CN110603304A - 改进的粘合性聚合物组合物 - Google Patents
改进的粘合性聚合物组合物 Download PDFInfo
- Publication number
- CN110603304A CN110603304A CN201880028847.7A CN201880028847A CN110603304A CN 110603304 A CN110603304 A CN 110603304A CN 201880028847 A CN201880028847 A CN 201880028847A CN 110603304 A CN110603304 A CN 110603304A
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- China
- Prior art keywords
- polymer composition
- adhesive polymer
- composition according
- adhesive
- elastomeric copolymer
- Prior art date
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- Granted
Links
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- JOWXNCPELQZFHF-UHFFFAOYSA-N 2-[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoyloxy]ethyl 3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoate Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(CC(=O)OCCOC(=O)CC(C)(C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 JOWXNCPELQZFHF-UHFFFAOYSA-N 0.000 description 3
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- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241001538365 Accipiter nisus Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical compound C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000001530 fumaric acid Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
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Abstract
本文公开了一种粘合性聚合物组合物,包含乙烯与一种或多种具有3至10个碳原子的共聚单体的非弹性体共聚物以及弹性体。基于所述粘合性聚合物组合物,所述非弹性体共聚物按重量以60%至95%的量存在,其具有:从50000g/mol至80000g/mol的重均分子量Mw、2.0至5.5的分子量分布Mw/Mn、从0.925g/cm3至0.945g/cm3的密度和至多0.1个乙烯基/1000个碳原子。所述非弹性体共聚物或所述非弹性体共聚物及所述弹性体使用酸接枝剂进行接枝。
Description
技术领域
本发明涉及一种包含酸接枝聚乙烯和弹性体的粘合性聚合物组合物,涉及一种包括粘合性聚合物组合物的层的制品,特别是多层管,如涂层金属管,以及涉及粘合性聚合物组合物用于制备粘合层,特别是管(如涂层金属管)的多层结构的粘合层的用途。
背景技术
所要解决的问题
包括两层、三层、四层、五层或更多层的多层结构以应用众多而闻名,例如管的防护涂层。在这些多层结构中,不同的层通常由不同的材料组成,不同的材料相应地具有不同的理化性质。这就导致了一个问题,相邻层没有彼此粘附或只是在不充分的程度上彼此粘附。因此,普遍共识为构造具有中间粘合层的多层结构,以提高由不同材料组成的相邻层的粘附力,由此避免分层。
