CN1242029A - Polyolefin compositions with balanced sealant properties and improved modulus and method for same - Google Patents

Polyolefin compositions with balanced sealant properties and improved modulus and method for same Download PDF

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CN1242029A
CN1242029A CN 97181099 CN97181099A CN1242029A CN 1242029 A CN1242029 A CN 1242029A CN 97181099 CN97181099 CN 97181099 CN 97181099 A CN97181099 A CN 97181099A CN 1242029 A CN1242029 A CN 1242029A
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film
ethylene polymer
polymer
composition
ethylene
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CN 97181099
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L·伯斯尔斯
J·A·德路特
L·T·卡勒
P-W·S·楚
S·A·得昆德
J·J·范邓
T·T·奥斯瓦德
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陶氏化学公司
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Abstract

本发明涉及包括至少两种乙烯聚合物组分材料的密封薄膜组合物。 The present invention relates to a sealing film composition comprising at least two ethylene polymer component materials. 本发明一方面涉及具有平衡密封性能并包括密封层和聚丙烯层的多层结构,其中密封层包括并由具有特定分子量特征的聚合物和第二种乙烯聚合物的聚合物组合物制备。 Aspect of the invention relates to a seal having a balance of properties and a multilayer structure comprising a polypropylene layer and a sealing layer, wherein the sealing layer comprises by having a specific molecular weight and a second polymer wherein the ethylene polymer prepared polymer composition. 本发明的一个优选实施方案涉及具有极好的低密封起始温度和改进的薄膜模量的平衡特性的中密度聚烯烃薄膜和组合物。 A preferred embodiment of the present invention is directed to having excellent low seal initiation temperature and an improved balance of film modulus characteristics and density polyolefin film compositions. 该薄膜和组合物由至少一种低密度均相支化乙烯聚合物和至少一种较高密度的非均匀相或均相支化乙烯聚合物组成和制备。 The composition and the film density of at least one homogeneously branched ethylene polymer and at least one high density non-homogeneous phase or homogeneous branched ethylene polymer composition and preparation. 本发明特别适用于其中要求密封时间快和良好包装尺寸稳定性的那些应用,如蒸煮包装、热填充包装、可流动物质包装盒、压缩填充包装、收缩薄膜包装和阻挡收缩薄膜包装,以及双轴取向聚丙烯(BOPP)薄膜结构。 The present invention is particularly applicable to the sealing requirements which time fast and good those applications the dimensional stability of the packaging, such as packaging retort, hot-fill package, flowable material packaging, filling compression packaging, shrink wrap packaging and barrier shrink film, and a biaxially oriented polypropylene (BOPP) film structures.

Description

具有平衡密封性能和改进的模量的聚烯烃组合物和其制备方法 Sealing performance with balanced modulus and improved polyolefin compositions and methods for preparing

本发明涉及包括至少两种乙烯聚合物组分的密封薄膜组合物。 The present invention relates to ethylene polymer component comprises at least two sealing film composition. 本发明一方面涉及具有平衡密封性能并包括密封层和聚丙烯层的多层结构,其中密封层包括并由具有特定分子量特征、并含有第二种乙烯聚合物的聚合物组合物制备。 Aspect of the invention relates to a seal having a balance of properties and a multilayer structure comprising a polypropylene layer and a sealing layer, wherein the sealing layer comprises a feature by having a specific molecular weight, and the preparation of ethylene polymers comprising the second polymer composition. 本发明的一个优选实施方案涉及具有极好的低密封起始温度和改进的薄膜模量的平衡特性的中密度聚烯烃薄膜和组合物。 A preferred embodiment of the present invention is directed to having excellent low seal initiation temperature and an improved balance of film modulus characteristics and density polyolefin film compositions. 该薄膜和组合物由至少一种低密度均相支化乙烯聚合物和至少一种较高密度的非均匀相或均相支化乙烯聚合物组成和制备。 The composition and the film density of at least one homogeneously branched ethylene polymer and at least one high density non-homogeneous phase or homogeneous branched ethylene polymer composition and preparation.

尽管早已发现乙烯聚合物可用于食品包装和食品贮存容器领域,但制造商和包装商得不到具有合适平衡性能的薄膜、涂料、层压或共挤出形式的聚烯烃组合物。 Although already found that ethylene polymers for food packaging and food storage containers field, manufacturers and packagers are not suitable film having a balance of properties, coatings, laminates or coextruded polyolefin composition form. 例如,在包装和贮存领域用作密封层的最佳乙烯聚合物组合物应具有多种关键性能,如低热密封和热发粘起始温度、高热粘强度、宽热粘密封温度范围、良好的层间粘结性能、高软化点和低的己烷可萃取量。 For example, as the optimal composition of the sealing layer of the ethylene polymer should have a number of key properties in the field of packaging and storage, such as low heat seal and hot tack initiation temperature, heat tack strength, hot tack wide sealing temperature range, good the interlayer adhesion properties, a high softening point and a low amount of hexane extractables.

尽管目前还不能满足这种要求,但工业上公知平衡密封性能的重要性。 Although not meet this requirement, but the importance of balancing the sealing properties known in the industry. 换言之,低热密封和热粘起始温度对于改进密封速度和降低所用的能量是重要的。 In other words, low heat seal and hot tack initiation temperatures are important for improved sealing speeds and reduced energy use. 在高热粘着强度下的宽热粘密封温度范围(即,其中热粘着强度大于或等于约46g/cm(通过Dupont弹簧方法测定)或大于或等于约3.31N/15mm(5.6N/in.)(用机械热粘性试验仪如Top Wave密封装置测定)的密封温度范围),对于确保包装完整性、密封装置的灵活性和低包装渗漏速率是重要的。 In the adhesion strength of heat seal broad hot tack temperature range (i.e., where the hot tack strength is greater than or equal to about 46g / cm (measured by spring Dupont method) or greater than or equal to about 3.31N / 15mm (5.6N / in.) ( Top Wave sealing means such as a mechanical measuring hot tack tester) sealing temperature range), to ensure package integrity, flexibility and low package leakage rates sealing device is important. 良好的层间粘结性对于确保物品包装完整性及物品包装或容器美观也是重要的。 Good interlayer adhesion and to ensure the integrity of the packaging article goods package or container aesthetics are important. 当在高温下包装物品,如用于热填充中时,高软化点或温度是所需的。 When packaging an article at an elevated temperature, such as for hot filling, a high softening point or temperature is desired. 对于接触食品的应用要求低己烷可萃取量。 For food contact applications requiring low amount of hexane extractables.

通常,当试图获得平衡的密封性能时,增强某一特定树脂性能需要有所牺牲另一重要性能。 Generally, when trying to get a balanced sealing performance, enhanced performance of a specific resin needs to be sacrificed to another important property. 例如,对于乙烯/α-烯烃聚合物,一般通过增加树脂的共聚单体含量达到所需的热封和热粘着起始温度。 For example, the ethylene / α- olefin polymer, typically by increasing the resin comonomer content desired heat seal initiation and hot tack temperatures. 相反,高Vicat软化点和低正己烷萃取量通常通过降低树脂的共聚单体含量达到。 Conversely, high Vicat softening points and low n-hexane extracted amount is usually achieved by reducing the comonomer content of the resin. 因此,改进树脂密封起始性能通常导致成比例地降低Vicat软化温度并成比例地增加可萃取量。 Hence, an improved performance of the resin generally results in the seal initiation proportionally reduced Vicat softening temperature and proportionally increased amount extracted.

几种重要的多层包装和贮存结构由聚丙烯层,特别是双轴取向的聚丙烯(BOPP)均聚物基层或芯层组成。 Several important multilayer packaging and storage structures by the layer of polypropylene, in particular biaxially oriented polypropylene (BOPP) base or core layer composed of a homopolymer. 通常,BOPP结构使用聚丙烯共聚物和三元聚合物作为密封材料(和/或粘合剂层)以确保与BOPP基层的良好层间粘结性。 Typically, BOPP structures polypropylene copolymers and terpolymers used as the sealing material (and / or adhesive layers) to insure good inter-layer adhesion to BOPP base layer. 尽管聚丙烯共聚物和三元聚合物确实能提供与BOPP基层的良好层间粘结性以及良好的热粘着强度性能,但这些共聚物和三元聚合物不可避免地显示不合适的高热密封和热粘着起始温度。 While polypropylene copolymers and terpolymers do provide good inter-layer adhesion to BOPP base layer and good hot tack strength properties, these copolymers and terpolymers inevitably show inappropriate heat seal and hot tack initiation temperature.

其它聚烯烃材料已用作多层包装和贮存结构的密封材料。 Other polyolefin materials have been used as a sealing material, multilayer packaging and storage structures. 然而,通常已知的聚烯烃密封材料不能提供所需的整体平衡性能和/或变换器和包装机所需的处理灵活性。 However, a polyolefin sealant generally known process does not provide the flexibility required for the desired overall balance of properties and / or converter and packaging machines.

此外,还未获得在层压或压缩填充领域中用作密封层的最佳聚烯烃树脂组合物,因为重要性能(即低热密封起始温度和中-高薄膜模量)对于普通聚烯烃组合物是相互排斥的。 In addition, laminated or has not been compressed in the art as the optimum filling in the polyolefin resin composition of the sealing layer, since the important properties (i.e., low heat seal initiation temperature and - a high film modulus) for ordinary polyolefin composition They are mutually exclusive. 换言之,具有所需低密封起始温度特性的组合物不可避免地具有较低的薄膜模量。 In other words, having a low seal initiation temperature characteristics of the desired composition of the film inevitably has a lower modulus. 相反,提供中-高薄膜模量的组合物不可避免地具有过高的密封起始温度特征。 Rather, - the high modulus film compositions inevitably has a high sealing initiation temperature characteristics.

基于多个原因,低密封起始温度和中-高(改进)薄膜模量是至关重要的性能。 Number of reasons, and in low seal initiation temperature - high (improved) film modulus is a critical performance. 要求改进的薄膜模量(薄膜劲度)以确保薄膜在包装制作、填充和/或密封操作中的良好薄膜可机加工性。 It requires improved modulus (stiffness film) thin film in order to ensure good film packaging production, filling and / or sealing operation may machinability. 例如,具有良好机加工性的薄膜甚至当切割设备如刀片和叶片不太锋利时,也能均匀且有效地切割,由此降低废料和/或减少设备更新要求。 For example, a film having good machine workability such as cutting apparatus even when the blade and blade less sharp, can cut uniformly and effectively, thereby reducing waste and / or reducing the update request apparatus. 在压缩填充中还要求中-高薄膜模量以确保良好的尺寸稳定性,由此使薄膜结构、塑料管等向上竖立,以有助于有效地填充要包装的物品。 In further compression of the packed requirements - a high modulus film to ensure a good dimensional stability, whereby the film structure erected upwardly plastic tube, to facilitate effective filling of items to be packaged.

为确保较高的包装速度,需要低密封起始温度。 To ensure a high packaging speeds, a low seal initiation temperature. 换言之,可形成高强度密封的温度越低,每单位时间可获得更多的包装单位以使生产率最大。 In other words, a seal may be formed of a high strength lower the temperature per unit time obtained more packaging units to allow for maximum productivity. 此外,较低的密封起始温度可要求精度较低的密封装置温度控制以及较低的密封能量消耗。 In addition, a lower seal initiation temperature may require a lower temperature control accuracy of the sealing means and lower sealing energy consumption.

尽管已经公开了用作密封材料的各种聚烯烃组合物,并且尽管由共挤出或层压薄膜结构组成的复合物据说令人满意,但已知的组合物(尤其是当用作单层薄膜结构时)通常不具有包括低密封起始温度和中-高薄膜模量重要性能的最佳平衡性。 Although various disclosed polyolefin composition is used as a sealing material, and despite reports satisfactory laminate film by a coextrusion or composite structures, but the known compositions (especially when used as a single layer when the thin film structure) comprising a generally do not have a low seal initiation temperature and - the optimum balance of high modulus important film properties. 例如,已知TAFMERTM树脂(由Mitsui Petrochemical出售)提供具有较低密封起始温度的密封剂。 For example, it is known TAFMERTM resin (sold by Mitsui Petrochemical) a sealant having a lower seal initiation temperature. 然而,已知TAFMERTM树脂无论用作单组分密封材料或用作聚合物共混组分材料,都不能提供总体所需的平衡性能。 However, it is known whether used as single component TAFMERTM resin sealing material or as a polymer blend component material, we can not provide the desired overall balance of properties. 已知TAFMERTM树脂也不能提供中-高薄膜模量。 Known resin can not provide the TAFMERTM - a high modulus film. TAFMERTM树脂的另一缺陷是,该树脂相当昂贵,并且供应量一直有限。 Another drawback is that TAFMERTM resin, the resin is relatively expensive, and the supply has been limited.

与TAFMERTM树脂相比,非均相支化乙烯聚合物如线性低密度聚乙烯(LLDPE)和超低密度聚乙烯容易获得。 Compared with TAFMERTM resin, heterogeneously branched ethylene polymers such as linear low density polyethylene (LLDPE) and ultra low density polyethylenes are readily available. 然而,非均相支化乙烯聚合物用作密封材料不能提供最优的所需总体性能平衡,因此它们特别不适合用作BOPP结构。 However, the heterogeneously branched ethylene polymer is used as a sealing material does not provide optimal overall balance of properties desired, and therefore they are not particularly suitable for use as BOPP structures. 例如,非均相支化线性低密度聚乙烯(LLDPE)(以及由这些聚合物制备的密封层)与聚丙烯层的层间粘结性特别差。 For example, the interlayer heterogeneously branched linear low density polyethylene (LLDPE) (as well as a sealing layer made of these polymers) and the polypropylene layer is particularly poor adhesion. 此外,非均相支化乙烯聚合物趋于具有中等-低密封起始温度和中等至低薄膜模量,因此并不特别适合其中要求良好薄膜机加工性能的高速包装操作。 Further, heterogeneously branched ethylene polymers tend to have a medium - low seal initiation temperature and low to medium modulus film, therefore, not particularly suitable for machining requiring good film properties of high-speed packaging operations therein.

均相支化乙烯聚合物如The Dow Chemical Company出售的AFFINITYTM树脂也适合用作密封材料。 AFFINITYTM resins homogeneously branched ethylene polymers such as sold by The Dow Chemical Company are also suitable as a sealing material. 尽管均相支化乙烯聚合物材料通常显示改进的密封起始性能,然而此类材料不可避免地具有相对低的薄膜模量。 Although the homogeneously branched ethylene polymer materials generally exhibit improved initial performance of the seal, but such a material inevitably has a relatively low modulus of the film.

