三分之二的长度垂直悬挂入烧杯中。烧杯中含有作为浴液的冰水。然后将滴点仪加热,使得从低于预计滴点约10℃起,以每分钟1℃均匀地升温。随着温度升高,样品逐渐软化。观察从螺纹接口流出的粘结剂到达试管底部时的温度。
根据DIN EN 1427的环/球软化点如下测定:
将两层浇注在带凸肩的由铜锌合金制成的环中的沥青层以受控温度改变在液体浴中加热。每层负载一个钢球。将软化点作为温度的算术平均值形式给出,在所述温度下,两层沥青层都已软化到被沥青包围的球已迁移了(25.0±0.4)mm测量距离的程度。
因此,软化点是材料在标准测试条件下达到规定稠度时的温度。聚烯烃蜡优选地具有1000-30000g/mol的重均分子量Mw和500-20000g/mol的数均分子量Mn。
重均分子量Mw、数均分子量Mn和所得的商Mw/Mn通过凝胶渗透色谱法在135℃下在1,2-二氯苯中测定。
热熔粘合剂优选含有作为聚烯烃蜡的由丙烯与0.1-30wt%的乙烯和/或0.1-50wt%的至少一种具有4-20个碳原子的支链或直链1-链烯烃构成的共聚物蜡,和所述共聚物蜡具有100-30000mPa.s的熔体粘度,所述熔体粘度在高于滴点或软化点10℃的温度下测量。
在另一个实施方式中,热熔粘合剂含有作为聚烯烃蜡的丙烯均聚物蜡,所述均聚物蜡具有100-30000mPa.s的熔体粘度,所述熔体粘度在高于滴点或软化点10℃的温度下测量。
在进一步的实施方式中,热熔粘合剂含有作为聚烯烃蜡的乙烯均聚物蜡。
热熔粘合剂也可含有作为聚烯烃蜡的由乙烯与0.1-30wt%的至少一种具有3-20个碳原子的支链或直链的1-链烯烃构成的共聚物蜡。
用于热熔粘合剂中的烯烃均聚物蜡和共聚物蜡可经极性改性。
热熔粘合剂可附加含有填料或助剂,诸如增塑剂、颜料和抗氧剂。合适的聚烯烃蜡包括乙烯或高级的1-烯烃的均聚物或它们彼此间的共聚物。所用的1-烯烃是具有3-18个碳原子,优选具有3-6个碳原子的直链或支链烯烃。这些烯烃可具有与烯烃双键共轭的芳族取代。它们的例子为丙烯、1-丁烯、1-己烯、1-辛烯或1-十八碳烯,和苯乙烯。乙烯或丙烯的均聚物或它们彼此间的共聚物是优选的。该共聚物的70-99.9wt%,优选80-99wt%由一种烯烃类型组成。
合适的烯烃均聚物和共聚物蜡是这样的蜡:具有1000-30000g/mol,优选2000-20000g/mol的重均分子量Mw,500-20000g/mol,优选1000-10000g/mol的数均分子量Mn,90-165℃,优选100-160℃的滴点或环/球软化点,和最大为40000mPa.s,优选100-20000mPa.s的熔体粘度,该熔体粘度在高于滴点或软化点10℃的温度下测量。
为了制备根据本发明所用的聚烯烃蜡,使用通式I的茂金属化合物。
此通式也包括通式Ia的化合物
通式Ib的化合物
和通式Ic的化合物
在通式I、Ia和Ib中,M1为元素周期表的第IVb、Vb或VIb族的金属,例如钛、锆、铪、钒、铌、钽、铬、钼、钨,优选钛、锆、铪。
R1和R2相同或不同,并且表示氢原子,C1-C10-,优选C1-C3-烷基,特别为甲基,C1-C10-,优选C1-C3-烷氧基,C6-C10-,优选C6-C8-芳基,C6-C10-,优选C6-C8-芳氧基,C2-C10-,优选C2-C4-链烯基,C7-C40-,优选C7-C10-芳烷基,C7-C40-,优选C7-C12-烷芳基,C8-C40-,优选C8-C12-芳基链烯基,或卤原子,优选氯原子。
R3和R4相同或不同,并且表示可与中心原子M1形成夹心结构的单核或多核烃基。R3和R4优选为环戊二烯基、茚基、四氢茚基、苯并茚基或芴基,其中母体结构还可带有附加的取代基或可相互桥连。此外,基团R3和R4之一可为取代的氮原子,其中基团R24具有R17的含义,并优选为甲基、叔丁基或环己基。
R5、R6、R7、R8、R9和R10相同或不同,并且表示氢原子,卤原子,优选氟、氯或溴原子,C1-C10-,优选C1-C4-烷基,C6-C10-,优选C6-C8-芳基,C1-C10-,优选C1-C3-烷氧基,基团-NR16 2、-SR16、-OSiR16 3、-SiR16 3或-PR16 2,其中R16为C1-C10-,优选C1-C3-烷基,或C6-C10-,优选C6-C8-芳基,或者在含Si或P的基团中,R16也可为卤原子,优选氯原子,或每两个相邻的基团R5、R6、R7、R8、R9或R10与连接它们的碳原子一起形成环。特别优选的配体是母体结构环戊二烯基、茚基、四氢茚基、苯并茚基或芴基的取代化合物。