例如,在金属管的涂层中,通常使用三层聚合物结构。其由环氧树脂层(旨在牢固粘附于管的金属壁的外表面)、中间粘合层和外部聚烯烃防护层(通常为聚乙烯或聚丙烯)组成。与先前已知的单层涂层相比,三层结构显示出了更好的性能。一方面,环氧树脂层对金属壁显示出了更好的粘合,避免了阴极剥离,并使氧渗透更少,而另一方面,外部聚烯烃基层提供了良好的机械保护和更少的水渗透。然而,为避免聚烯烃层和环氧树脂层的分层,该分层会导致多层的损坏,在两层之间涂覆粘合层是必须的。
用于制备此类层的粘合层及材料可从例如WO99/37730 A1中获知,其公开了一种包含乙烯共聚物组分和从2wt%至35wt%的接枝茂金属聚乙烯的粘合剂组合物。
JP 8208915 A描述了一种包含接枝的乙烯/α-烯烃共聚物的粘合性聚乙烯组合物,作为覆盖物用于例如电缆和钢管。
EP 0896044 A1涉及一种粘合性树脂组合物,尤其是用于层压材料。此树脂包含α-烯烃/芳香族乙烯基化合物的无规共聚物,其部分或全部接枝修饰。
EP 0791628 B1提供了一种粘合剂组合物,包含具有增粘剂的接枝长链支化乙烯-α-烯烃共聚物,或乙烯-醋酸乙烯共聚物,用作粘附诸如金属的膜层。
EP 1316598 B1公开了一种粘合性聚合物组合物,包含使用单位点催化剂制备的酸接枝聚乙烯,其含量为组合物的至少40wt%。
WO 2009/103516 A2公开了一种粘合性聚合物组合物,包含酸接枝聚乙烯,其具有:从6至30的Mw/Mn、从0.93至0.955g/cm3的密度、从20000至500000g/mol的Mw、从0.01至20个CH3/1000个碳原子且至少0.6个乙烯基/1000个碳原子,含量为组合物的至少50wt%
尽管存在现有技术,但对于用于制备多层结构的粘合层的具有改进粘附性能的粘合性聚合物组合物,仍然保有需要。
发明内容
本发明提供了一种粘合性聚合物组合物,包含:
a)乙烯与一种或多种具有3至10个碳原子的共聚单体的非弹性体共聚物,其中,基于所述粘合性聚合物组合物,所述非弹性体共聚物按重量以60%至95%的量存在,其具有:从50000g/mol至80000g/mol的重均分子量Mw、2.0至5.5的分子量分布Mw/Mn、从0.925g/cm3至0.945g/cm3的密度和至多0.1个乙烯基/1000个碳原子;以及
b)弹性体,
其中,所述非弹性体共聚物或所述非弹性体共聚物及所述弹性体使用酸接枝剂(acid grafting agent)进行接枝。
本发明还提供了一种制品,特别是一种多层管,包括含有所述粘合性聚合物组合物的粘合层。
本发明还提供了所述粘合性聚合物组合物用于制备粘合层、尤其是管的粘合层的用途。
具体实施方式
本发明的粘合性聚合物组合物显示出了改进的粘附性能,特别是用作粘合层时。例如,当共挤出作为用于金属管涂层的三层结构的粘合层时,粘合性聚合物组合物在23℃下显示出了改进的剥离强度值。
本发明的粘合性聚合物组合物的非弹性体共聚物为乙烯与一种或多种α-不饱和烯烃共聚单体的非弹性体共聚物。优选地,α-烯烃共聚单体包含从3至20个碳原子,更优选从2至12个碳原子,以及最优选从3至8个碳原子。
α-烯烃共聚单体的示例包括丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-癸烯及其混合物。特别优选的共聚单体是1-丁烯、1-己烯及1-辛烯。
典型地,非弹性体共聚物内的共聚单体的量为按重量从1%至30%,更优选为按重量从1%至5%。
基于粘合性聚合物组合物,非弹性体共聚物按重量以60%至95%的量存在。在进一步优选的实施方式中,基于粘合性聚合物组合物,非弹性体共聚物按重量以70%至90%的量存在。
非弹性体共聚物具有从40000g/mol至90000g/mol的重均分子量Mw,更优选从50000g/mol至80000g/mol。
非弹性体共聚物具有从2.0至5.5的分子量分布Mw/Mn,更优选从2.5至5.0。
非弹性体共聚物具有从0.920g/cm3至0.950g/cm3的密度,更优选从0.925g/cm3至0.945g/cm3,还更优选从0.930g/cm3至0.942g/cm3。
非弹性体共聚物具有从0至0.1个乙烯基/1000个碳原子,优选从0.01至0.07个乙烯基/1000个碳原子。
非弹性体共聚物可以没有长支链或具有长支链。典型地,长支链的量取决于催化剂和所采用的工艺条件。术语“长支链”是指通过聚合条件产生的支链,而不是由可聚合的共聚单体种类引入的支链。
非弹性体共聚物可以于包含本领域已知的任意催化剂的工艺中制备,更优选于包含本领域已知的任意单位点催化剂的工艺中制备。