Shibata等人的US4,429,079公开了一种乙烯/α-烯烃共聚物共混组合物,它包括(A)95-40wt%乙烯与具有5至10个碳原子的α-烯烃的无规共聚物,和(B)5至60wt%乙烯与具有3至10个碳原子的α-烯烃的无规共聚物的混合物,所述无规共聚物(A)具有熔体指数0.1至20g/10min.,密度0.910至0.940g/cc,结晶度(通过X-射线测定)40-70%,熔点115至130℃,乙烯含量94至99.5mol%;所述无规共聚物(B)具有熔体指数0.1至50g/10min.,密度0.870至0.900g/cc,结晶度(通过X-射线测定)5-40%,熔点40至100℃,乙烯含量85至95mol%;据说(A)组分聚合物通过钛催化剂体系生产,(B)组分聚合物通过钒催化剂生产。 Shibata et al. US4,429,079 discloses an ethylene / α- olefin copolymer blend composition comprising (A) 95-40wt% of ethylene and alpha] -olefin having 5-10 carbon atoms and a random copolymer of and (B) 5 to 60wt% mixture of ethylene and α- olefin random copolymer having 3 to 10 carbon atoms, the random copolymer (a) has a melt index of 0.1 to 20g / 10min., a density from 0.910 to 0.940g / cc, a crystallinity of 40-70%, a melting point of 115 to 130. deg.] C, an ethylene content of 94 to 99.5 mol% (measured by X- ray); the random copolymer (B) has a melt index of 0.1 to 50g / 10min, a density from 0.870 to 0.900g / cc, a crystallinity (measured by X- ray) 5-40%, temperature 40 to 100 deg.] C, an ethylene content of 85 to 95mol%;. is said (A) component polymer by production titanium catalyst system, (B) component polymer is produced by a vanadium catalyst. 这两种催化剂体系都称为Ziegler-Natta型催化剂,用于生产线性乙烯/α-烯烃聚合物。 Both catalyst systems are known as Ziegler-Natta type catalysts for the production of linear ethylene / α- olefin polymer. 换言之,该聚合物将具有线性分子主链,而不存在任何长链支化。 In other words, the polymer will have a linear molecular backbone without any long chain branching. 此外,(A)组分聚合物还预期具有非均相支化短链分布,而(B)组分聚合物具有均相支化短链分布。 Further, (A) component polymer is also expected to have a heterogeneously branched short chain distribution, while the (B) component polymer has a homogeneously branched short chain distribution. 由Shibata等人的组合物生产的薄膜据说具有良好的低温热密封性能、热密封强度、耐针孔性、透明性和冲击强度。 Shibata et al., The film produced compositions are said to have good low-temperature heat sealability, heat seal strength, pinhole resistance, transparency and impact strength. 然而,Shibata等人未公开具有高极限热粘着强度(即数值≥3.11N/mm)的薄膜,也未公开具有中等至高模量的薄膜。 However, Shibata et al., Does not disclose a high ultimate hot tack strength (i.e., the value ≥3.11N / mm) of the film, it is not disclosed having moderate to high modulus film. 此外,对Shibata等人提供的实施例中公开的数据分析显示,薄膜的热密封性能有所增加且随共混组分聚合物的密度线性变化。 Further, the data analysis embodiments Shibata et al discloses a display provided in the heat sealing property and an increase in the density of the film varies linearly with the polymer blend components.

Naito等人的US4,981,760公开了密度0.900至0.930g/cc和熔体流动速率0.1至100g/10in的聚乙烯混合物,该混合物包括(I)60至90重量份乙烯/α-烯烃无规共聚物,和(II)1至40重量份密度至少0.945g/cc的高密度聚乙烯,其中(I)和(II)的量之和为100重量份,所述无规共聚物包括乙烯和具有4至10个碳原子的α-烯烃,该共聚物具有α-烯烃含量为2.0至10mol%,密度0.895至0.915g/cc,所述共聚物的程序温度差热分析图(共聚物完全熔化接着逐渐冷却后用差示扫描量热法测定)在75°至100℃范围内显示吸热峰,在所述峰处的吸热量与总吸热量的比例为至少0.8,所述高密度聚乙烯的程序温度差热分析图(该聚合物完全熔化并使其冷却后用差示扫描量热法测定)在120℃或更高温度处显示吸热峰。 Naito et al. US4,981,760 discloses a polyethylene mixture density to 0.900 0.930g / cc and a melt flow rate of 0.1 to 100g / 10in, which mixture comprises (I) 60 to 90 parts by weight of an ethylene / α- olefin random copolymer thereof, and (II). 1 to 40 parts by weight of a density of at least 0.945g / cc high density polyethylene, wherein (I) and (II), and the amounts of 100 parts by weight, the random copolymer comprising ethylene and having α- olefin 4-10 carbon atoms, the copolymer having α- olefin content of 2.0 to 10mol%, a density 0.895 to 0.915g / cc, a temperature program of FIG differential thermal analysis of the copolymer (the copolymer is completely melted and then measured by differential scanning calorimetry after gradual cooling) shows an endothermic peak in the range of 75 ° to 100 deg.] C, the ratio of the heat absorption peak at a total amount of heat absorption of at least 0.8, said high-density polyethylene FIG programmed temperature differential thermal analysis ethylene (the polymer is completely melted and allowed measured after cooling differential scanning calorimetry) shows a temperature at or above 120 deg.] C endotherm peak. 据说组分聚合物(1)用钒催化剂制备,薄膜具有改进的热密封性和热粘着性。 It is said that the polymer component (1) Preparation of a vanadium catalyst, a thin film having improved heat sealability and hot tack. Naito等人未公开包括密度低于0.945g/cc的组分聚合物的加工薄膜。 Naito et al., Unpublished film composition comprising a lower density than the polymer processing 0.945g / cc's. 此外,Naito等人公开了当较低密度组分聚合物(I)的浓度相当高(即≥85重量份)时具有低热密封或热粘性起始温度的薄膜,该薄膜预期具有较低的Vicat软化点以及;较低的薄膜模量。 Also, Naito et al discloses a film when the concentration of the lower density component polymer (I) is quite high (i.e., ≥85 parts by weight) having a low heat seal or hot tack initiation temperature, the film is expected to have lower Vicat and a softening point; lower film modulus.

Hodgson等人的US5,206,075公开了包括基层和铺于该基材一面或两面上的可热密封层的多层可热密封薄膜。 Hodgson et al. US5,206,075 disclosed comprising a base layer and plated on one surface of the substrate film or a heat-sealable multilayer heat sealable layer on both sides. 作为基层,Hodgson等人公开了一种如下组分的共混物:(a)密度大于0.915g/cc的烯烃聚合物;和(b)乙烯与C3-C20α-单烯烃的共聚物,其中共聚物(b)具有密度约0.88至约0.915g/cc,熔体指数约0.5至约7.5dg/min,分子量分布不大于约3.5,组成分布宽度指数大于约70%,作为可热密封层,Hodgson公开了包括基材中作为(b)的共聚物。 As a base layer, Hodgson et al., Discloses a blend of one of the following components: (a) a density greater than 0.915g / cc olefin polymer; and (b) a copolymer of ethylene with C3-C20α- mono-olefin, wherein the copolymer (b) is having a density of from about 0.88 to about 0.915g / cc, a melt index of from about 0.5 to about 7.5dg / min, a molecular weight distribution not greater than about 3.5, a composition distribution breadth index greater than about 70%, as the heat sealable layer, Hodgson It discloses a copolymer comprising as a substrate of (b). Hodgson未公开将诸如基层(a)中所用的共混物作为合适的密封层,用作基层组分(a)的优选烯烃聚合物(a)为丙烯与约1-10mol%乙烯的共聚物。 Hodgson does not disclose the blend of base layer (a) used in such as a suitable sealing layer, preferably an olefin polymer (a) the base layer is used as component (a) is a propylene and about 1 to 10 mol% ethylene. 因此,此公开文献限制了如此公开的热密封材料的用途,因为该文献教导合适多层可热密封薄膜必须包括基层和具有类似烯烃化学性能的密封层。 Accordingly, this publication limits the usefulness of heat-sealable material so disclosed, because this document teaches Suitable heat-sealable multilayer film comprising a base layer and a sealing layer must have similar chemical properties olefins.

Shibata等人、Naito等人和Hodgson等人公开的材料以及其它已知密封材料不是在这一方面,就是在那一方面存在缺陷。 Material Shibata et al., Naito et al. And Hodgson et al disclosed and other sealing materials are not known in this regard, is that there is a defect in one hand. 这些材料不能提供包括低密封起始温度和改进的薄膜模量的平衡密封性能。 These materials do not provide the sealing performance includes a balanced low seal initiation temperature and improved modulus of the film. 这些材料也不特别适合在BOPP结构中用作密封材料。 These materials are not particularly suitable for use as a sealing material BOPP structures. 因此,需要具有与聚丙烯的良好层间粘结性、低热密封和热粘着起始温度、高热粘着强度和宽的高热粘着密封温度范围特性的聚合物组合物。 Therefore, polypropylene having good inter-layer adhesion, low heat seal polymer composition and hot tack initiation temperature, heat adhesion strength and a wide temperature range of heat seal adhesive characteristics. 还分别需要显示低热密封起始温度和中等至高薄膜模量的适合用于层压、共挤出和压缩填充包装领域的薄膜和薄膜组合物。 They are also to be displayed low heat sealing initiation temperature and a moderate to high modulus films suitable for lamination, co-extrusion and compression films and film compositions filling packaging art. 还需要具有低己烷萃取量,即低于15wt%,优选低于10wt%,更优选低于6wt%,最优选低于3wt%的聚合物密封组合物,这样此组合物可用于与食品直接接触的领域中。 Also required to have a low amount of hexane-extracted, i.e., less than 15wt%, preferably less than 10wt%, more preferably less than 6wt%, most preferably less than 3wt% polymeric sealing composition, such compositions may be used directly with the food field in contact.

作为本发明第一方面,我们发现一种由聚合物组合物构成的新多层结构,所述组合物包括并由至少两种乙烯聚合物组分制备,其中第一种乙烯聚合物组分的特征在于具有优化的高分子量和均匀短链支化或组成分布。 As a first aspect of the present invention, we have found a new multilayer structure of a polymer composition consisting of, by preparing a composition comprising at least two ethylene polymer component, wherein the first ethylene polymer component characterized in that the high molecular weight and having an optimized homogeneous short chain branching distribution or composition. 该聚合物组合物提供具有平衡性能的适合用于多层包装和贮存结构的改进密封层。 The polymer composition is suitable for providing an improved balance of properties of the sealing layer having a multilayer packaging and storage structures. 该平衡密封性能包括与聚丙烯的良好层间粘结性、低热密封和热粘着起始温度,宽的高热粘着密封温度范围,和对于给定聚合物密度,较高的软化温度以(例如)防止与纵向取向辊粘连或提供良好的机加工性。 The balance between good sealing properties include polypropylene layer adhesion, low heat seal and hot tack initiation temperature, broad heat seal temperature range of the adhesive, and for a given polymer density, higher softening temperature (e.g.) preventing adhesions or longitudinal orientation roller provides good machinability. 此改进的密封剂特别适合用于包括聚丙烯层、特别是双轴取向聚丙烯(BOPP)薄膜层的多层结构。 This improvement is particularly suitable for the sealant layer include polypropylene, in particular biaxially oriented polypropylene (BOPP) multilayer structure of the film layers.

作为本发明另一方面,我们还发现一种由至少两种乙烯聚合物组分构成和制备的薄膜和薄膜组合物,其中第一种乙烯聚合物具有密度低于0.89克/厘米3(g/cc)特征,第二种乙烯聚合物具有密度0.94g/cc至0.97g/cc特征。 As another aspect of the present invention, we have found that a film composition and a film of at least two ethylene polymer component of the composition and preparation, wherein the first ethylene polymer having a density of less than 0.89 g / cm 3 (g / cc) wherein, a second ethylene polymer having a density of 0.94g / cc to 0.97g / cc feature. 新发现的薄膜组合物提供中等至高薄膜模量(即改进的模量)的适用于多层包装领域如层压、共挤出和涂布的密封薄膜。 The new film composition was found to provide moderate to high modulus film (i.e., improved modulus) is applied to areas such as a multilayer packaging laminate, coextrusion and coating the sealing film. 该密封与模量性能之间的平衡还允许其在各种应用,如其中可实现更高速密封以及良好的机加工和尺寸稳定性的压缩填充应用中作为单层薄膜。 The balance between the seal and modulus properties which allows a variety of applications, such as sealing may be implemented at a higher speed and good machinability and dimension stability of a compression fill applications as single-layer film.

本发明的一个广泛方面为密封薄膜组合物,它包括并由如下组分制备:5至95wt%的至少一第一种乙烯聚合物(按组合物总重量计),其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度0.85至0.92g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn小于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和5至95wt%的至少一第二种乙烯聚合物(按组合物总重量计),其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度低于0.97g/cc,其中组合物的特征是具有密度0.89g/cc至0.95g/cc(按照ASTMD-792测量),和至少一第一种乙烯聚合物的I2熔体指数低于至少一第二种乙烯聚合物 A broad aspect of the present invention is a sealing film composition, comprising the following components was prepared by: 5 to 95wt% of at least one of a first ethylene polymer (by weight of the total composition), which is a homogeneously branched substantially the linear ethylene polymer or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having:. i I2 melt index of 0.001g / 10min to 2g / 10min, according to ASTM D-1238 condition 190 ℃ /2.16kg measured, ii. a density of 0.85 to 0.92g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn is less than 3.5, as measured by gel permeation chromatography, iv. short chain branching distribution index (The SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and 5 to 95wt% of at least one second ethylene polymer (by weight of the total composition), which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymers, wherein the second ethylene polymer is characterized in having a density of less than 0.97g / cc, wherein the composition is characterized in having a density of 0.89g / cc to 0.95g / cc (measured in accordance with ASTMD-792), and at least a first ethylene polymer has a melt index I2 is lower than the at least one second ethylene polymer I2熔体指数。 I2 melt index.