R13为:
=BR17、=AlR17、-Ge-、-Sn-、-O-、-S-、=SO、=SO2、=NR17、=CO、=PR17或=P(O)R17,其中R17、R18和R19相同或不同,并且为氢原子,卤原子,优选氟、氯或溴原子,C1-C30-,优选C1-C4-烷基,特别是甲基,C1-C10-氟烷基,优选CF3基团,C6-C10-氟芳基,优选五氟苯基,C6-C10-,优选C6-C8-芳基,C1-C10-,优选C1-C4-烷氧基,特别是甲氧基,C2-C10-,优选C2-C4-链烯基,C7-C40-,优选C7-C10-芳烷基,C8-C40-,优选C8-C12-芳基链烯基,或C7-C40-,优选C7-C12-烷芳基,或者,R17与R18或R17与R19在每种情况下与连接它们的原子一起形成环。
M2为硅、锗或锡,优选硅和锗。R13优选为=CR17R18、=SiR17R18、=GeR17R18、-O-、-S-、=SO、=PR17或=P(O)R17。
R11和R12相同或不同,并具有对于R17所述的含义。m和n相同或不同,并且为0、1或2,优选0或1,其中m+n为0、1或2,优选0或1。
R14和R15具有R17和R18的含义。
合适的茂金属的例子是:
双(1,2,3-三甲基环戊二烯基)二氯化锆、
双(1,2,4-三甲基环戊二烯基)二氯化锆、
双(1,2-二甲基环戊二烯基)二氯化锆、
双(1,3-二甲基环戊二烯基)二氯化锆、
双(1-甲基茚基)二氯化锆、
双(1-正丁基-3-甲基环戊二烯基)二氯化锆、
双(2-甲基-4,6-二异丙基茚基)二氯化锆、
双(2-甲基茚基)二氯化锆、
双(4-甲基茚基)二氯化锆、
双(5-甲基茚基)二氯化锆、
双(烷基环戊二烯基)二氯化锆、
双(烷基茚基)二氯化锆、
双(环戊二烯基)二氯化锆、
双(茚基)二氯化锆、
双(甲基环戊二烯基)二氯化锆、
双(正丁基环戊二烯基)二氯化锆、
双(十八烷基环戊二烯基)二氯化锆、
双(五甲基环戊二烯基)二氯化锆、
双(三甲基甲硅烷基环戊二烯基)二氯化锆、
双环戊二烯基二苄基锆、
双环戊二烯基二甲基锆、
双四氢茚基二氯化锆、
二甲基甲硅烷基-9-芴基环戊二烯基二氯化锆、
二甲基甲硅烷基双-1-(2,3,5-三甲基环戊二烯基)二氯化锆、
二甲基甲硅烷基双-1-(2,4-二甲基环戊二烯基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基-4,5-苯并茚基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基-4-乙基茚基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基-4-异丙基茚基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基-4-苯基茚基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基-茚基)二氯化锆、
二甲基甲硅烷基双-1-(2-甲基四氢茚基)二氯化锆、
二甲基甲硅烷基双-1-茚基二氯化锆、
二甲基甲硅烷基双-1-茚基二甲基锆、
二甲基甲硅烷基双-1-四氢茚基二氯化锆、
二苯基亚甲基-9-芴基环戊二烯基二氯化锆、
二苯基甲硅烷基双-1-茚基二氯化锆、
亚乙基双-1-(2-甲基-4,5-苯并茚基)二氯化锆、
亚乙基双-1-(2-甲基-4-苯基茚基)二氯化锆、
亚乙基双-1-(2-甲基四氢茚基)二氯化锆、
亚乙基双-1-(4,7-二甲基茚基)二氯化锆、
亚乙基双-1-茚基二氯化锆、
亚乙基双-1-四氢茚基二氯化锆、
茚基环戊二烯基二氯化锆、
异丙叉(1-茚基)(环戊二烯基)二氯化锆、
异丙叉(9-芴基)(环戊二烯基)二氯化锆、
苯基甲基甲硅烷基双-1-(2-甲基茚基)二氯化锆、
和这些茂金属二氯化物各自的烷基或芳基衍生物。