非弹性体共聚物也可以于包含单位点催化剂和其他具有相同或不同性质的催化剂的混合物的工艺中制备。至于单位点催化剂和不同性质的催化剂的混合物,优选粘合性聚合物组合物的非弹性体共聚物的至少90%通过单位点催化剂制备。
优选地,非弹性体共聚物于包含茂金属催化剂的工艺中制备。进一步优选地,催化剂包含于载体上的茂金属组分和铝氧烷组分。
可以使用任意已知工艺来制备非弹性体共聚物,例如浆料、气相或溶液工艺或前述工艺的组合。
更典型地,可以于浆料工艺中制备非弹性体共聚物,例如,如US 3248179 A中所公开的。
聚合步骤之前可以具有预聚合步骤。预聚合步骤可在环流反应器中进行。此外,预聚合优选在惰性稀释剂中进行,典型地在烃类稀释剂中,例如甲烷、乙烷、丙烷、正丁烷、异丁烷、戊烷、己烷、庚烷、辛烷等,或其混合物。优选地,稀释剂为具有从1至4个碳原子的低沸点烃类或这些烃类的混合物。预聚合步骤中的温度典型地为从0℃至90℃,优选从20℃至80℃,更优选从50℃至75℃。压力并非关键,典型地从1巴至150巴,优选从40巴至80巴。预聚合步骤期间乙烯进料的量典型地从100g/h至6000g/h,优选从2000g/h至4000g/h。1-丁烯作为共聚单体加入,且预聚合步骤期间共聚单体进料的量为从10g/h至400g/h,优选从50g/h至200g/h。预聚合期间的氢气的量从0g/h变化至2g/h,优选从0g/h变化至0.4g/h。
聚合阶段优选以浆料聚合来进行。聚合步骤可在环流反应器中进行。浆料聚合通常在惰性稀释剂中发生,典型地在烃类稀释剂中,例如甲烷、乙烷、丙烷、正丁烷、异丁烷、戊烷、己烷、庚烷、辛烷等,或其混合物。优选地,稀释剂为具有从1至4个碳原子的低沸点烃类或这些烃类的混合物。特别优选的稀释剂为丙烷,可含有微量的甲烷、乙烷和/或丁烷。浆料的液相中的乙烯含量可以为按摩尔从1%至约50%,优选按摩尔从约2%至约20%,特别是按摩尔从约2%至约10%。聚合阶段中的温度典型地为从60℃至100℃,优选从70℃至90℃。压力为从1巴至150巴,优选从40巴至80巴。达到预期MFR所需的氢气的量取决于所使用的催化剂以及聚合条件。聚合期间氢气与乙烯的摩尔比典型地从0g/h至4g/h,优选从0g/h至1g/h。达到预期密度所需的共聚单体的量取决于共聚单体的类型、所使用的催化剂以及聚合条件。
在本发明的粘合性聚合物组合物中,弹性体为弹性体乙烯共聚物。弹性体可以为乙丙橡胶(EPR)、乙烯α-烯烃弹性体或塑性体、或乙丙二烯单体橡胶(EPDM)。优选地,弹性体包括乙烯与一种或多种极性单体的弹性体共聚物。此类弹性体的优选示例为乙烯-烷基丙烯酸酯和乙烯-烷基醋酸酯。进一步优选地,共聚单体具有式–O(CO)C1-C6-烷基或–C(O)-OC1-C6-烷基的极性部分。特别优选的弹性体为乙烯-醋酸乙烯酯(EVA)、乙烯-丙烯酸甲酯(EMA)、乙烯-甲基丙烯酸甲酯(EMMA)、乙烯-丙烯酸丙酯以及乙烯-丙烯酸丁酯(EBA),特别为EBA。
弹性体可以通过本领域已知的任意工艺来制备,也包括含有单位点催化剂的工艺。丙烯酸酯共聚物于自由基工艺中制备。
关于酸接枝剂,可使用本领域技术人员已知的适用此目的的任意此类试剂。
优选地,酸接枝剂为不饱和羧酸或其衍生物,例如酸酐、酯和盐(金属和非金属兼有)。优选地,不饱和基团与羧基基团共轭。此类接枝剂的示例包括丙烯酸、甲基丙烯酸、富马酸、马来酸、纳迪克酸(nadic acid)、柠康酸、衣康酸、巴豆酸及其酸酐、金属盐、酯、酰胺或酰亚胺。优选的接枝剂为马来酸,其衍生物如马来酸酐,特别是马来酸酐。
接枝可以通过本领域已知的任意工艺进行,例如,在没有溶剂的熔体中、或在溶液或分散液中、或在流化床中进行的接枝。典型地,以例如在US 3236917 A、US 4639495 A、US4950541 A或US 5194509 A中所描述的,在加热的挤出机或混合机中进行接枝。这些文件的内容通过引用并入本文之中。典型地,以US 4950541 A中所描述的,在双螺杆挤出机中进行接枝。
接枝可以于存在或不存在自由基引发剂的情况下进行,但优选于存在自由基引发剂(例如有机过氧化物、有机过酸酯或有机氢过氧化物)的情况下进行。
基于粘合性聚合物组合物,在接枝前加入至粘合性聚合物组合物中的所述酸接枝剂的量优选为从0.01重量份至3.0重量份,更优选从0.03重量份至1.5重量份。
接枝可应用于非弹性体共聚物或非弹性体共聚物和弹性体的共混物。优选地,接枝应用于非弹性体共聚物和弹性体的共混物。
优选地,接枝前的非弹性体共聚物具有从1g/min至20g/min的熔体流动速率MFR2,更优选从1g/min至10g/min。