本发明第二方面为包括聚丙烯层和密封层的多层结构,所述密封层具有平衡性能,包括与聚丙烯的极好层间粘结性能,含有并由如下组分制备(A)5至95wt%的至少一第一种乙烯聚合物(按密封层的总重量计),其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.14g/10min至低于0.67g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度0.85至0.92g/cc,按照ASTM D-792测量,iii. I10/I2熔体流动比6至12,按照ASTM D-1238条件190℃/2.16kg和条件190℃/10kg测定,iv.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,v.在-30至150℃之间的单一差示扫描量热DSC熔化峰,vi.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(B)5至95wt%的至少一第二种乙烯聚合物(按密封层总重量计),其为均相支化乙烯聚合物或非均相支 The second aspect of the present invention is a multilayer structure comprising a polypropylene layer and a sealing layer, said sealing layer having a balance of properties, including excellent adhesion properties between layers of polypropylene, prepared by containing the following components (A) 5 to 95wt% of at least one of a first ethylene polymer (by total weight of the sealing layer), substantially linear ethylene polymer or homogeneously branched linear ethylene polymer is a homogeneously branched, wherein the first ethylene polymerization characterized in that the composition has:. i I2 melt index of 0.14g / 10min to less than 0.67g / 10min, measured according to ASTM D-1238 condition 190 ℃ / 2.16kg, ii density of 0.85 to 0.92g / cc, according to ASTM D. -792 measurement, iii. I10 / I2 melt flow ratio of from 6 to 12, according to ASTM D-1238 condition 190 ℃ / 2.16kg and conditions of 190 ℃ / 10kg measured, iv. a molecular weight distribution Mw / Mn below 3.5, by gel permeation chromatography, v. a single differential scanning calorimetry DSC melting peak between -30 deg.] C to 150, vi. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and ( B) 5 to 95wt% of at least one second ethylene polymer (by total weight of the sealing layer), which is a homogeneously branched ethylene polymer or homogeneously branched 线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.89g/cc至0.965g/cc,其中密封层的特征是具有密度0.89g/cc至0.93g/cc(按照ASTMD-792测量),和I2熔体指数1g/10min至5g/10min(按照ASTM D-1238条件190℃/2.16kg测定),和其中至少一第一种乙烯聚合物(A)的分子量高于至少一第二种乙烯聚合物(B)的分子量。 Linear ethylene polymers, wherein the second ethylene polymer is characterized in having a density of 0.89g / cc to 0.965g / cc, wherein the sealing layer is characterized in having a density of 0.89g / cc to 0.93g / cc (measured in accordance with ASTMD-792 ), and I2 melt index of 1g / 10min to 5g / 10min (190 ℃ / 2.16kg measured according to ASTM D-1238 condition), and wherein the molecular weight of the at least one first ethylene polymer (a) is higher than at least a second species molecular weight ethylene polymer (B) is.

本发明第三方面为具有改进模量或组成密度的薄膜或薄膜层,所述薄膜或薄膜层包括并由如下组分制备:(C)20至60wt%的至少一第一种乙烯聚合物(按薄膜或薄膜层的总重量计),其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTM D-1238条件190℃/2.16kg测定, A third aspect of the present invention is a composition having an improved modulus or density of the film or film layer, said film or film layer comprising the following components was prepared by: (C) 20 to 60wt% of at least one of a first ethylene polymer ( film or film layer by total weight), which is a homogeneously branched substantially linear ethylene polymers or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having:. i I2 melt index 0.001g / 10min to 2g / 10min, according to ASTM D-1238 condition 190 ℃ / 2.16kg measured,

ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn小于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(D)40至80wt%的至少一第二种乙烯聚合物(按薄膜或薄膜层总重量计),其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTM D-792测量,其中至少一第一种乙烯聚合物(C)的I2熔体指数等于或低于至少一第二种乙烯聚合物(D)的I2熔体指数,和薄膜或薄膜层的特征是具有组成密度0.915g/cc至0.95g/cc(按照ASTM D-792测量)。 ii. a density less than 0.89g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn is less than 3.5, measured according to gel permeation chromatography, iv. short chain branching distribution index (The SCBDI) greater than 50%, with elution fractionation temperature measurement, and (D) 40 to 80wt% of at least one second ethylene polymer (film or film layer by total weight), which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymers, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc, measured according to ASTM D-792, wherein the at least one first ethylene polymer (C) is melt I2 index equal to or lower than at least a second ethylene polymer (D) is I2 melt index, and a film or film layer characterized in having a composition density of 0.915g / cc to 0.95g / cc (measured according to ASTM D-792) .

本发明第四方面为制备具有改进模量并包括至少一薄膜层的密封薄膜,该方法包括如下步骤:提供由如下组分构成或制备的聚合物组合物(C)20至60wt%的至少一第一种乙烯聚合物(按薄膜的总重量计),其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn小于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(D)40至80wt%的至少一第二种乙烯聚合物(按薄膜总重量计),其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTM D-792测量其中至少一第一种乙烯聚合物(C)的I2熔体指数 A fourth aspect of the present invention is a product having an improved modulus and sealing membrane comprising at least one film layer, the method comprising the steps of: providing a composition comprising a polymer consisting of or prepared (C) 20 to 60wt% of at least one of a first ethylene polymer (by total weight of the film), which is a homogeneously branched substantially linear ethylene polymers or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having: i . I2 melt index of 0.001g / 10min to 2g / 10min, 190 ℃ / 2.16kg measured according to ASTM D-1238 conditions, ii. a density less than 0.89g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn less than 3.5, measured according to gel permeation chromatography, iv. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and (D) 40 to 80wt% of at least one second ethylene polymerization composition (by weight of total film), which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc measuring at least a first ethylene polymer (C) according to ASTM D-792 I2 melt index 于或低于至少一第二种乙烯聚合物(D)的I2熔体指数,和薄膜的特征是具有组成密度0.915g/cc至0.95g/cc(按照ASTM D-792测量);挤出该聚合物组合物形成至少一薄膜层的薄膜;和收集包括至少一薄膜层的薄膜。 Wherein at least at or below a second ethylene polymer (D) a melt index I2, and the film composition having a density 0.915g / cc to 0.95g / cc (measured according to ASTM D-792); extruding the the polymer composition forming at least a thin film layer; and at least one thin film comprising a collection layer.

本发明第五方面为提供改进薄膜模量的可热密封组合物,该组合物包括并由如下组分制备:(C)20至60wt%的至少一第一种乙烯聚合物(按组合物总重量计),其为基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn小于3.5,按照凝胶渗透色谱测定,iv. 短链支化分布指数(SCBDI)大于50,用温升洗脱分级测量,和(D)40至80wt%的至少一第二种乙烯聚合物(按组合物总重量计),其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTM D-792测量,其中至少一第一种乙烯聚合物(C)的I2熔体指数等于或低于至少一第二种乙烯聚合物(D)的I2熔体指数 A fifth aspect of the present invention to provide an improved modulus film heat sealable composition, the composition comprising the following components was prepared by: (C) 20 to 60wt% of at least one of a first ethylene polymer (the total composition by weight), which is a substantially linear ethylene polymer or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having:. i I2 melt index of 0.001g / 10min to 2g / 10min, according to ASTM D-1238 condition 190 ℃ / 2.16kg measured, ii. a density less than 0.89g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn is less than 3.5, measured by gel permeation chromatography, iv. a short chain branching distribution index (the SCBDI) greater than 50, with a temperature rise elution fractionation measurement, and (D) 40 to 80wt% of at least one second ethylene polymer (by weight of the total composition), which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc, measured according to ASTM D-792, wherein the at least one first ethylene I2 melt index of polymer (C) equal to or below the at least one second ethylene polymer (D) a melt index I2 of 和组合物的特征是具有组成密度0.915g/cc至0.95g/cc(按照ASTM D-792测量)。 And compositions characterized by having a composition density of 0.915g / cc to 0.95g / cc (measured according to ASTM D-792).

令人吃惊的是,尽管由非均相支化乙烯聚合物制备的密封层具有密封起始温度显著高于其相应软化温度特征,但本发明的改进密封层具有可与其热密封起始温度比拟的Vicat软化点。 Surprisingly, although the sealing layer of the heterogeneously branched ethylene polymer prepared having a sealing initiation temperature significantly higher than the respective softening temperature profile, but the present invention is to improve the sealing layer having heat sealing initiation temperature compared therewith the Vicat softening point. 换言之,对于最低1.8N/15mm密封强度,密封层具有等于或至少低于其Vicat软化温度4.5℃,和更令人吃惊地在特定实施方案中等于或低于(其Vicat软化温度-6℃)的薄膜密封起始温度。 In other words, for minimum 1.8N / 15mm seal strength and sealing layer at least equal or below its Vicat softening temperature 4.5 ℃, and even more surprisingly lower than or equal to (Vicat softening temperature thereof -6 deg.] C) In certain embodiments seal initiation temperature of the film.

作为本发明另一出人意料的结果,尽管普通密封薄膜具有相对于其相应密度(和/或其相应薄膜模量)具有较高密封起始温度特征,但本发明的改进密封薄膜或薄膜层对于给定薄膜模量或密度具有较低的密封起始温度。 As a further surprising result of the present invention, although an ordinary film having a seal relative to its respective density (and / or the corresponding film modulus) having a higher seal initiation temperature characteristics, but improve sealing film or film layer of the present invention for a given modulus or film having a low density sealing initiation temperature. 换言之,与普通薄膜相比,本发明的薄膜在相同的密封起始温度下获得较高的模量,或在相同的薄膜密度或模量下获得较低的密封起始温度。 In other words, compared with the conventional film, the film of the present invention to obtain a higher modulus at the same sealing initiation temperature, or to obtain a lower seal initiation temperature of the film at the same density or modulus. 对于本发明,不是在较低密封起始温度与中等-至高薄膜模量之间进行简单的折衷,因为所得到的性能不是简单地加合或根据重量分数的预期值。 For the present invention, the sealing initiation temperature is not lower and medium - simple compromise between a high modulus film, since the resulting performance is not simply an additive or according to the weight fraction of the expected value.

虽然本发明不仅限于此,本发明提供一种薄膜组合物、密封薄膜、密封薄膜层、涂料、用于包装、贮存、展览和保护目的的热成型制品或模塑制品。 Although the present invention is not limited thereto, the present invention provides a film composition, a sealing film, the sealing film layer, a coating, for packaging, storage, protection and exhibition purposes thermoformed article or a molded article. 这些用途包括但不限于蒸煮袋、用于可流动物品的袋、阻挡收缩和非阻挡收缩薄膜,瓶盖、包装容器盖和包装薄膜密封层。 These uses include, but are not limited to cooking bags, bags can be used for movement of goods, non-blocking and barrier shrink film shrinkage, caps, packaging film and a packaging container lid sealing layer.

本发明这些和其它实施方案将在下面详细描述。 These and other embodiments of the present invention embodiment will be described in detail below.

图1为实施例1的分析温升洗脱分级(ATREF)曲线-响应图。 Analysis of FIG. 1 is a temperature rise elution fractionation of Example 1 (an ATREF) curve of - in response FIG.

图2为实施例1的拟合凝胶渗透色谱(GPC)曲线-响应图。 FIG 2 is a curve fitting gel permeation chromatography EXAMPLE 1 (GPC) Embodiment - FIG response.

图3为作为第一种聚合物组分(A)的I2熔体指数(单位g/10min)的函数的热粘着强度(单位N/15mm)图。 3 is a first polymeric component (A) has a melt index I2 (in g / 10min) is a function of hot tack strength (in N / 15mm) FIG.

图4为作为均相支化乙烯聚合物组分(C)重量百分比含量的函数的本发明和对比薄膜实施例的热密封起始温度图。 FIG 4 is a thin film of the present invention and comparative homogeneously branched as a function (C) percentage by weight of the ethylene polymer components of the heat sealing initiation temperature embodiment of FIG.

图5为作为组成密度函数的本发明和对比薄膜实施例的热密封起始温度图。 5 is a film composition of the present invention and the comparative density function of the embodiment of the heat sealing initiation temperature FIG.

图6为作为薄膜模量函数的本发明和对比薄膜实施例的热密封起始温度图。 FIG 6 is a thin film of the present invention and a comparative film modulus as a function of the heat sealing initiation temperature embodiment of the embodiment of FIG.

图7为作为组成密度函数的本发明薄膜和对比薄膜的薄膜模量图。 7 is a thin film of the present invention and the comparative composition density function modulus of the film in FIG.

这里使用的术语“组成密度”是指单一组分聚合物或第一种与第二种乙烯聚合物的聚合物组合物密度(按照ASTM D-792测量)。 Herein, the term "composition density" refers to a single component polymer or the first ethylene polymer and the second polymer composition a density (measured in accordance with ASTM D-792). 术语“组成密度”是指粒料、薄膜或模制品的固态密度测量值,区别于熔体密度测量值。 The term "composition density" refers to pellets, film or molded article of the solid state density measurement values, different from the melt density measurements.

这里使用的术语“聚合物组合物”是指组分(A)与组分(B)或组分(C)与组分(D)的掺混物。 As used herein, the term "polymer composition" means that the components (A) and component (B) or component (C) to the blend component (D) is. 本发明的薄膜和组合物包括并由组分A和组分,和/或由掺混物本身的性能如组成密度定义的聚合物组合物制备。 Films and compositions of the present invention comprising component ingredients, and prepared by A and / or the blend itself, by the performance of the composition as defined density of the polymer composition.

这里使用的术语“聚合物”是指通过聚合相同或不同类型的单体制备的聚合材料。 As used herein, the term "polymer" refers to the same or can be prepared by polymerizing different types of monomers of the polymeric material. 因此一般性术语“聚合物”包括术语“均聚物”、“共聚物”、“三元聚合物”以及“共聚体”。 The generic term "polymer" embraces the term "homopolymer", "copolymer", "terpolymer" as well as "interpolymer."

这里使用的术语“共聚体”是指通过聚合至少两种不同类型的单体制备的聚合物。 The term used herein "interpolymer" means a polymer prepared by polymerization of at least two different types of monomers. 因此一般性术语“共聚体”包括“共聚物”(通常用于指由两种不同类型单体制备的聚合物)和术语“三元聚合物”(通常用于指由三种不同类型单体制备的聚合物)。 The generic term "interpolymer" includes "copolymers" (commonly used to refer to polymers prepared from two different types of monomers), and the term "terpolymer" (usually employed to refer to three different types of monomers polymers prepared).