使用合适的助催化剂以活化单中心催化剂体系。通式I的茂金属的合适的助催化剂是有机铝化合物,特别是铝氧烷,或无铝体系,诸如R20 xNH4-xBR21 4、R20 xPH4-xBR21 4、R20 3CBR21 4或BR21 3。在这些通式中,x是1-4的数,基团R20相同或不同,优选相同,并为C1-C10-烷基或C6-C18-芳基,或两个R20基团与连接它们的原子一起形成环,和基团R21相同或不同,优选相同,并为可由烷基、卤代烷基或氟取代的C6-C18-芳基。特别地,R20为乙基、丙基、丁基或苯基,以及R21为苯基、五氟苯基、3,5-双三氟甲基苯基、基、二甲苯基或甲苯基。
此外,经常需要第三组分以保持防止极性催化剂中毒。合适的上述组分包括有机铝化合物,如三乙基铝、三丁基铝及其它,以及混合物。
视方法而定,还可以使用负载的单中心催化剂。优选其中载体材料和助催化剂在产品中的残留含量不超过100ppm浓度的催化剂体系。
为制备本发明的热熔粘合剂,可使用未改性的或极性改性形式的茂金属聚烯烃蜡。可通过已知方法由非极性原料,通过用含氧的气体,如空气氧化,或者通过与极性单体,如马来酸或其衍生物的接枝反应,而获得极性改性的蜡。茂金属聚烯烃蜡通过用空气氧化的极性改性,例如描述在EP 0 890 583A1中,通过接枝的改性,例如描述在US-A-5,998,547中。
热熔粘合剂中含有的聚烯烃蜡的重量比例为0.1-100%。其它可能的组分有,作为骨架物质的非极性或极性聚合物,如乙烯-醋酸乙烯酯共聚物、无规立构聚α-烯烃(APAO)、聚异丁烯、苯乙烯-丁二烯-苯乙烯嵌段聚合物或苯乙烯-异戊二烯-苯乙烯嵌段聚合物,或者对于特别高负荷的粘合还有聚酰胺或聚酯。可包含的树脂组分的例子为,松香树脂及其衍生物或烃树脂。热熔粘合剂可进一步包含填料或助剂,诸如增塑剂、颜料和抗氧剂。
实施例
重均分子量Mw、数均分子量Mn和所得的商Mw/Mn通过凝胶渗透色谱法在135℃下在1,2-二氯苯中测定。熔体粘度根据DIN53019使用旋转粘度计测定,滴点根据DIN51801/2测定,和环/球软化点根据DIN EN 1427测定。酸值(在极性改性的蜡的情况下)根据DIN53402测定。
根据DIN53402的方法用于测定树脂、油、脂肪、脂肪酸和其它工业有机物质和物质混合物的酸值。酸值在此说明在规定条件下用以中和1克待测试样品所需的那个以毫克计的氢氧化钾的数量。
操作步骤:
称取精确至0.001g的样品放入滴定容器中,并将该样品溶于50ml的溶剂混合物中。必要时,将溶液冷却至室温,并在加入2至3滴酚酞溶液后,用KOH醇溶液快速滴定直至存在显现红色至少10s。
根据本发明所用的茂金属聚烯烃蜡,其列于表1中,是通过EP-A-0571 882中说明的方法制备的。它们都具有1000-30000g/mol的重均分子量Mw和500-20000g/mol的数均分子量Mn。
表1:所用的聚烯烃蜡
产品类型 | 聚合催化剂或方法 | 滴点℃ | 酸值mg KOH/g | 粘度mPa.s | |
实施例1 | 乙烯均聚物蜡 | 茂金属 | 125 | - | 60/140℃ |
实施例2 | 乙烯/丙烯共聚物蜡 | 茂金属 | 116 | - | 680/140℃ |
实施例3 | 丙烯-乙烯共聚物蜡 | 茂金属 | 120 | - | 460/140℃ |
实施例4 | 氧化的乙烯-丙烯共聚物蜡* | 茂金属 | 105 | 18 | 250/120℃ |
实施例5 | 得自实施例1的茂金属乙烯均聚物的MSA接枝产物 | - | 121 | 11 | 110/140℃ |
对比例1 | 乙烯均聚物蜡 | 齐格勒 | 125 | - | 200/140℃ |
对比例2 | 乙烯/丙烯共聚物蜡 | 齐格勒 | 118 | - | 600/140℃ |
对比例3 | 丙烯均聚物蜡 | 齐格勒 | 158 | - | 710/170℃ |
对比例4 | 氧化的乙烯-丙烯共聚物蜡** | 齐格勒 | 108 | 18 | 250/120℃ |
对比例5 | 得自对比例1的齐格勒-乙烯均聚物蜡的MSA接枝产物 | - | 122 | 9 | 610/140℃ |
*由空气氧化的实施例2的蜡
**由空气氧化的对比例2的蜡
应用技术测试结果
使用列于表1中的蜡制备热熔粘合剂。为此,在玻璃烧杯中熔融下述物质组成的混合物并在180℃下搅拌1小时:
47.5gElvax220(DuPont)(熔体粘度230000mPa.s/140℃),