非弹性体共聚物可以为单峰或多峰聚乙烯。优选地,非弹性体共聚物为单峰聚乙烯。
“聚合物的形态”的表述是指其分子量分布(MWD)曲线的形状,即聚合物重量分数作为其分子量的函数的图形表现。如果聚合物是在一个或多个反应器中制备的,且一个或多个反应器具有遍及反应器的相似条件,则使用单位点催化剂仅制备了一种类型的聚合物。在这种情况下,制得的聚合物是单峰的。
在优选的实施方式中,粘合性聚合物组合物具有从0.1g/min至10g/min的MFR2值(接枝后),更优选从1.0g/min至6.0g/min。
粘合性聚合物组合物具有从0.925g/cm3至0.945g/cm3的密度,更优选从0.930g/cm3至0.940g/cm3。
粘合性聚合物组合物包含如前文所描述的非弹性体共聚物和弹性体。除了这些组分之外,常规的添加剂也可以少量存在于粘合性聚合物组合物之中,优选高至按重量最多4%。例如,抗氧剂可以以至多10000ppm的量存在于粘合性聚合物组合物之中,更优选至多5000ppm,最优选至多3000ppm。
优选地,粘合性聚合物组合物不含常规的添加剂而由非弹性体共聚物和弹性体组成,即在接枝之前或之后没有更多的聚合物组分加入。常规的添加剂可以在接枝之前或之后加入。
本发明的粘合性聚合物组合物作为共挤出粘合剂是最有用的,但不排除其他用途。
本发明还涉及一种制品,其包括包含如前文所描述的粘合性聚合物组合物的粘合层。此类制品,例如,包括管、电缆、薄膜、通过挤出涂布制得的制品以及工程应用中使用的制品。在后者中,粘合性聚合物组合物还可用于提供不同层或部分之间的相容性。
在优选的实施方式中,制品中的粘合层与聚烯烃层相邻。本发明特别涉及一种多层管(即包括涂覆有两层、三层、四层、五层或更多层的多层的管),其包括聚烯烃层以及与聚烯烃层相邻的包含如前文所描述的本发明粘合性聚合物组合物的粘合层。
在优选的实施方式中,本发明还涉及一种涂层金属管,包括聚烯烃层以及极性聚合物层,特别是环氧树脂层,其中在这些层之间存在有包含根据任意前述实施方式的粘合性聚合物组合物的粘合层。特别地,本发明还涉及一种具有三层防护涂层的金属管,所述三层防护涂层由内部环氧树脂层、包含本发明的粘合性聚合物组合物的中间粘合层以及外部聚烯烃层(例如聚乙烯或聚丙烯层)组成。
此外,本发明涉及如前文所描述的粘合性聚合物组合物用于制备粘合层的用途。优选地,本发明还涉及粘合性聚合物组合物用于制备制品(例如,管、电缆、薄膜、通过挤出涂布制得的制品以及工程应用中使用的制品)中的粘合层的用途。在这些制品的后者中,粘合性聚合物组合物还可用于提供不同层或部分之间的相容性。
在优选的实施方式中,本发明还涉及粘合性聚合物组合物用于制备管的粘合层的用途。特别地,本发明还涉及粘合性聚合物组合物用于制备前述具有三层防护涂层的金属管的涂层的粘合层的用途。
在制备具有三层涂层的涂层金属管时,优选地,通过将粉末或液体形式、一种或两种组分形式的环氧树脂喷涂在已加热的金属壁外表面上来首先制备环氧树脂层。由此,环氧树脂形成牢固粘附金属表面的薄层。随后,在环氧树脂层上共挤出粘合剂和优选是聚乙烯或聚丙烯层的聚烯烃层。还可以通过向环氧树脂层上喷涂粉末形式的粘合剂来施加粘合剂。
方法
熔融指数
根据ISO 1133-1方法B于190℃在2.16kg负荷下测定熔体流动速率(MFR)并以g/10min表示。
密度
根据ISO 1183-1方法A使用压塑试样测定聚合物的密度。
通过NMR光谱法的微观结构定量:乙烯-丁烯以及乙烯-己烯共聚单体
使用定量核磁共振(NMR)光谱法定量聚合物的共聚单体含量。
使用Bruker Advance III 500NMR光谱仪,对1H和13C而言分别在500.13和125.76MHz下进行操作记录熔融状态的定量13C{1H}NMR光谱。在150℃下使用氮气用于所有气动并使用13C优化的7mm魔角旋转(MAS)探头来记录所有光谱。将大约200mg的材料装入7mm外径的二氧化锆MAS旋翼并在4kHz下旋转。选择此设置主要是由于快速鉴定和精确定量所需的高灵敏度(Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006;207:382.,Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007;208:2128.,Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373)。