本发明中使用的第一种乙烯聚合物组分(组分(A)或(C)一般为用均相催化剂体系,如金属茂催化剂体系、钒催化剂体系或束缚几何催化剂体系制备的乙烯聚合物。第一种乙烯聚合物特别为至少一种均相支化基本上线性乙烯聚合物或至少一种均相支化线性乙烯聚合物。第二种组分聚合物为至少一种非均相支化乙烯聚合物,或至少一种均相支化乙烯聚合物(即用均相催化剂体系制备的乙烯聚合物)。然而,优选第一种乙烯聚合物组分(A)或(C)为至少一种基本上线性乙烯共聚体,第二种乙烯聚合物组分(B)或(D)为至少一种非均相支化线性乙烯共聚体。更优选第一种和第二种乙烯共聚体都用连续溶液聚合方法,特别是连续低压溶液聚合方法制备。 A first ethylene polymer component (component (A) or (C) in the present invention is a homogeneous catalyst system is generally used, such as metallocene catalyst systems, vanadium geometry catalyst system or catalyst system prepared ethylene polymer bound . The first ethylene polymer of at least one in particular homogeneously branched substantially linear ethylene polymer or at least one homogeneously branched linear ethylene polymers. The second polymer component is at least one heterogeneously branched ethylene polymers, or at least one homogeneously branched ethylene polymers (i.e. ethylene polymers prepared using a homogeneous catalyst system). However, preferably the first ethylene polymer component (a) or (C) is at least A substantially linear ethylene interpolymer, the second ethylene polymer component (B) or (D) is at least one heterogeneously branched linear ethylene interpolymers. more preferably the first and second ethylene interpolymer They are continuous solution polymerization process, particularly a solution polymerization method preparing continuous low pressure.

基本上线性乙烯共聚体通常优选用作第一种乙烯聚合物组分(A)或(C),原因在于其改进的熔体挤出可加工性和独特的流变性能,如Lai等人在US5,272,236和5,278,272中描述的,这两份专利公开的内容这里作为参考引入。 Substantially linear ethylene interpolymer preferably is generally used as the first ethylene polymer component (A) or (C), the reason the extrusion processability and unique rheological properties in its improved melt, as in the Lai et al. described in US5,272,236 and 5,278,272, the contents of these two patents disclosed herein are incorporated by reference. 非均相支化乙烯共聚体优选用作第二种乙烯聚合物组分(即组分(B)和(D))。 Heterogeneously branched ethylene interpolymer is preferably used as the second ethylene polymer component (i.e., component (B) and (D)).

聚烯烃聚合物的分子量可方便地按照ASTM D-1238,条件190℃/2.16kg(以前称为“条件E”,又称为I2)用熔体指数测量值表示。 The molecular weight of polyolefin polymers is conveniently in accordance with ASTM D-1238, condition 190 ℃ / 2.16kg (formerly known as "Condition E", also known as I2) indicated by melt index measurements. 熔体指数与聚合物的分子量成反比。 The melt index of the polymer molecular weight is inversely proportional. 因此,分子量越高,熔体指数越低,尽管此关系不是线性的。 Thus, the higher the molecular weight, the lower the melt index, although this relationship is not linear.

对于本发明提供具有平衡密封性能(包括与聚丙烯的极好层间粘结性)的密封层方面,第一种乙烯聚合物(A)具有的I2熔体指数大于0.14g/10min至小于0.67g/10min,优选大于或等于0.15g/10min.至小于或等于0.65g/10min.,更优选大于或等于0.16g/10min.至小于或等于0.6g/10min.,最优选大于或等于0.16g/10min.至小于或等于0.5g/10min.。 For the present invention to provide a balanced sealing properties (including the excellent adhesion between layers of polypropylene) aspects of sealing layer, a first ethylene polymer (A) has a melt index I2 of greater than 0.14g / 10min to less than 0.67 g / 10min, preferably greater than or equal to 0.15g / 10min. to less than or equal to 0.65g / 10min., more preferably greater than or equal to 0.16g / 10min. to less than or equal to 0.6g / 10min., most preferably greater than or equal to 0.16g / 10min. to less than or equal to 0.5g / 10min ..

组分(A)和组分(B)可独立地用I2熔体指数表征。 Component (A) and component (B) may independently be characterized by a melt index I2. 术语“独立地表征”是指组分(A)的I2熔体指数不必与组分(B)的I2熔体指数相同。 The term "independently characterized" refers to a component (A) is not necessarily the same I2 melt index I2 melt index of component (B) is. 第二种乙烯聚合物(B)可具有的I2熔体指数大于或等于0.01g/10min至小于或等于500g/10min,优选大于或等于0.1g/10min.至小于或等于50g/10min.,更优选大于或等于1g/10min.至小于或等于20g/10min.,最优选大于或等于1g/10min.至小于或等于10g/10min.。 The second ethylene polymer (B) may have a melt index I2 of greater than or equal to 0.01g / 10min to less than or equal to 500g / 10min, preferably greater than or equal to 0.1g / 10min. To less than or equal to 50g / 10min., More preferably greater than or equal to 1g / 10min. to less than or equal to 20g / 10min., most preferably greater than or equal to 1g / 10min. to less than or equal to 10g / 10min ..

基于组分(A)和(B)的聚合物组合物的总体熔体指数优选为1至5g/10min.,更优选2至4g/10min。 Based on components (A) and (B) an overall polymer composition melt index is preferably 1 to 5g / 10min., More preferably 2 to 4g / 10min.

用于表征基本上线性乙烯共聚体和均聚物的其它测量值涉及具有较高荷重的熔体指数测定值,例如ASTM D-1238,条件190℃/10kg(以前称为“条件N”,又称为I10)。 For characterizing a substantially linear ethylene interpolymers and homopolymers other measurements involves melt index measurement value having a high load, e.g. ASTM D-1238, condition 190 ℃ / 10kg (formerly known as "Condition N", and known as I10). 较高荷重熔体指数测定值与较低荷重测定值的比例称为熔体流动比,对于测定的I10和I2熔体指数值,熔体流动比例方便地表示为I10/I2。 High load melt index ratio of the measured value and the measured value is referred to as a low load melt flow ratio, I10 and I2 melt index for the measured value of a melt flow ratio is conveniently expressed as I10 / I2. 对于用于制备本发明薄膜的基本上线性乙烯聚合物,熔体流动比例表示长链支化程度,即I10/I2熔体流动比例越高,聚合物中的长链支化越多。 For substantially linear ethylene polymers used in the preparation of films according to the present invention, the melt flow ratio indicates the degree of long chain branching, i.e., the higher the I10 / I2 melt flow ratio, the more long chain branching in the polymer. 除了表示更多的长链支化外,较高的I10/I2比也是较高拉伸粘度的标志。 In addition to showing more long chain branching Outsider, higher I10 / I2 ratio is also relatively high elongational viscosity flag.

对于平衡密封性能,高分子量、高程度的长链支化和/或高拉伸粘度通常是优选的。 For a balanced sealing performance, high molecular weight, high degree of long chain branching and / or high extensional viscosity are generally preferred. 我们已发现,相应于这些聚合物各性能,特别是相应于第一种乙烯聚合物组分(A)的分子量具有最佳范围。 We have found that, corresponding to each of the properties of these polymers, in particular to a molecular weight corresponding to a first ethylene polymer component (A) with the best range. 尽管第一种乙烯聚合物组分(A)的最佳分子量范围由上面的具体I2熔体指数范围定义,但据信本发明中用作第一种乙烯聚合物组分(A)的基本上线性乙烯聚合物的并定义为I10/I2熔体流动比例的最佳长链支化范围为大于6至约小于12,特别是大于7至小于10。 Although the first ethylene polymer component (A) is the optimum molecular weight range defined by a melt index I2 above specific range, it is believed that the present invention is used as the first ethylene polymer component (A) is substantially line ethylene polymer and is defined as the best long chain branching range I10 / I2 melt flow ratio is more than 12 to less than about 6, in particular more than 7 to less than 10. 满足该特定熔体指数范围、同时也满足上述I10/I2范围的实施方案是本发明特别优选的实施方案。 The melt index satisfies specific range, but also satisfying the above-described embodiments of the I10 / I2 ranges are particularly preferred embodiments of the present invention.

第一种乙烯聚合物组分(A)通常构成聚合物组合物的5至95wt%,优选15至75wt%,更优选30至5wt%(按聚合物组合物的总重量计)。 A first ethylene polymer component (A) typically constitute from 5 to 95wt% of the polymer composition, preferably 15 to 75wt%, more preferably 30 to 5wt% (by total polymer composition weight).

第一种乙烯聚合物组分(A)具有密度范围0.85至0.92g/cc,优选0.87至0.915g/cc,更优选约0.885至0.905g/cc(按照ASTMD-792测量)。 A first ethylene polymer component (A) having a density in the range 0.85 to 0.92g / cc, preferably from 0.87 to 0.915g / cc, more preferably from about 0.885 to 0.905g / cc (measured in accordance with ASTMD-792). 第二种乙烯聚合物组分(B)具有密度范围0.90至0.96g/cc,优选0.91至0.95g/cc,更优选0.92至0.93g/cc(按照ASTMD-792测量)。 The second ethylene polymer component (B) having a density in the range 0.90 to 0.96g / cc, preferably from 0.91 to 0.95g / cc, more preferably 0.92 to 0.93g / cc (measured in accordance with ASTMD-792). 此外,优选至少一第一种乙烯聚合物组分(A)的密度低于至少一第二种乙烯聚合物组分(B)的密度。 Further, preferably a density of at least a first ethylene polymer component (A) is less than the density of the at least one second ethylene polymer component (B) is.

基于组分(A)和组分(B)的聚合物组合物的总体密度优选为0.90至0.92g/cc,更优选0.905至0.925g/cc,最优选0.91至0.92g/cc(按照ASTM D-792测量)。 The overall density is preferably based on component (A) and the component (B) in the polymer composition is 0.90 to 0.92g / cc, more preferably 0.905 to 0.925g / cc, most preferably 0.91 to 0.92g / cc (according to ASTM D -792 measurement).

对于本发明提供具有平衡性能和改进模量的密封层方面,第一种乙烯聚合物(C)具有I2熔体指数范围0.001g/10min至2g/10min,优选0.01g/10min.至1.5g/10min.,更优选0.01g/10min.至1.2g/10min.,最优选0.05g/10min.至1g/10min.。 For the present invention provides a balance of properties and improved sealing layer modulus aspect, a first ethylene polymer (C) having a melt index I2 range of 0.001g / 10min to 2g / 10min, preferably from 0.01g / 10min. To 1.5g / 10min., more preferably 0.01g / 10min. to 1.2g / 10min., most preferably 0.05g / 10min. to 1g / 10min .. 第二种乙烯聚合物(D)具有I2熔体指数范围0.01g/10min至30g/10min,优选0.5g/10min.至20g/10min.,更优选1g/10min.至10g/10min.,最优选约1g/10min.至5g/10min.。 The second ethylene polymer (D) having a melt index I2 range of 0.01g / 10min to 30g / 10min, preferably 0.5g / 10min. To 20g / 10min., More preferably from 1g / 10min. To 10g / 10min., Most preferably about 1g / 10min. to 5g / 10min ..

基于组分(C)和组分(D)的聚合物组合物的总体熔体指数优选为0.1至50g/10min,更优选0.5至20g/10min,最优选0.7至6g/10min。 Based on overall melt composition (C) and component (D) of the polymer composition index is preferably 0.1 to 50g / 10min, more preferably 0.5 to 20g / 10min, and most preferably 0.7 to 6g / 10min.

对于本发明提供具有平衡密封性能和改进模量的方面,我们已发现基本上线性乙烯聚合物的I10/I2熔体流动比例应高至使可挤出加工性最大,且应低至使热粘着性能最小。 For the present invention to provide a balanced sealing performance and modulus improvements, we have discovered that substantially linear ethylene polymers I10 / I2 melt flow ratio should be high so that the maximum extrusion processability, and should be so low that the heat tack The minimum performance. 因此,应特别小心地优化第一种乙烯聚合物(C)的I10/I2比例,以确保良好的挤出可加工性和所需的良好热粘着性能之间的良好平衡。 Thus, I10 should be optimized first ethylene polymer (C) is / I2 ratio being very careful to ensure a good balance between good extrusion processability and good hot tack properties desired.

薄膜或组合物通常包括20至60wt%,优选20至55wt%,更优选25至45wt%,最优选约25至40wt%的至少一第一种乙烯聚合物组分(C)(按薄膜、薄膜层或组合物总重量计)(或由其制备)。 Film or compositions generally include 20 to 60wt%, preferably 20 to 55wt%, more preferably 25 to 45wt%, most preferably about 25 to 40wt% of at least one of a first ethylene polymer component (C) (by the film, the film layer, or the total weight of the composition) (or prepared therefrom). 同时,薄膜或组合物通常包括40至80wt%,优选45至80wt%,更优选55至75wt%,最优选60至75wt%的至少一第二种乙烯聚合物组分(D)(按薄膜、薄膜层或组合物总重量计)(或由其制备)。 Meanwhile, the film or composition generally comprises 40 to 80wt%, preferably 45 to 80wt%, more preferably 55 to 75wt%, most preferably 60 to 75wt% of at least one second ethylene polymer component (D) (by film, film layers or the weight of the total composition) (or prepared therefrom).

第一种乙烯聚合物组分(C)具有的密度低于0.89g/cc,在0.85至0.89g/cc范围内(按照ASTM D-792测量)。 A first ethylene polymer component (C) having a density of less than 0.89g / cc, in the 0.85 to 0.89g / cc range (measured according to ASTM D-792). 第二种乙烯聚合物组分(D)具有密度范围0.94至0.97g/cc,优选0.94至0.96g/cc,更优选0.945至0.955g/cc(按照ASTM D-792测量)。 The second ethylene polymer component (D) having a density in the range 0.94 to 0.97g / cc, preferably from 0.94 to 0.96g / cc, more preferably 0.945 to 0.955g / cc (measured according to ASTM D-792).

基于组分(C)和组分(D)的聚合物组合物的总体密度优选为0.92至0.95g/cc,更优选0.925至0.945g/cc,最优选0.925至0.94g/cc(按照ASTM D-792测量)。 The overall density is preferably based on the component (C) and the polymer composition component (D) is 0.92 to 0.95g / cc, more preferably 0.925 to 0.945g / cc, most preferably 0.925 to 0.94g / cc (according to ASTM D -792 measurement).

用作第二种乙烯聚合物组分(B)的合适乙烯聚合物为乙烯的均聚物和共聚体,包括基本上线性乙烯聚合物、均相支化线性乙烯聚合物,非均相支化线性乙烯聚合物(即线性低密度聚乙烯(LLDPE)、中密度聚乙烯(MDPE)、和高密度聚乙烯(HDPE),如用Ziegler-Natta催化剂体系制备的那些),及其掺混物或混合物。 As the second ethylene polymer component (B) Suitable ethylene polymers are homopolymers of ethylene and interpolymers, comprising substantially linear ethylene polymers, homogeneously branched linear ethylene polymers, heterogeneously branched linear ethylene polymers (i.e., linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), such as those prepared by Ziegler-Natta catalyst system), and blends thereof, or mixture.