47.3gResin 835A(Abieta Chemie GmbH)和
5.0g各测试蜡,以及
0.4gHostanox 0 10(Clariant GmbH)。
根据DIN53281,用这些混合物涂覆和粘合铝箔。粘合力根据DIN53282(角度剥离试验)测量。
DIN53282规定了铝合金样品粘合面的预处理,所述样品用于金属粘合剂和金属粘合体的比较性测试。粘合面预处理包括清洗、脱脂、化学处理、冲洗以及在粘合剂施用前粘合面的隔离。粘合面必须使用有机溶剂(蒸气浴或浸浴)脱脂或用无机脱脂剂(在低温浴、热浴或电解槽中,例如用缓冲的碱性溶液)脱脂。粘合应尽可能在粘合面预处理后立即进行。在能确保遵从规定的凝固条件(温度、贴紧压力、时间)的设备中进行粘合。温度必须在粘合层中或在粘合层上测量。对粘合面的贴紧压力必须均匀分布,并且它能采用机械方式、液压方式或在高压釜中通过真空来施加。
根据DIN53282的角度剥离试验用于测定金属粘合体对剥离力的阻力。测试主要用于粘合剂和粘合体的比较性评价,并且也用于监控粘合面的预处理。为此,将T-形的成角度的粘合样品使用拉伸试验机在它的未粘合的两臂上长时间加载拉力,直到粘合层撕裂以及样品的两半部分相互分离为止。将上述所需的力在同时测量在夹持头之间的长度变化的情况下记录在剥离曲线图中。为了测定低温柔韧性,制备250×10mm大的测试件并将其弯曲绕在心轴上。从0℃开始以1°的间隔降温。所用的测量参数是测试件断裂时的那个温度。
表2:配方混合物的性能/应用技术结果
使用的蜡 | R/K软化点℃ | 在180℃下的粘度mPa.s | 粘合力N/mm | 低温柔韧性℃ |
实施例1 | 91 | 1700 | 0.8 | -5 |
对比例1 | 82 | 3200 | 0.3 | 0 |
实施例2 | 87 | 3300 | 1.2 | -10 |
对比例2 | 87 | 3500 | 0.8 | 0 |
实施例3 | 73 | 3400 | 1.4 | -15 |
对比例3 | 101 | 5050 | 1.2 | -5 |
实施例4 | 84 | 2200 | 1.3 | -10 |
对比例4 | 85 | 2800 | 1.1 | -10 |
实施例5 | 76 | 4400 | 1.8 | -20 |
对比例5 | 78 | 5000 | 1.7 | -10 |
当与对比例比较时,使用茂金属蜡制备的配方一般具有更高的粘合力和主体上的更好的低温柔韧性。
Claims (8)
1、一种热熔粘合剂,其含有聚烯烃蜡,其中所述聚烯烃蜡使用茂金属催化剂制备,以未改性形式使用并具有80-165℃的滴点或环/球软化点和最大为40000mPa.s的熔体粘度,所述熔体粘度在高于滴点或软化点10K的温度下测量,并含有至少一种选自如下的其它组分:乙烯-醋酸乙烯酯共聚物、无规立构聚α-烯烃、聚异丁烯、苯乙烯-丁二烯-苯乙烯嵌段聚合物、苯乙烯-异戊二烯-苯乙烯嵌段聚合物、聚酰胺、聚酯、松香树脂及其衍生物或烃树脂或这些物质的组合。
2、根据权利要求1的热熔粘合剂,其特征在于,聚烯烃蜡具有90-160℃的滴点或环/球软化点和最大为30000mPa.s的熔体粘度,所述熔体粘度在高于滴点或软化点10K的温度下测量。
3、根据权利要求1的热熔粘合剂,其特征在于,聚烯烃蜡具有1000-30000g/mol的重均分子量Mw和500-20000g/mol的数均分子量Mn。
4、根据权利要求1-3中任一项的热熔粘合剂,其含有作为聚烯烃蜡的由丙烯与0.1-30wt%的乙烯和/或0.1-50wt%的至少一种具有4-20个碳原子的支链或直链的1-链烯烃构成的共聚物蜡,所述共聚物蜡具有100~30000mPa.s的熔体粘度,该熔体粘度在高于滴点或软化点10K的温度下测量。
5、根据权利要求1-3中任一项的热熔粘合剂,其含有作为聚烯烃蜡的丙烯均聚物蜡,所述均聚物蜡具有100-30000mPa.s的熔体粘度,该熔体粘度在高于滴点或软化点10K的温度下测量。
6、根据权利要求1-3中任一项的热熔粘合剂,其含有作为聚烯烃蜡的乙烯均聚物蜡。
7、根据权利要求1-3中任一项的热熔粘合剂,其含有作为聚烯烃蜡的由乙烯与0.1-30wt%的至少一种具有3-20个碳原子的支链或直链的1-链烯烃构成的共聚物蜡。