利用3s短循环延迟下的瞬态NOE(Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.,Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006;207:382.)以及RS-HEPT去耦合方案(Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239,Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,和Brown,S.P.,Mag.Res.in Chem.200745,S1,S198)来使用标准单脉冲激发。每个光谱获得总共1024(1k)个瞬态。选择此设置是由于其对于低共聚单体含量的高灵敏度。
对定量13C{1H}NMR光谱进行处理、积分并使用专有光谱分析自动化程序来测定定量性质。所有的化学位移内部参照在30.00ppm处的本体亚甲基信号(δ+)(J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201)。
乙烯-丁烯共聚物中的共聚单体含量定量:
观察到对应1-丁烯的结合的特征信号(J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.)并计算出关于存在于聚合物中的所有其他单体的所有含量。
观察到孤立的1-丁烯结合(即EEBEE共聚单体序列)产生的特征信号。孤立的1-丁烯结合使用39.84ppm处信号的积分来定量,指定为*B2位点,在每一共聚单体报告位点的数目的占比:
B=I*B2
当观察到连续的1-丁烯结合(即EBBE共聚单体序列)产生的特征信号时,此连续的1-丁烯结合使用39.4ppm处信号的积分来定量,指定为ααB2B2位点,在每一共聚单体报告位点的数目的占比:
BB=2*IααB2B2
当同样观察到非连续的1-丁烯结合(即EBEBE共聚单体序列)产生的特征信号时,此非连续的1-丁烯结合使用24.7ppm处信号的积分来定量,指定为ββB2B2位点,在每一共聚单体报告位点的数目的占比:
BEB=2*IββB2B2
由于孤立的1-丁烯结合(EEBEE)和非连续的1-丁烯结合(EBEBE)各自的*B2和*βB2B2位点的重叠,基于存在的非连续的1-丁烯结合的量对孤立的1-丁烯结合的总量进行校正:
B=I*B2-2*IββB2B2
没有观察到其他共聚单体序列(即丁烯链引发)的其他指示性信号的情况下,仅仅基于孤立的(EEBEE)、连续的(EBBE)和非连续的(EBEBE)1-丁烯共聚单体序列的量来计算总的1-丁烯共聚单体含量:
B总=B+BB+BEB
观察到饱和端基产生的特征信号。使用分别指定为2s和3s位点的22.84ppm和32.23ppm处信号的积分平均值来定量此饱和端基的含量:
S=(1/2)*(I2S+I3S)
使用30.00ppm处的本体亚甲基(δ+)信号的积分来定量乙烯的相对含量:
E=(1/2)*Iδ+
总的乙烯共聚单体含量的计算是基于本体亚甲基信号以及存在于其他所观察到的共聚单体序列或端基中的乙烯单元的占比。
E总=E+(5/2)*B+(7/2)*BB+(9/2)*BEB+(3/2)*S
于是,聚合物中的1-丁烯的总摩尔分数计算为:
fB=(B总/(E总+B总)
以常规方法由摩尔分数计算按摩尔百分比计的1-丁烯的总共聚单体结合:
B[mol%]=100*fB
以标准方法由摩尔分数计算按重量百分比计的1-丁烯的总共聚单体结合:
B[wt%]=100*(fB*56.11)/((fB*56.11)+((1-fB)*28.05))
乙烯-己烯共聚物中的共聚单体含量定量:
观察到对应于1-己烯的结合的特征信号(J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.)并计算出关于存在于聚合物中的所有其他单体的所有含量。
观察到孤立的1-己烯结合(即EEHEE共聚单体序列)产生的特征信号。孤立的1-己烯结合使用38.29ppm处信号的积分来定量,指定为*B4位点,在每一共聚单体报告位点的数目的占比:
H=I*B4
当观察到连续的1-己烯结合(即EHHE共聚单体序列)产生的特征信号时,此连续的1-己烯结合使用40.46ppm处信号的积分来定量,指定为ααB4B4位点,在每一共聚单体报告位点的数目的占比:
HH=2*IααB4B4
当观察到非连续的1-己烯结合(即EHEHE共聚单体序列)产生的特征信号时,此非连续的1-己烯结合使用24.7ppm处信号的积分来定量,指定为ββB4B4位点,在每一共聚单体报告位点的数目的占比:
HEH=2*IββB4B4
由于分别来自孤立的(EEHEE)和非连续的(EHEHE)结合的1-己烯的*B4和*βB4B4位点的信号的重叠,基于存在的非连续的1-己烯的量对孤立的1-己烯结合的总量进行校正:
H=I*B4-2*IββB4B4
没有观察到其他共聚单体序列(即1-己烯链引发)的其他指示性信号的情况下,仅仅基于含有孤立的(EEHEE)、连续的(EHHE)和非连续的(EHEHE)1-己烯共聚单体的序列的量来计算总的1-己烯共聚单体含量:
H总=H+HH+HEH
观察到饱和端基产生的特征信号。使用分别指定为2s和3s位点的22.84和32.23ppm处信号的积分平均值来定量此饱和端基的含量:
S=(1/2)*(I2S+I3S)
使用30.00ppm处的本体亚甲基(δ+)信号的积分来定量乙烯的相对含量:
E=(1/2)*Iδ+
总的乙烯共聚单体含量的计算是基于本体亚甲基信号以及存在于其他所观察到的共聚单体序列或端基中的乙烯单元的占比。
E总=E+(5/2)*H+(7/2)*HH+(9/2)*HEH+(3/2)*S
于是,聚合物中的1-己烯的总摩尔分数计算为:
fH=(H总/(E总+H总)
以常规方法由摩尔分数计算按摩尔百分比计的1-己烯的总共聚单体结合:
H[mol%]=100*fH
以标准方法由摩尔分数计算按重量百分比计的1-己烯的总共聚单体结合:
H[wt%]=100*(fH*84.16)/((fH*84.16)+((1-fH)*28.05))
平均分子量、分子量分布(Mn、Mw、Mz、MWD)
根据ISO 16014-1:2003、ISO 16014-2:2003、ISO 16014-4:2003以及ASTM D6474-12通过凝胶渗透色谱法(GPC)使用以下公式测定平均分子量(Mz、Mw及Mn)、分子量分布(MWD)及其宽度,用多分散指数描述,PDI=Mw/Mn(其中Mn是数均分子量且Mw是重均分子量):
对于恒定洗脱体积间隔ΔVi(其中Ai和Mi为色谱峰切片面积和聚烯烃分子量(Mw)),分别与洗脱体积Vi相关,其中的N等于获自色谱图在积分极限之间的数据点的数目。按照ISO 16017-1:2003进行峰值积分,这意味着在1000g/mol以下的油和抗氧剂的峰没有被列入MWD的计算之中。
使用来自PolymerChar(西班牙,巴伦西亚)的装配有红外(IR)检测器(IR5)的高温GPC仪器,其还装配有3×Agilent-PLgel Olexis柱以及1×Agilent-PLgel Olexis Guard柱。使用以250mg/L 2,6-二叔丁基-4-甲基苯酚稳定后的1,2,4-三氯苯(TCB)作为溶剂和流动相。色谱系统在160℃以及1mL/min的恒定流动速率下进行操作。每次分析注入200μL样品溶液。使用PolymerChar的GPCone软件进行数据收集。
使用19种0.5kg/mol至11500kg/mol范围内的窄MWD聚苯乙烯(PS)标准品对此柱组进行普适校准(根据ISO 16014-2:2003)。将PS标准品在160℃下溶解15min。通过使用马克·霍温克方程以及下列马克·霍温克常数来完成聚苯乙烯峰位分子量向聚烯烃分子量的转化:
KPS=19×10-3mL/g,αPS=0.655
KPE=39×10-3mL/g,αPE=0.725
KPP=19×10-3mL/g,αPP=0.725
使用三阶多项式拟合来拟合校准数据。
以0.5-1mg/ml的浓度范围制备所有样品,并在连续的温和摇动下于160℃溶解3小时。
剥离强度
剥离强度指示环氧树脂层和粘合层之间的粘合相对强度。使用Zwick Roell拉力测试机根据ISO21809-1:2011在23℃下测试涂层组合物的剥离强度,测试方法具有以下变化:对剥离强度记录三分钟,然后计算此三分钟全部记录的剥离强度的平均值。此平均值对应于组合物的报告剥离强度。
不饱和
使用定量核磁共振(NMR)光谱法定量聚合物中存在的不饱和基团的含量。
使用Bruker Advance III 400NMR光谱仪在400.15MHz下进行操作记录溶液状态的定量1H NMR光谱。在125℃下使用氮气用于所有气动并使用13C优化的10mm选择性激发探头来记录所有光谱。使用约3mg的Hostanox 03(CAS 32509-66-3)作为稳定剂,将约250mg的材料溶于1,2-四氯乙烷-d2(TCE-d2)中。利用30度脉冲、10s的弛豫延迟以及10Hz样品旋转以采用标准单脉冲激发。使用4次空扫,每个光谱获得总共128个瞬态。选择此设置主要是由于不饱和定量所需的高分辨率以及亚乙烯基基团的稳定性。(He,Y.,Qiu,X,和Zhou,Z.,Mag.Res.Chem.2010,48,537-542.,Busico,V.等人,Macromolecules,2005,38(16),6988-6996)使用5.95ppm处的残余质子化溶剂产生的信号,所有的化学位移均间接参照0.00ppm处的TMS。