基本上线性乙烯聚合物分别由The Dow Chemical Company和Dupont Dow Elastomers以商品名AFFINITYTM和ENGAGETM树脂出售。 Respectively, by a substantially linear ethylene polymers and The Dow Chemical Company under the trade name of Dupont Dow Elastomers and ENGAGETM AFFINITYTM resins sold. 均相支化线性乙烯聚合物分别由Mitsui Chemical Corporation以商品名TAFMERTM和Exxon Chemical Corporation以商品名EXACTTM和EXCEEDTM出售。 Homogeneously branched linear ethylene polymers are trade names TAFMERTM Exxon Chemical Corporation and sold by Mitsui Chemical Corporation and under the trade name EXACTTM EXCEEDTM. 合适非均相支化线性乙烯聚合物由The Dow ChemicalCompany以商品名DOWLEXTM出售。 Suitable heterogeneously branched linear ethylene polymers sold by The Dow ChemicalCompany under the trade name DOWLEXTM. 合适的中密度聚乙烯树脂和高密度聚乙烯树脂(如乙烯的共聚体或均聚物)可从多家生产厂商,包括以商品名MARLEXTM树脂从The Dow Chemical Company和PhillipsChemical Corporation购买。 Suitable medium-density polyethylene resins and high density polyethylene resin (e.g. ethylene interpolymer or homopolymer) may include trade name MARLEXTM resin available from a number of manufacturers and from The Dow Chemical Company PhillipsChemical Corporation.

术语“均相支化线性乙烯聚合物”是指常规意义上的线性乙烯共聚体,其中共聚单体无规分布于给定聚合物分子中,且其中基本上所有聚合物分子具有相同的乙烯与共聚单体的比例。 The term "homogeneously branched linear ethylene polymer" refers in the conventional sense linear ethylene interpolymer in which the comonomer is randomly distributed within a given polymer molecule and wherein substantially all of the polymer molecules have the same ethylene to the copolymerization ratio of the monomers. 该术语涉及具有较高短链支化分布指数(SCBDI)或组成分布指数(CDBI)的乙烯聚合物。 The term relates to ethylene polymers having a relatively high short chain branching distribution index (The SCBDI) or composition distribution index (CDBI of) a. 换言之,该共聚体的SCBDI大于或等于50%,优选大于或等于70%,更优选大于或等于90%。 In other words, the copolymer The SCBDI greater than or equal to 50%, preferably greater than or equal to 70%, more preferably greater than or equal to 90%. 然而,优选均相支化乙烯聚合物的进一步特征在于基本上无可测量的高密度(结晶)聚合物级分(用温升洗脱分级技术测定)。 However, preferred homogeneously branched ethylene polymer is further characterized in that substantially no measurable high density (crystalline) polymer fraction (measured by the temperature rise elution fractionation techniques).

SCBDI定义为具有共聚单体含量在总共聚单体摩尔含量中值的50%范围内的聚合物分子的重量百分比,并表示共聚单体在聚合物中的分布与Bernoullian分布预期的共聚单体分布的对比。 SCBDI is defined as having a comonomer content by weight percent of the polymer molecules in the range of the median total molar comonomer content of 50%, and said monomer copolymerizable comonomer distribution in the polymer Bernoullian distribution with the expected distribution contrast. 共聚体的SCDBI可方便地由温升洗脱分级技术(简称为“TREF”)计算,如描述于Wild等人聚合物科学期刊,聚合物物理分册(Journal ofPolymer Science,Poly. Phy. Ed.),Vol. 20,p.441(1982),或US4,798,081;5,008,204;或LDCady,“共聚单体类型和分布对LLDPE产品性能的影响”,SPE Regional Technology Conference,Quaker Squaker Hilton,Akron,Ohio,1985年10月1-2日,pp.107-119中,其公开的内容这里都作为参考引入。 SCDBI copolymer may conveniently be a temperature rise elution fractionation technique (abbreviated as "TREF") is calculated, as described in Wild et al, Journal of Polymer Science, Polymer Physics Volume (Journal ofPolymer Science, Poly. Phy. Ed.) ., Vol 20, p.441 (1982), or US4,798,081; 5,008,204; or LDCady, "Effects of the type and distribution of comonomer LLDPE product performance", SPE Regional Technology Conference, Quaker Squaker Hilton, Akron, Ohio, October 1985 1-2 days, pp.107-119, the disclosures of which are incorporated herein by reference. 然而,在SCDBI计算中优选的TREF技术不包括清机量。 However, the preferred TREF calculation SCDBI art does not include the amount of cleaning machines. 更优选地,共聚体的共聚单体分布和SCDBI通过按照描述于US5,292,845和JCRandall,高分子化学物理综述(Rev. Macromol. Chem. Phys.),C29,pp.201-317中的技术用13C NMR分析测定。 More preferably, the comonomer and comonomer distribution SCDBI body as described in US5,292,845 and by JC Randall, Polymer Chemistry Physics Review (Rev. Macromol. Chem. Phys.), C29, the technique pp.201-317 13C NMR analysis.

除了涉及均相(或窄)短链支化分布外,术语“均相支化线性乙烯聚合物”还指无长链支化的共聚体。 Addition involving homogeneous (or narrow) short chain branching distribution, the term "homogeneously branched linear ethylene polymer" means no further long chain branched copolymer. 换言之,该乙烯共聚体不存在长链支化和具有通常意义上的“线性”聚合物主链。 In other words, the absence of the ethylene interpolymers having long chain branching "linear" polymer backbone in the usual sense. 然而,术语“均相支化线性乙烯聚合物”不是指本领域熟练技术人员已知的具有多个长链的高压支化聚乙烯。 However, the term "homogeneously branched linear ethylene polymers" does not mean known to the person skilled in the high-pressure polyethylene having a plurality of long branched chains. 均相支化线性乙烯聚合物可用提供均匀(窄)短链支化分布的聚合方法(例如Elston在US3,645,992中描述的)制备。 Homogeneously branched linear ethylene polymer can provide uniform (narrow) short chain polymerization process branching distribution (e.g. as described in US3,645,992 Elston) is prepared. 在他的聚合方法中,Elston使用可溶性钒催化剂体系制备这些聚合物,然而,其它人,如Mitsui Chemical Industries和Exxon ChemicalCompany,已报道使用所谓单点催化剂体系制备具有类似结构的聚合物。 In his polymerization process, Elston prepared using these polymers soluble vanadium catalyst systems, however, others such as Mitsui Chemical Industries and Exxon ChemicalCompany, it has been reported a so-called single site catalyst systems prepared using a polymer having a similar structure. 均相支化线性乙烯聚合物可在溶液、淤浆或气相方法中用铪、锆或钒催化剂体系制备。 Hafnium, zirconium prepare branched linear ethylene polymers can be used in solution, slurry or gas phase process, or a homogeneous vanadium catalyst systems. Ewen等人在US4,937,299中描述了用金属茂催化剂制备的方法。 The method of preparing the metallocene catalysts described in Ewen, et al. In US4,937,299.

这里使用术语“非均相支化线性乙烯聚合物”指通常意义上的涉及具有较低短链支化分布指数的线性乙烯共聚体。 As used herein, the term "heterogeneously branched linear ethylene polymer" refers generally relates to sense linear ethylene interpolymer having a low short chain branching distribution index. 换言之,该共聚体具有相当宽的短链支化分布。 In other words, the copolymer having a relatively broad short chain branching distribution. 非均相支化线性乙烯聚合物的SCBDI小于50%,通常小于30%。 Heterogeneously branched linear ethylene polymers SCBDI less than 50%, typically less than 30%.

非均相支化乙烯聚合物是线性聚合物领域技术人员所公知的。 Heterogeneously branched ethylene polymer is a linear polymer known to those skilled in the art. 非均相支化线性乙烯聚合物用常规溶液、淤浆或气相聚合方法(在高或低压下)在Ziegler-Natta配位金属催化剂存在下按照例如Anderson等人在US4,076,698中的描述的方法制备。 Heterogeneously branched linear ethylene polymer with a conventional solution, slurry or gas phase polymerization process (at high or low pressure) according to the method described in Anderson et al. US4,076,698, for example, in the presence of complex metal Ziegler-Natta catalyst preparation. 这些常规Ziegler-Natta线性乙烯聚合物不是“均相支化的”,不具有任何长链支化,因此具有术语“线性”的通常意义上的线性聚合物主链。 These conventional Ziegler-Natta linear ethylene polymers are not "homogeneously branched", it does not have any long chain branching, and therefore a linear polymer backbone having the usual sense of the term "linear" is.

通常,均相支化线性乙烯聚合物和非均相支化乙烯聚合物是乙烯/α-烯烃共聚体,其中α-烯烃为至少一种C3-C20α-烯烃(如丙烯、1-丁烯、戊烯、4-甲基-1-戊烯、1-己烯、1-辛烯等),并优选该至少一种C3-C20α-烯烃为1-辛烯。 Typically, homogeneously branched linear ethylene polymers and heterogeneously branched ethylene polymer is an ethylene / α- olefin interpolymer, wherein the at least one alpha] -olefin is a C3-C20α- olefins (such as propylene, 1-butene, pentene, 4-methyl-1-pentene, 1-hexene, 1-octene) and preferably the at least one C3-C20α- olefin is 1-octene. 最优选该乙烯/α-烯烃共聚体为乙烯与C3-C20α-烯烃的共聚物,特别是乙烯与C4-C6α-烯烃的共聚物,更特别是乙烯/1-辛烯的共聚物。 Most preferably, the ethylene / [alpha] -olefin interpolymer is a copolymer of ethylene with C3-C20α- olefins, particularly ethylene and C4-C6α- olefin, more particularly an ethylene / 1-octene copolymers.

本文所用的术语“基本上线性乙烯聚合物”是指均相支化乙烯聚合物(共聚体和均聚物),其具有窄的短链支化分布并含有长支链以及可归因于均相共聚单体加入的短支链。 As used herein, the term "substantially linear ethylene polymer" refers to homogeneously branched ethylene polymers (homopolymers and copolymers) having a narrow short chain branching distribution and contain long chain branching and are attributable to with the added comonomer short chain branching. 长支链具有与聚合物主链相同的结构并比短支链长。 Long-chain branched polymer backbone having the same structure and length than the short chain branching. 基本上线性α-乙烯聚合物具有0.01个-3个长支链/1000个碳原子。 Substantially linear ethylene polymers having α- -3 0.01 long chain branches / 1000 carbon atoms. 优选用于本发明的基本上线性聚合物具有0.01个长支链/1000个碳原子至1个长支链/1000个碳原子,更优选0.05个长支链/1000个碳原子至1个长支链/1000个碳原子。 Substantially linear polymers useful in the present invention preferably has 0.01 long chain branches / 1000 carbons to 1 long chain branches / 1000 carbon atoms, more preferably from 0.05 long-chain branches / 1000 carbons to 1 long branches / 1000 carbon atoms.

本文定义长链支化为具有至少7个碳原子的链长度,大于此长度不能用13C核磁共振谱分辨。 Long chain branching is defined herein into having a chain length of at least 7 carbon atoms, above which the length can not be distinguished using 13C nuclear magnetic resonance spectroscopy. 长支链可与其所连的聚合物主链的长度一样长。 Long chain branches can be as long as the length of the polymer backbone to which it is connected. 长支链的长度明显比因加入共聚单体导致的短支链长。 Obviously the length of a long chain branch is longer than the short chain branching due to comonomer incorporation caused.

用13C核磁共振谱(NMR)可确定在乙烯均聚物中存在长链支化,并可用Randall在高分子化学物理综述,C29,v.2 & 3,P285-297中所述的方法定量。 By 13C nuclear magnetic resonance spectroscopy (NMR) can determine the presence of long chain branching in an ethylene homopolymer, and review available physical Randall in Polymer Chemistry, C29, v.2 & amp; quantitative method described in 3, P285-297 .

实际上,目前的13C核磁共振谱不能测定超过6个碳原子的长支链长度。 In fact, current 13C nuclear magnetic resonance spectrum was measured not more than 6 carbon atoms, branched long chain length. 然而,存在用于测定乙烯聚合物(包括乙烯/1-辛烯共聚体)中存在的长支链的其它已知方法。 However, for determining the presence of ethylene polymer (including an ethylene / 1-octene interpolymers) other known methods of long chain branching present. 两种这样的方法是凝胶渗透色谱与小角度激光散射检测器连用(GPC-LALLS)和凝胶渗透色谱与微分粘度检测器连用(GPC-DV)。 Two such methods are gel permeation chromatography coupled with low angle laser light scattering detector used in conjunction (GPC-LALLS) and gel permeation chromatography in conjunction with a differential viscometer detector (GPC-DV). 这些技术在长支链检测中的应用和依据的理论已详细描述于文献中。 Theory and applications of these techniques based on the detection of long chain branching have been described in detail in the literature. 例如,参见Zimm,GH和Stockmayer,WH,化学物理期刊(J. Chem. Phys.),17,1301(1949)和Rudin,A.,聚合物现代表征方法(Modern Methods of PolymerCharacterization),John Wiley & Sons,New York(1991)pp.103-112中。 For example, See, Zimm, GH and Stockmayer, WH, Journal of Chemical Physics (J. Chem. Phys.), 17,1301 (1949) and Rudin, A., Modern polymer characterization (Modern Methods of PolymerCharacterization), John Wiley & amp ; Sons, New York (1991) pp.103-112 of.

The Dow Chemical Company的A. Willem deGroot和P. SteveChum在1994年10月4日于St. Louis,Missouri举行的联邦分析化学和光谱学会(Federation of Analytical Chemistry andSpectroscopy Society)(FACCS)会议上,给出的数据证明GPC-DV是定量分析基本上线性乙烯聚合物中存在长支链的适用技术。 The Dow Chemical Company of A. Willem deGroot and P. SteveChum chemical and spectral analysis at the federal Institute in St. Louis, Missouri held on October 4, 1994 (Federation of Analytical Chemistry andSpectroscopy Society) (FACCS) meeting, given the data demonstrate that GPC-DV is a quantitative analysis technique suitable long chain branches in substantially linear ethylene polymer is present. 特别是,deGroot和Chum发现,用Zimm-Stockmayer方程测量的在基本上线性乙烯聚合物中存在的长支链的量与用13C-NMR测量的长支链量的结果吻合得很好。 In particular, deGroot and Chum found that the amount of long chain branching present in the substantially linear ethylene polymers Zimm-Stockmayer equation with the measured results of the amount of long chain branches measured 13C-NMR in good agreement.