8、根据权利要求1-3中任一项的热熔粘合剂,其特征在于,其另外含有增塑剂、颜料和/或抗氧剂作为填料或助剂。
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EP (1) | EP1631641B1 (zh) |
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2004
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- 2004-05-18 CN CNB2004800144835A patent/CN1330728C/zh not_active Expired - Lifetime
- 2004-05-18 JP JP2006529853A patent/JP2007501320A/ja active Pending
- 2004-05-18 US US10/533,475 patent/US20060235134A1/en not_active Abandoned
- 2004-05-18 EP EP04733539A patent/EP1631641B1/de not_active Expired - Lifetime
- 2004-05-18 WO PCT/EP2004/005322 patent/WO2004104128A1/de active IP Right Grant
- 2004-05-18 ES ES04733539T patent/ES2284013T3/es not_active Expired - Lifetime
- 2004-05-24 TW TW093114645A patent/TWI359155B/zh active
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2006
- 2006-10-18 HK HK06111429A patent/HK1090658A1/xx not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5081322A (en) * | 1989-02-15 | 1992-01-14 | Hoechst Aktiengesellschaft | Polypropylene wax and process for the production thereof |
US5998547A (en) * | 1996-11-26 | 1999-12-07 | Clariant Gmbh | Polypropylene waxes modified so as to be polar |
US6211303B1 (en) * | 1997-07-11 | 2001-04-03 | Clariant Gmbh | Process for the oxidation of polyethylene waxes |
Also Published As
Publication number | Publication date |
---|---|
DE502004003288D1 (de) | 2007-05-03 |
DE502004003288C5 (de) | 2016-09-01 |
DE10323617A1 (de) | 2004-12-23 |
TW200427701A (en) | 2004-12-16 |
EP1631641A1 (de) | 2006-03-08 |
CN1795250A (zh) | 2006-06-28 |
ES2284013T3 (es) | 2007-11-01 |
WO2004104128A1 (de) | 2004-12-02 |
JP2007501320A (ja) | 2007-01-25 |
US20060235134A1 (en) | 2006-10-19 |
TWI359155B (en) | 2012-03-01 |
HK1090658A1 (en) | 2006-12-29 |
EP1631641B1 (de) | 2007-03-21 |
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