观察到末端脂肪族乙烯基(R-CH=CH2)的存在所对应的特征信号,数量使用4.95、4.98和5.00及5.05ppm处的两个耦合的非等价末端CH2质子(Va和Vb)的积分来定量,在每一官能基团报告位点的数目的占比:
N乙烯基=IVab/2
观察到内部亚乙烯基(RR’C=CH2)的存在所对应的特征信号,数量使用4.74ppm处的两个CH2质子(D)的积分来定量,在每一官能基团报告位点的数目的占比:
N亚乙烯基=ID/2
当观察到内部顺式亚乙烯基(E-RCH=CHR’)或其相关结构的存在所对应的特征信号时,数量则使用5.39ppm处的两个CH质子(C)的积分来定量,在每一官能基团报告位点的数目的占比:
N顺式=IC/2
当没有从视觉上观察到内部顺式亚乙烯基(E-RCH=CHR’)或其相关结构的存在所对应的特征信号时,则这些基团不被计入,并不使用参数N顺式。
观察到内部反式亚乙烯基(Z-RCH=CHR’)的存在所对应的特征信号,数量使用5.45ppm处的两个CH质子(T)的积分来定量,在每一官能基团报告位点的数目的占比:
N反式=IT/2
观察到内部三元取代亚乙烯基(RCH=CR’R”)或其相关结构的存在所对应的特征信号,数量使用5.14ppm处的CH质子(Tris)的积分来定量,在每一官能基团报告位点的数目的占比:
N三元=ITris
Hostanox 03稳定剂使用6.92、6.91、6.69ppm处以及6.89ppm处的芳香族质子的多重峰的积分来定量,在每一分子报告位点的数目的占比:
H=IA/4
尽管通过1H NMR光谱法进行了定量,正如对于聚烯烃中的不饱和定量是典型的一样,不饱和的量也可以关于总的碳原子来测定。这就允许与直接由13CNMR光谱法得到的其他微观结构数量的直接比较。
碳原子的总量的计算来自:具有对来自稳定剂的甲基信号的补偿的在2.85和-1.00ppm之间的本体脂肪族信号的积分以及没有被此区域所包含的与不饱和官能性相关的碳原子:
NC总=(I本体–42*H)/2+2*N乙烯基+2*N亚乙烯基+2*N顺式+2*N反式+2*N三元
不饱和基团的含量(Ux)计算为每一千总碳(kCHn)的聚合物中的不饱和基团的数目:
Ux=1000*Nx/NC总
特别地,乙烯基的含量U乙烯基计算为每一千总碳(kCHn)的聚合物中的乙烯基的数目:
U乙烯基=1000*N乙烯基/NC总
实施例
聚乙烯A(本发明)
使用单位点催化剂制备中等密度聚乙烯。作为催化剂使用的是来自雅宝公司(Albemarle Corporation)的具有加强的活化剂技术的含茂金属双(1-甲基-3-正丁基环戊二烯基)氯化锆(IV)的负载催化剂,其含有铝氧烷。
在第一个浆料环流反应器中进行预聚合,然后在第二个浆料环流反应器中进行聚合。聚合条件可见表1。
表1
聚乙烯B(对比)
使用按照WO 95/12622 A1的实施例1制备的单位点催化剂制备中等密度聚乙烯。按照EP 1316598 B1的实施例1进行聚合过程。
聚乙烯C(对比)
使用混合的铁催化剂和单位点催化剂制备中等密度聚乙烯。按照WO 2009/103516A2的实施例4制备催化剂并进行聚合过程。
本发明的聚乙烯以及对比的聚乙烯的性质概括于表2中。
表2
组合物1和2(本发明)
将粘合性共混物组合物在Werner&Pfleiderer ZSK 30mm同向双螺杆挤出机中进行接枝。组合物1和2使用聚乙烯A。粘合性共混物组合物显示于表3中。
加入密度为0.926g/cm3、MFR2为4.5g/10min以及丙烯酸丁酯含量为27wt%的乙烯丙烯酸丁酯弹性体以提高柔性。通过加入不同量的马来酸酐来实现接枝。以10%的异癸烷溶液的形式进料过氧化物引发剂(Perkadox 14S-fl,Akzo Nobel)。挤出机的温度在170℃和210℃之间变化,且螺杆速度设定在200rpm。
组合物3(对比)
按照EP 1316598 B1的实施例2、组合物2制备组合物3。
组合物4(对比)
组合物4使用聚乙烯C。按照WO 2009/103516 A2的实施例6制备组合物4。
表3
组合物1-2的加工