此外,Degroot和Chum发现,辛烯的存在不改变聚乙烯样品在溶液中的流体动力学体积,因此,可通过已知样品中的辛烯mol%计算属于辛烯短支链的分子量增加。 Further, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, therefore, the molecular weight can be increased by the known samples octene mol% of which belong to octene short chain branches. DeGroot和Chum发现,通过扣除归属于1-辛烯的短支链对分子量增加的贡献,GPC-DV可用于定量基本上线性乙烯/辛烯共聚物中的长支链量。 DeGroot and Chum found by subtracting the short chain branches attributable to 1-octene of the contribution of increased molecular weight, GPC-DV may be used to quantify the amount of long-chain branched substantially linear ethylene / octene copolymer.

Degroot和Chum还证明,作为Log(GPC重均分子量)函数的Log(I2,熔体指数)图(通过GPC-DV测定)描述了基本上线性乙烯聚合物的长链支化情况(但不是长链支化含量)与那些高压、高支化低密度聚乙烯(LDPE)的长链支化相当,且明显区别于用Ziegler型催化剂如钛配合物和普通均相催化剂如铪和钒配合物生产的乙烯聚合物。 Degroot and Chum also showed, as Log (GPC weight average molecular weight) function Log (I2, melt index) images (measured by GPC-DV) describes long chain branched substantially linear ethylene polymers cases (but not length chain branching content) and those of high pressure, highly branched low density polyethylene (LDPE) relatively long chain branching and distinct from a Ziegler-type catalysts such as titanium complexes and ordinary homogeneous catalysts such as hafnium and vanadium complexes production ethylene polymer.

用于本发明的基本上线性乙烯聚合物为进一步定义于US5,272,236,流水号07/776,130(申请日1991年10月15日)和US5,279,272,流水号07/939,281(申请日1992年9月2日)中的一类独特化合物。 Substantially linear ethylene polymers used in the present invention are further defined in US5,272,236, Serial No. 07 / 776,130 (filed October 15, 1991) and US5,279,272, Serial No. 07 / 939,281 (filed May 9, 1992 a unique class of compound 2 May) was added.

基本上线性乙烯聚合物明显不同于上述和(例如)Elston在US3,645,992中描述的均相支化线性乙烯聚合物。 Substantially linear ethylene polymers described above and significantly different from (e.g.) Elston described in US3,645,992 of homogeneously branched linear ethylene polymers. 作为一个重要区别,基本上线性乙烯聚合物不具有均相支化线性乙烯聚合物中具有的术语“线性”通常所指的线性聚合物主链。 As an important distinction, substantially linear ethylene polymers do not have a linear polymer backbone homogeneously branched linear ethylene polymer having the term "linear" is generally referred to. 基本上线性乙烯聚合物也明显不同于通常称为非均相支化传统Ziegler聚合线性乙烯共聚体(例如超低密度聚乙烯、线性低密度聚乙烯或用Anderson等人在US4,076,698中公开的技术制备的高密度聚乙烯)的一类聚合物,原因在于基本上线性乙烯共聚体为均相支化聚合物;换言之,基本上线性乙烯聚合物具有SCBDI大于或等于50wt%,优选大于或等于70%,更优选大于或等于90%。 Substantially linear ethylene polymers are also commonly referred to as distinct from heterogeneously branched traditional Ziegler polymerized linear ethylene interpolymers (e.g. ultra low density polyethylene, linear low density polyethylene or disclosed by Anderson et al. In US4,076,698 of technology to prepare high density polyethylene) of a polymer, because the substantially linear ethylene interpolymer is a homogeneously branched polymers; that is, substantially linear ethylene polymer has a SCBDI greater than or equal to 50wt%, preferably greater than or equal to 70%, more preferably greater than or equal to 90%. 基本上线性乙烯聚合物也不同于非均相支化乙烯聚合物类,原因是基本上线性乙烯聚合物基本上无可用温升洗脱分级技术测量的高密度或结晶性聚合物级分。 Substantially linear ethylene polymers also differ from heterogeneously branched ethylene polymers, substantially linear ethylene polymers because essentially no free rise elution fractionation techniques for measuring the high density or crystalline polymer fraction.

基本上线性乙烯聚合物也明显不同于游离基引发的一类聚合物,如高支化高压低密度乙烯均聚物和乙烯共聚体,如乙烯-丙烯酸(EAA)共聚物和乙烯-乙酸乙烯酯(EVA)共聚物。 Substantially linear ethylene polymers are also significantly different from a polymer of a radical initiator, such as a highly branched high pressure low density ethylene homopolymer and ethylene interpolymers such as ethylene - acrylic acid (EAA) copolymers and ethylene - vinyl acetate (EVA) copolymers. 换言之,基本上线性乙烯聚合物不与高压、游离基引发的乙烯聚合物具有相同程度的长链支化,并用单点催化剂体系,而不是游离基过氧化物催化剂体系制备。 In other words, substantially linear ethylene polymers is not as high pressure, free radical initiated ethylene polymer having the same degree of long chain branching, and with a single site catalyst system, a free radical peroxide catalyst system prepared instead.

金属茂单点聚合催化剂(例如Canich在US5,026,798或Canich在US5,055,438中描述的单环戊二烯基过渡金属烯烃聚合催化剂)或束缚几何催化剂(例如,Steven等人在US5,064,802中描述的)可用于制备基本上线性乙烯聚合物,只要制备和使用与US5,272,236和US5,278,272中描述的方法一致的金属茂催化剂即可。 The metallocene single site polymerization catalyst (monocyclopentadienyl transition metal olefin e.g. Canich described in US5,026,798 or US5,055,438 polymerization catalyst Canich) or binding geometry catalysts (e.g., Steven et al., Described in US5,064,802 a) it can be used to prepare substantially linear ethylene polymers, as long as a metallocene catalyst and methods of making and using same in US5,272,236 and US5,278,272 described. 这些聚合方法还描述于PCT/US92/08812(申请日1992年10月15日)中。 These polymerization methods are also described in PCT / US92 / 08812 in (filed October 15, 1992). 然而,基本上线性乙烯聚合物优选用合适的束缚几何催化剂,特别是例如US申请流水号545,403(申请日1990年7月3日)、US5,132,380、US5,064,802、US5,153,157、US5,470,993、US5,453,410、US5,374,696、US5,532,394、US5,494,874和US5,189,192中的那些束缚几何催化剂制备。 However, substantially linear ethylene polymers is preferably bound with a suitable geometry catalysts, in particular, for example, US Application Serial No. 545,403 (filed on July 3, 1990), US5,132,380, US5,064,802, US5,153,157, US5,470,993 , US5,453,410, US5,374,696, US5,532,394, US5,494,874 and US5,189,192 geometric those bound by the catalyst preparation.

这里使用的合适助催化剂包括但不限于(例如)聚合或低聚铝氧烷,特别是甲基铝氧烷或改性甲基铝氧烷(例如,在US5,041,584、US4,544,762、5,015,749和/或5,041,585中描述的)以及惰性相容非配位离子形成化合物。 Suitable cocatalysts for use herein include, but are not limited to (e.g.) polymeric or oligomeric aluminoxanes, especially methyl aluminoxane or modified methyl aluminoxane (e.g., in US5,041,584, US4,544,762,5,015,749 and / or) and an inert, compatible, noncoordinating ion forming compounds described in 5,041,585. 优选的助催化剂为惰性非配位硼化合物。 Preferred cocatalysts are inert, noncoordinating, boron compounds.

本发明中用于制备基本上线性乙烯聚合物的聚合条件优选为连续溶液聚合方法中所用的那些条件,尽管本发明申请不限于此。 Preparation conditions are those conditions that the polymerization is preferably substantially linear ethylene polymers is a continuous solution polymerization process used in the present invention is used, although the present invention is not limited to this application. 还可使用连续淤浆和气相聚合方法,只要使用合适的催化剂和聚合条件即可。 Also continuous slurry and gas phase polymerization processes, as long as using a suitable catalyst and polymerization conditions can be. 为聚合适用于本发明的基本上线性乙烯聚合物,可以使用上面提及的单点和束缚几何催化剂;然而,对于基本上线性乙烯聚合物,聚合方法应在确实形成基本上线性乙烯聚合物的条件下操作。 Polymerization substantially linear ethylene polymers suitable for the present invention, a single point and the bound geometry catalysts mentioned above; however, for the substantially linear ethylene polymers, the polymerization process should be actually formed in a substantially linear ethylene polymer under operating conditions. 换言之,甚至当使用相同的催化剂时,并非所有聚合条件都当然制得基本上线性乙烯聚合物。 In other words, even when using the same catalyst, of course, not all polymerization conditions were substantially linear ethylene polymers prepared. 例如,在用于制备基本上线性乙烯聚合物的聚合方法的一个实施方案中,使用连续聚合方法,而不是间歇聚合方法。 For example, in one embodiment of the preparation method of the polymerization for the substantially linear ethylene polymers, the polymerization method using a continuous, rather than intermittent throughout the polymerization process.

概而言之,用于本发明的基本上线性乙烯聚合物具有如下特征:(a)熔体流动速率I10/I2≥5.63(b)通过凝胶渗透色谱测定,分子量分布Mw/Mn由如下方程定义:(Mw/Mn)≤(I10/I2)-4.63(c)使基本上线性乙烯聚合物表面熔体破裂开始时的临界剪切速率比线性乙烯聚合物表面熔体破裂开始时的临界剪切速率大至少50%的气体挤出流变性能,其中基本上线性乙烯聚合物和线性乙烯聚合物包括相同的共聚单体,线性乙烯聚合物具有的I2、Mw/Mn和密度值在基本上线性乙烯聚合物的上下10%范围内,和其中基本上线性乙烯聚合物和线性乙烯聚合物的相应临界剪切速率在相同的熔体温度下使用气体挤出流变仪测定,(d)在-30至140℃之间的单个差示扫描量热DSC熔化峰,和(e)短链支化分布指数大于约50%。 In summary, the substantially linear ethylene polymers used in the present invention has the following characteristics: (a) a melt flow rate I10 / I2≥5.63 (b) measured by gel permeation chromatography, the molecular weight distribution Mw / Mn by the equation definitions: (Mw / Mn) ≤ (I10 / I2) -4.63 (c) that the substantially linear ethylene polymer surface melt fracture critical shear critical shear rate at the start at the start of fracture than linear ethylene polymers melt surface cut rate of at least 50% of the gas extrusion rheological properties, wherein a substantially linear ethylene polymer and the linear ethylene polymer comprise the same comonomer, linear ethylene polymers having I2, Mw / Mn and density values ​​substantially line within a distance of 10% of an ethylene polymer, and wherein the respective critical shear rates substantially linear ethylene polymers and linear ethylene polymers using a gas extrusion rheometer at the same melt temperature, (d) in a single differential scanning calorimetry DSC melting peak between -30 and 140 ℃, and (e) a short chain branching distribution index greater than about 50%.

用于本发明(特别是用作至少一第一种乙烯聚合物)的优选均相支化乙烯聚合物为均相支化共聚体(即不是均聚物),且通过合适的TREF技术测量基本上无可测量的“高密度”或结晶聚合物级分。 Preferably used in the present invention (in particular, as at least a first ethylene polymer) of the polymer is a homogeneously branched ethylene homogeneously branched interpolymer (i.e., not a homopolymer), and measured by a suitable technique substantially TREF on no measurable "high density" or crystalline polymer fractions. 优选的均相支化乙烯共聚体为具有窄短链分布(即高SCBD指数)的基本上线性乙烯聚合物。 Preferred homogeneously branched ethylene interpolymer having a narrow short chain distribution (i.e., a high SCBD index) of substantially linear ethylene polymers. 基本上线性乙烯聚合物不含支化度低于或等于2个甲基/1000个碳原子的聚合物级分。 The degree of branching is substantially free of linear ethylene polymers is less than or equal to 2 methyls / 1000 carbon atoms of polymer fractions. 换言之,特征在于由均匀聚合物级分组成的基本上线性乙烯共聚体不含高密度或结晶性聚合物级分,其中将特征在于无短链支化或短链支化度低于或等于2个甲基/1000个碳原子的聚合物级分认为是“高密度”或“结晶性的”。 In other words, characterized in that a homogeneous substantially linear ethylene polymer fractions the composition is free of a copolymer of high density or crystalline polymer fraction, characterized in that where no short chain branching or short chain branching less than or equal to 2 methyls / 1000 carbon atoms of polymer stage partial considered "high density" or "crystalline." 然而,当将均相支化乙烯聚合物用作第二种乙烯聚合物组分(规定其密度为0.94g/cc至0.97g/cc)且该聚合物为均聚物或含有非常少的共聚单体时,该聚合物自然被此方法表征为具有“高密度”或“结晶性”的聚合物级分。 However, the homogeneously branched ethylene polymer used as the second ethylene polymer component (which predetermined density 0.94g / cc to 0.97g / cc) and the polymer is a homopolymer or copolymer contains very little monomer, the natural polymer is characterized as having a "high density" or "crystalline" polymer fraction method.

用于本发明的基本上线性乙烯共聚体为乙烯均聚物和乙烯与至少一种C3-C20α-烯烃和/或C4-C18二烯烃的共聚体。 Substantially linear ethylene interpolymers used in the present invention is an ethylene homopolymer and ethylene with at least one C3-C20α- olefin and / or a copolymer of C4-C18 diolefins. 乙烯与C3-C20α-烯烃的共聚物是特别优选的。 Ethylene with C3-C20α- -olefin are especially preferred. 上面讨论的术语“共聚体”这里用于表示共聚物、或三元聚合物或其类似物,其中至少一种另外的共聚单体与乙烯或丙烯共聚制备共聚体。 Discussed above, the term "interpolymer" used herein refers to a copolymer or terpolymer or an analog thereof, wherein at least one additional comonomer with ethylene propylene copolymer or interpolymer prepared.