表4显示了接枝后的粘合性共混物组合物的性质以及涂覆于钢管上的共挤出粘合剂的粘附性能。
当旋转的钢制管道(8m/min)的温度在200-220℃时,在其上喷涂环氧树脂粉末作为腐蚀防护。将粘合性共混物组合物以及常规的高密度聚乙烯外层共挤出至环氧树脂层上。该共挤出在KrausMaffei 45mm和Barmag 45mm单螺杆挤出机中进行。在各自模具中的粘合性共混物组合物和高密度聚乙烯的温度约为220℃。使用硅树脂压辊将粘合性共混物组合物和高密度聚乙烯层均牢固滚压在涂层表面上。环氧树脂层的厚度值为145μm,粘合性共混物组合物的厚度值为430μm,聚乙烯外层的厚度值为4.0mm。通过使用Zwick Roell拉力测试机测试其剥离强度来评价冷却后的三层组合。
组合物3的加工
按照EP 1316598 B1的实施例3完成组合物3的加工。
组合物4的加工
按照WO 2009/103516 A2的实施例完成钢板的涂覆以及剥离强度的测试。
表4
相较于对比实施例的组合物,接枝后的共混物组合物1和2在23℃下的剥离强度更佳。
Claims (15)
1.一种粘合性聚合物组合物,包含:
a)乙烯与一种或多种具有3至10个碳原子的共聚单体的非弹性体共聚物,基于所述粘合性聚合物组合物,所述非弹性体共聚物按重量以60%至95%的量存在,所述非弹性体共聚物具有:从50000g/mol至80000g/mol的重均分子量Mw、2.0至5.5的分子量分布Mw/Mn、从0.925g/cm3至0.945g/cm3的密度和至多0.1个乙烯基/1000个碳原子;以及
b)弹性体,
其中,所述非弹性体共聚物或所述非弹性体共聚物及所述弹性体使用酸接枝剂进行接枝。
2.根据权利要求1所述的粘合性聚合物组合物,其特征在于,基于所述粘合性聚合物组合物,所述非弹性体共聚物按重量以70%至90%的量存在。
3.根据权利要求1和2所述的粘合性聚合物组合物,其特征在于,所述非弹性体共聚物具有从1g/10min至20g/10min的MFR2,更优选从1g/10min至10g/10min。
4.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述组分a)具有从0.930g/cm3至0.942g/cm3的密度。
5.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述非弹性体共聚物为具有单峰分子量分布的聚乙烯。
6.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述非弹性体共聚物于使用单位点催化剂的工艺中制备。
7.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述单位点催化剂包含于载体上的茂金属组分和铝氧烷组分。
8.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述粘合性聚合物组合物具有从0.1g/10min至10g/10min的MFR2值,优选从1.0g/10min至6.0g/10min。
9.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述粘合性聚合物组合物具有从0.925g/cm3至0.945g/cm3的密度,更优选从0.930g/cm3至0.940g/cm3。
10.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述酸接枝剂为不饱和羧酸或其衍生物,更优选为马来酸或其衍生物,特别为马来酸酐。
11.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,基于所述粘合性聚合物组合物,所述酸接枝剂以从0.01重量份至3.0重量份的量存在,更优选从0.03重量份至1.5重量份。
12.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述弹性体包含弹性体乙烯共聚物。
13.根据前述权利要求任一项所述的粘合性聚合物组合物,其特征在于,所述弹性体包含具有极性共聚单体群组的弹性体乙烯共聚物。
14.一种制品,特别为一种多层管,包括粘合层,所述粘合层包含根据前述权利要求任一项所述的粘合性聚合物组合物。
15.根据权利要求1-13任一项所述的粘合性聚合物组合物用于制备粘合层、优选管的粘合层的用途。
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