用于与乙烯聚合的合适不饱和共聚单体包括(例如)烯属不饱和单体,共轭或非共轭二烯烃,多烯烃等。 Suitable for the polymerization of ethylene and unsaturated comonomers include (for example) an ethylenically unsaturated monomer, conjugated or non-conjugated dienes, polyenes and the like. 合适的共聚单体的例子包括C3-C20α-烯烃,如丙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯等。 Examples of suitable comonomers include C3-C20α- olefins such as propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 - nonene, 1-decene and the like. 优选的共聚单体包括丙烯、1-丁烯、4-甲基-1-戊烯和1-辛烯,特别优选1-辛烯。 Preferred comonomers include propylene, 1-butene, 4-methyl-1-pentene and 1-octene, particularly preferably 1-octene. 其它合适的单体包括苯乙烯、卤素或烷基取代苯乙烯、四氟乙烯、乙烯基苯并环丁烷、1,4-己二烯、1,7-辛二烯,和环烯如环戊烯、环己烯和环辛烯。 Other suitable monomers include styrene, halo or alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and cycloalkenyl rings as pentene, cyclohexene and cyclooctene.

涉及熔体破裂的临界剪切速率和临界剪切应力以及其它流变性能如“流变加工指数”(PI)测定用气体挤出流变仪(GER)进行。 It relates to melt fracture critical shear rate and critical shear stress and other rheological such as "rheological processing index" (the PI) was measured extrusion rheometer (GER) gas performance. 气体挤出流变仪由M.Shida,RNShroff和LV Cancio描述于聚合物工程科学(Polymer Engineering Science),Vol.17,No.11,p.770(1977)中,并由John Dealy,描述于“熔融塑料流变仪(Rheometers for Molten Plastics)”(Van Nostrand Reinhold Co出版,(1982))pp.97-99中。 A gas extrusion rheometer M.Shida, RNShroff described and LV Cancio in Polymer Engineering Science (Polymer Engineering Science), the Vol.17, No.11, p.770 (1977), by John Dealy, described in "molten plastic rheometer (rheometers for molten plastics)" (Van Nostrand Reinhold Co Publishing, (1982)) pp.97-99 in. GER实验在温度约190℃、氮气压力250至5500 psig(1.7至37.9Mpa)下用具有入口角180°的直径0.0754mm,L/D 20∶1模头进行。 GER experiments, L / D 20:1 die head having a diameter of 0.0754mm an inlet angle of 180 ° at a temperature of about 190 ℃, under a nitrogen pressure of 250 to 5500 psig (1.7 to 37.9 MPa). 对于这里使用的基本上线性乙烯聚合物,PI为通过GRE在表观剪切速率2.15×106dyne/cm2下测量的材料的表观粘度(单位:千泊)。 For substantially linear ethylene polymers used herein, PI is the apparent viscosity by GRE apparent shear rate of 2.15 × 106dyne / cm2 measured material (unit: kpoise). 用于本发明的基本上线性乙烯聚合物具有PI约0.01千泊至约50千泊,优选约15千泊或更低。 Substantially linear ethylene polymers used in the present invention have a PI of about 0.01 kpoise to about 50 kpoise, preferably about 15 kpoise or less. 这里使用的基本上线性乙烯聚合物的PI低于或等于其I2、Mw/Mn和密度在基本上线性乙烯聚合物相应值上下10%范围内的线性乙烯聚合物(如Elston在US3,645,992中描述的常规Ziegler催化共聚体或线性均相支化共聚体)的PI的约70%。 PI used herein, substantially linear ethylene polymer is less than or equal to I2, Mw / Mn and density of the substantially linear ethylene polymer US3,645,992 value corresponding linear ethylene polymer within a distance of 10% (e.g., Elston from about 70% PI a conventional Ziegler catalyst described interpolymer or homogeneously branched linear interpolymers) of.

表观剪切应力与表观剪切速率图用于确定熔体破裂现象及定量乙烯聚合物的临界剪切速率和临界剪切应力。 Apparent shear stress and apparent shear rate diagram for determining critical shear rate and critical shear stress in the melt fracture phenomena and quantify the ethylene polymer. 根据Ramamurthy在流变学期刊(Journal of Rheology),30(2),337-357,1986中的描述,在高于某一临界剪切速率时,在流变仪挤出物中可观察到挤出物不规则性,该不规则性可分为两种类型:表面熔体破裂和总体熔体破裂。 Ramamurthy in Journal of Rheology (Journal of Rheology), 30, 337-357, 1986 is described in (2), above a certain critical shear rate, the observed extrudate rheometer according to the squeeze effluent irregularities, the irregularities can be divided into two types: surface melt fracture and overall melt fracture.

表面熔体破裂在表观稳定流动条件下出现,其范围从镜面薄膜光泽降低至更严重的“鲨皮斑”形式。 Surface melt fracture at an apparent steady flow conditions occur, ranging from reducing specular film gloss to the more severe "sharkskin" form. 这里当用上述GER测定时,表面熔体破裂开始(OSMF)用挤出物光泽开始降低表征,其中挤出物的表面粗糙度可方便地在40倍放大下检测。 Here, when the above-described GER measurement start surface melt fracture (OSMF) starts to decrease extrudate gloss characterized by, wherein the surface roughness of the extrudate can be conveniently detected at 40 times magnification. 基本上线性乙烯共聚体的表面熔体破裂开始时的临界剪切速率比具有基本上相同的I2和Mw/Mn的线性乙烯共聚体表面熔体破裂开始时的大至少50℃%。 Substantially linear ethylene interpolymers of surface melt fracture critical shear rate at the start than having substantially the same I2 and Mw / linear ethylene interpolymer Mn of surface melt fracture at least at the start of a large 50 ℃%.

总体熔体破裂在不稳定挤出流动条件下出现,其范围从规则(交替粗糙和光滑、螺旋面等)至无规变形。 In general melt fracture occurs under unstable extrusion flow conditions, ranging from regular (alternating rough and smooth, helical surfaces, etc.) to random deformation. 为在工业上可接受并得到最佳密封剂性能,表面缺陷(若存在)应最小。 Acceptable and optimum sealant performance, surface defects in the industry (if present) should be minimized. 用于本发明的基本上线性乙烯聚合物,即密度低于约0.91g/cc的那些聚合物的总体熔体破裂开始时的临界剪切应力大于4×106dyn/cm2。 Substantially linear ethylene polymers used in the present invention, i.e., a density less than about 0.91g / cc of those polymers generally melt fracture critical shear stress at the start of greater than 4 × 106dyn / cm2. 这里使用的表面熔体破裂开始(OSMF)时和总体熔体破裂开始(OGMF)时的临界剪切速率基于由GER挤出的挤出物的表面粗糙度和构型变化。 Start (OSMF) overall melt fracture critical shear rate at the start (OGMF) based on the surface roughness of extrudates extruded by a GER and conformational changes of surface melt fracture for use herein. 在本发明中,基本上线性乙烯聚合物优选用其邻界剪切速率,而不是临界剪切应力表征。 In the present invention, preferably substantially linear ethylene polymers with a shear rate of its neighborhood boundaries, rather than the critical shear stress characterization.

优选的均相乙烯聚合物,如所有基本上线性乙烯聚合物的进一步特征是由单一聚合物组分组成并具有单个DSC熔化峰。 Preferred homogeneous ethylene polymer is further characterized as all substantially linear ethylene polymer is a single polymer component and having a single DSC melting peak. 该单个熔化峰用铟和去离子水校准的差示扫描量热计测定。 The single melting peak measured with indium and deionized water calibrated differential scanning calorimetry. 该方法采用5-7mg样品量,“第一次加热”至140℃,在此温度下保持4min,按10°/min冷却至-30℃,在此温度下保持3min,并以10℃/min加热至140℃(“第二次加热”)。 The method uses 5-7mg sample size, "first heat" to 140 deg.] C, held at this temperature for 4min, by 10 ° / min was cooled to -30 deg.] C, held at this temperature for 3min, and at 10 ℃ / min was heated to 140 deg.] C ( "second heat"). 该单个熔化峰取自“第二次加热”时热焓与温度曲线。 When the temperature enthalpy profile of the single melting peak is taken from the "second heat." 聚合物的总熔化热由曲线下的面积计算。 Total heat of fusion of the polymer is calculated from the area under the curve.

对于具有密度0.875g/cc至约0.91g/cc的基本上线性乙烯共聚体,根据设备的灵敏度,该单个熔化峰可在低熔化一侧出现“肩”或“驼”峰,它构成聚合物总熔化热的12%以下,通常低于9%,更通常低于6%。 For a density of 0.875g / cc to about 0.91g / cc substantially linear ethylene interpolymers, depending on the sensitivity of the device, the single melting peak may be a "shoulder" or a "camel" peak low melting side that constitutes the polymer 12% or less of the total heat of fusion, typically less than 9 percent, more typically less than 6%. 这种伴随峰(artifact)对于均相支化聚合物如EXACTTM可观察到,并基于单个熔化峰的斜率经该伴随峰的熔化区单调变化辨认。 Such concomitant peak (artifact) for the homogeneously branched polymers such as EXACTTM can be observed, and based on the slope of the single melting peak accompanied by the melting peak area varies monotonically identified. 该伴随峰出现在单个熔化峰熔化点的34℃、通常27℃、更通常20℃范围内。 The peak at 34 ℃ accompanying single melting peak melting point, typically 27 ℃, more typically in the range of 20 ℃. 属于伴随峰的熔化热可通过专门积分其在热焓~温度曲线下的相关面积,单独测定。 The heat of fusion of peaks belonging to the accompanying specialized integration through its associated area under the curve of the temperature - enthalpy, determined separately.

乙烯聚合物的分子量分布通过凝胶渗透色谱(GPC)在装有混合多孔柱的Waters 150C高温色谱单元上测定。 Distribution of molecular weight ethylene polymer measured on Waters 150C high temperature chromatographic unit equipped with mixing porous column by gel permeation chromatography (GPC). 色谱柱由PolymerLaboratories出售,通常按颗粒尺寸103、104、105和106A堆积。 Column sold by PolymerLaboratories, usually in particle size 103, 104, and 106A accumulation. 溶剂为1,2,4-三氯苯,由该溶剂制备用于注射的待测聚合物试样的0.3wt%溶液。 The solvent is 1,2,4-trichlorobenzene, 0.3wt% solution of the polymer to be tested for the preparation of an injection of a sample by the solvent. 流速为1.0ml/min,单元操作温度为约140℃,注射量为100μl。 The flow rate was 1.0ml / min, unit operating temperature is about 140 ℃, injection volume was 100μl.

相对于聚合物主链的分子量分布测定通过用窄分子量分布聚苯乙烯标准物(购自Polymer Laboratories)和其洗脱体积推导。 With respect to the molecular weight distribution of the polymer backbone as determined by polystyrene standards with narrow molecular weight distribution (available from Polymer Laboratories), and eluted volume deduced. 当量聚乙烯分子量用聚乙烯和聚苯乙烯的合适Mark-Houwink系数(如Williams和Word在聚合物科学期刊,聚合物通讯,Vol.6,p.621(1968)中描述的)导出的如下方程测定:M聚乙烯=a*(M聚苯乙烯)6在该等式中,a=0.4316,b=1.0。 The equivalent polyethylene molecular weights derived polyethylene and polystyrene appropriate Mark-Houwink coefficients (as described by Williams and Word in Journal of Polymer Science, Polymer Communications, Vol.6, p.621 (1968)) of the following equation Determination: M polyethylene = a * (M polystyrene) 6 in this equation, a = 0.4316, b = 1.0. 重均分子量Mw和数均分子量Mn按照常规方式通过公式Mj=(Σwi(Mij))j计算,其中wi为洗脱自GPC柱的第i个级分的具有Mi的分子的重量分数,当计算Mw时,j=1,计算Mn时,j=-1。 The weight average molecular weight Mw and the number average molecular weight Mn in a conventional manner by the formula Mj = (Σwi (Mij)) j is calculated, where wi eluting from the GPC column i-th stage divided the weight fraction of the molecules with Mi, when calculating when Mw, j = 1, when calculating Mn, j = -1.

对于用于本发明的基本上线性乙烯聚合物和均相支化线性乙烯聚合物,Mw/Mn通常低于3.5,优选低于3.0,更优选低于2.5,特别是1.5至2.5,尤其是1.8至2.3。 For the present invention, substantially linear ethylene polymers and homogeneously branched linear ethylene polymer, Mw / Mn typically less than 3.5, preferably less than 3.0, more preferably less than 2.5, in particular 1.5 to 2.5, in particular 1.8 to 2.3.

已经知道基本上线性乙烯聚合物具有极好的可加工性,尽管其分子量分布较窄(即Mw/Mn比例通常低于3.5)。 Substantially linear ethylene polymers has been known to have excellent processability, despite its narrow molecular weight distribution (i.e. Mw / Mn ratio is typically less than 3.5). 令人吃惊的是,与均相和非均相支化线性乙烯聚合物不同,基本上线性乙烯聚合物的熔体流动比例(I10/I2)可基本上不依赖于其分子量分布Mw/Mn而变化。 Surprisingly, the homogeneous and heterogeneous branched linear ethylene polymers having different, the melt flow ratio substantially linear ethylene polymers (I10 / I2) can be substantially independent of its molecular weight distribution Mw / Mn and Variety. 因此,特别是需要良好的挤出加工性时,用于本发明的优选基本上线性乙烯聚合物为基本上线性乙烯聚合物,特别是基本上线性乙烯共聚体。 Thus, in particular the need for good extrusion processability, the present invention is preferably used in the substantially linear ethylene polymer is a substantially linear ethylene polymer, especially a substantially linear ethylene interpolymer.

本发明特别优选的薄膜、薄膜层或组合物的进一步特征是,具有低于15%、优选低于10%、更优选低于6%、最优选低于3%(按混合物的总重量计)的组成己烷萃取量。 A particularly preferred film of the present invention, a film or layer compositions are further characterized by having less than 15%, preferably less than 10%, more preferably less than 6%, most preferably less than 3% (by weight of the total mixture) hexane extracted amount of the composition.

另一特别优选的薄膜、薄膜层或组合物的进一步特征是,具有Vicat软化点至少75℃,优选至少85℃,更优选至少90℃。 Another particularly preferred film, or a film layer composition is further characterized by having a Vicat softening point of at least 75 ℃, preferably at least 85 ℃, more preferably at least 90 ℃.

在另一优选实施方案中,当需要良好的热强度时,本发明密封层一般性特征在于,在最小密封强度1.8N/15mm时,具有密封起始温度等于或低于(层Vicat软化温度-4.5℃),更优选在具体实施方案中,薄膜热密封起始温度等于或低于(层Vicat软化温度-6℃),最优选低于(层Vicat软化温度-10℃)。 In another preferred embodiment, when the required good thermal strength, general characteristics of the present invention wherein the sealing layer, at the minimum seal strength of 1.8N / 15mm, having (Vicat softening temperature of the sealing layer is equal to or lower than the initiation temperature - 4.5 ℃), and more preferably in a particular embodiment, the film heat sealing initiation temperature lower than or equal to (Vicat softening temperature of the layer of -6 deg.] C), most preferably less than (layer Vicat softening temperature -10 ℃).

本发明另一方面是加工单层或多层薄膜结构的方法,或将本发明的聚合物组合物加工为薄膜、薄膜层、涂料、热成型或模制品的方法。 Another aspect is a method of processing a single layer or multilayer film structure, or a polymer composition according to the present invention, the processing method of forming a molded article or a film, film layer, coating, heat. 该方法包括层压和共挤出技术或其结合,或包括仅使用聚合物组合物或混合物,且对于加工密封材料还可具体包括吹膜、流延膜、挤压涂装、注塑、吹塑、热成型、型材挤出、拉挤成型、压塑、滚塑、或注坯吹塑操作或其结合等。 The method comprises laminating and coextrusion techniques or combinations thereof, or a composition comprising only the polymer or mixture, and for further processing the sealing material comprises blown film, cast film, extrusion coating, injection molding, blow , thermoforming, profile extrusion, pultrusion, compression molding, rotomolding, or injection blow molding operation or combinations thereof and the like.

本发明的聚合物组合物或混合物可通过任何常规方法,包括将各组分干混接着在混炼机中熔混,或将所有组分直接在混炼机(例如Banbury混炼机、Haake混炼机、Brabender密炼机、或单或双螺杆挤出机,包括配料挤出机和直接在共聚步骤下游使用的侧臂挤出机)中混合形成。 Polymer composition or mixture of the invention may be by any conventional method, including dry blending the individual components and then melt blending in a kneading machine, or all the components directly in the kneader (e.g. Banbury mixer, a Haake mixing mill, Brabender mixer, or a single or twin screw extruder, an extruder and the ingredients comprising directly side-arm extruder used in the copolymerization step downstream) are mixed to form.

本发明的聚合物组合物或混合物(以及至少一第一种乙烯聚合物和至少一第二种乙烯聚合物)可在现场在至少一个反应器中使用单点催化剂,优选单点束缚几何催化剂,在至少另一反应器中使用单点催化剂、优选单点束缚几何催化剂,或Ziegler-Natta型催化剂聚合乙烯形成。 Or mixtures of the polymer composition (ethylene and at least one first polymer and at least one second ethylene polymer) of the present invention may employ a single site catalyst in at least one reactor in the field, preferably bound by a single site geometry catalysts, single site catalyst in at least one other reactor, preferably bound by a single point geometry catalysts, or Ziegler-Natta type catalyst for the polymerization of ethylene is formed. 对于现场聚合,反应器可按顺序或平行方式操作。 For in situ polymerization, the reactor may be sequential or parallel manner. 一个现场聚合方法的例子公开于PCT专利申请94/01052中,其公开的内容这里作为参考引入。 Examples of the polymerization method of a scene is disclosed in PCT Patent Application No. 94/01052, the disclosure of which is incorporated herein by reference.

本发明的聚合物组合物(以及至少一第一种乙烯聚合物或至少一第二种乙烯聚合物)可进一步通过如下方法形成:通过从非均相支化乙烯聚合物中将非均相乙烯聚合物分级为特定聚合物级分的方式分离组分(A)、(B)、(C)和/或(D)(或从均相支化乙烯聚合物中通过将均相乙烯聚合物分级为聚合物级分的方式分离组分(A)或(C)),选取满足组分(A)、(B)、(C)或(D)特定要求的合适级分,并将选取的级分按合适量与至少一第一种乙烯聚合物组分(A)或(C)或至少一第二种乙烯聚合物组分(B)或(D)混合。 Polymer compositions (a first and at least one ethylene polymer or at least one second ethylene polymer) of the present invention may further be formed by the following method: The heterogeneous ethylene polymers will be ethylene homogeneously branched from the non- polymer is fractionated into specific polymer fractions embodiment the component (a), (B), (C) and / or (D) (or by the homogeneously branched ethylene polymer in the homogeneous ethylene polymer grade separation of component (a) is a fraction of the polymeric or (C)), selecting components satisfy (a), (B), (C) or a suitable fraction (D) of the specific requirements, and the selected level suitable divided by the amount of the at least one first ethylene polymer component (a) or (C) or at least one second ethylene polymer component (B) or (D) mixture. 该方法明显不如现场聚合方法或上述共混机/挤出机混合技术经济,然而可用于获得本发明聚合物组合物或混合物以及至少一第一种乙烯聚合物和至少一第二种乙烯聚合物。 This method was not as good in situ polymerization method or said blender / extruder mixing technical and economic, but may be used to obtain a polymer composition or mixture according to the invention and at least one first ethylene polymer and at least one second ethylene polymer .

然而无论如何制备聚合物混合物、至少一第一种乙烯聚合物或至少一第二种乙烯聚合物制备,认为该组合物或组分聚合物为基于上面对非均相支化和均相支化(即SCBDI)定义的并基于整个组合物分析(如ATREF结果)而不是分级分析或制造技术的均相支化乙烯聚合物或非均相支化乙烯聚合物。 However, in any case prepare a mixture, at least a first ethylene polymer prepared in at least a second ethylene polymer or polymers, that the polymer composition or component-based face heterogeneously branched and homogeneously branched (i.e. the SCBDI) is defined and analyzed (e.g. ATREF results) based on the whole composition and not fractionation analysis or homogeneous manufacturing techniques branched ethylene polymers or homogeneously branched ethylene polymer.

添加剂,如抗氧剂(例如受阻酚IRGANOXTM1010或IRGANOXTM1076,由Ciba Geigy出售)、亚磷酸酯(例如IRGAFOSTM168,同样由Ciba Geigy出售)、粘着添加剂(例如PIB)、SANDOSTABPEPQTM(由Sandoz出售)、颜料、着色剂、填料、抗静电剂、加工助剂等也可包括于本发明聚合物混合物或由其形成的薄膜中。 Additives such as antioxidants (e.g., hindered phenols or IRGANOXTM1010 IRGANOXTM1076, sold by Ciba Geigy), phosphites (e.g. IRGAFOSTM168, also sold by the Ciba Geigy), cling additives (e.g., PIB), SANDOSTABPEPQTM (sold by Sandoz), pigments, colorants, fillers, antistatic agents, processing aids, etc. may also be included in the film or the polymer mixture of the present invention formed therefrom. 尽管通常不是必需的,由本发明聚合物混合物形成的薄膜、涂料和模制品还可含有增强防粘、脱模和摩擦系数特性的添加剂,包括但不限于未处理和处理的二氧化钛、滑石、碳酸钙和粘土,以及伯、仲和取代脂肪酰胺、脱模剂、硅氧烷涂布剂等。 Although generally not required, films, coatings and moldings formed from the polymer mixture according to the present invention may further contain additives to enhance release, mold release and coefficient of friction characteristics including, but not limited to, untreated and treated titanium dioxide, talc, calcium carbonate and clay, and primary, secondary and substituted fatty acid amides, release agents, silicone coating agents. 还可加入其它添加剂,如单一季铵化合物或它与乙烯-丙烯酸(EAA)共聚物或其它官能聚合物的掺混物以增强由本发明聚合物混合物形成的薄膜、涂料和模制品的抗静电特性,并使这些聚合物混合物可用于(例如)重载包装电学敏感物品。 Other additives may be added, such as a single compound or its ammonium season and ethylene - acrylic acid blend (EAA) copolymers or other functional polymers to enhance the antistatic characteristics of films, coatings and moldings formed from the polymer mixture of the invention , and mixtures of these polymers may be used (e.g.) electrical overload sensitive goods packaging.

本发明的薄膜、薄膜层或组合物可进一步包括回收和废弃材料以及稀释聚合物,加入量应保持平衡密封剂性能和模量性能。 Film of the invention, the thin film layer, or may further comprise recovering the composition and waste material and polymer is diluted, added in an amount should be balanced sealant properties and modulus properties. 稀释材料的例子包括(例如)弹性体、橡胶、和酸酐改性聚乙烯(例如聚丁烯和马来酸酐接枝LLDPE和HDPE),以及高压聚乙烯如低密度聚乙烯(LDPE)、乙烯/丙烯酸(EAA)共聚体、乙烯/乙酸乙烯酯(EVA)共聚体和乙烯/甲基丙烯酸酯(EMA)共聚体,及其混合物。 Examples of the diluent include (e.g.) an elastomer, rubber, and anhydride modified polyethylene (e.g., polybutylene and maleic anhydride grafted LLDPE and HDPE), low density polyethylene and a high pressure polyethylenes such as (LDPE), ethylene / acrylic acid (EAA) interpolymers, ethylene / vinyl acetate (EVA) interpolymers and ethylene / methacrylate (EMA) interpolymers, and mixtures thereof.

本发明的薄膜、薄膜层或组合物可发现在各种领域中的用途。 Film, film layer, or composition of the invention may find use in various fields. 据信合适的应用包括但不限于单层包装薄膜;由其它材料组成的多层包装结构,例如用于收缩薄膜和阻挡收缩中的双轴取向聚丙烯或双轴取向乙烯聚合物;通过形成/填充/密封机加工形成的包装物;可剥离密封包装结构;蒸煮食品包装结构;压缩填充包装物;可热密封的拉伸包装膜,如新鲜产品包装和新鲜瘦肉零售包装;衬里和袋子,如谷类食品衬里、杂物/购物袋、重载商品包装和垃圾罐衬里(袋子)、垫圈和包装容器盖。 It is believed Suitable applications include, but are not limited to a single layer packaging film; multilayer packaging structures consisting of other materials, for example, biaxially oriented polypropylene or biaxially shrink film and barrier shrink in the orientation of the ethylene polymer; forming a / package filling / sealing machined is formed; peelable seal packaging structures; retort food packaging structure; filling and packaging compressed material; heat sealable stretch wrap film, such as fresh produce packaging and fresh meat retail packaging; bags and liners, such as cereal liners, debris / shopping bags, heavy duty packaging and trash can liners (bags), gaskets, and packing the container lid.

单层和多层双轴取向薄膜结构的用途基于其增强的强度、透明、光泽、劲度、阻挡和/或收缩性能。 The use of single and multi-layer biaxially oriented film structure based on their increased strength, transparency, gloss, stiffness, barrier and / or shrinkage properties. 发现该双轴取向薄膜结构可用于非食品和食品如大块和分割肉、火腿、家禽、腊肉、奶酪等的包装和贮存。 Found that the biaxially oriented film structure may be used as food and non-food chunks and cut meat, ham, poultry, bacon, cheese and other packaging and storage. 使用本发明聚合物薄膜、薄膜层或组合物的典型多层双轴取向薄膜结构可为包括本发明密封薄膜层、外层(如非均相支化线性低密度或超低密度聚乙烯),和位于本发明密封薄膜层与外层之间的芯层(如双轴取向聚丙烯均聚物或氯乙烯聚合物)的两层至七层结构。 A polymer film, or a film layer composition of the present invention are typically multilayer biaxially oriented film structure of the present invention may comprise a sealing thin film layer, an outer layer (such as heterogeneously branched linear low density or very low density polyethylene), and a core layer positioned between the sealing layer and the outer layer film of the present invention (e.g., biaxially oriented polypropylene homopolymer or a vinyl chloride polymer) to seven two-layer structure.

包括本发明薄膜、薄膜层或组合物的多层结构还可包括增粘粘结层(例如购自The Dow Chemical Company的PRIMACORTM乙烯-丙烯酸(EAA)共聚物)。 Comprises a film, film layer, or a multilayer structure of the present invention compositions may also include a solubilizing junction sticky layer (e.g., available from The Dow Chemical Company of PRIMACORTM ethylene - acrylic acid (EAA) copolymer). 该多层结构还可包括另一些结构层,如购自The DowChemical Company的AFFINITYTM聚烯烃塑性体,购自Dupont DowElastomer的ENGAGETM聚烯烃弹性体,购自The Dow ChemicalCompany的DOWLEXTMLLDPE,购自The Dow Chemical Company的ATTANETMULDPE,或这些聚合物相互或与另一聚合物如EVA共聚物的任何共混物。 The multilayer structure may further comprise other layer structures, such as AFFINITYTM polyolefin plastomers available from The DowChemical Company, and available from the Dupont DowElastomer ENGAGETM polyolefin elastomers available from The Dow ChemicalCompany of DOWLEXTMLLDPE, available from The Dow Chemical Company the ATTANETMULDPE, or combinations of these polymers with each other or with any other polymers such as EVA copolymer blend.

包括本发明薄膜、薄膜层或组合物的多层结构(无论是否双轴取向)通常可包括但不限于阻挡层、粘结层和/或结构层。 The present invention comprises a thin membrane layer or multi-layer structure composition (whether or biaxially oriented) may generally include but are not limited to barrier layers, tie layers, and / or structural layers. 各种材料可用于这些层,其中某些材料可在相同的多层结构中用作一层以上。 Various materials can be used for these layers, in which certain materials may be used as the above in the same layer of the multilayer structure. 某些合适的材料包括:箔、尼龙、乙烯/乙烯醇(EVOH)共聚物、聚偏二氯乙烯(PVDC)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(特别是取向聚丙烯(0PP),尤其是双轴取向聚丙烯)、乙烯/乙酸乙烯酯(EVA)共聚物、乙烯/丙烯酸(EAA)共聚物、乙烯/甲基丙烯酸(EMAA)共聚物、ULDPE、LLDPE、HDPE、MDPE、LMDPE、LDPE、离聚物、接枝改性的聚合物(例如马来酸酐接枝的聚乙烯)、和纸。 Some suitable materials include: foil, nylon, ethylene / vinyl alcohol (EVOH) copolymers, polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), polypropylene (especially oriented polyethylene propylene (0PP), in particular biaxially oriented polypropylene), an ethylene / vinyl acetate (EVA) copolymers, ethylene / acrylic acid (EAA) copolymers, ethylene / methacrylic acid (the EMAA) copolymers, ULDPE, LLDPE, HDPE , MDPE, LMDPE, LDPE, ionomers, graft-modified polymers (e.g., maleic anhydride grafted polyethylene), and paper. 通常本发明的多层结构可包括2至约7层,或预定用途所需的任何层数或材料或聚合物。 The multilayer structure of the present invention generally may comprise about 2 to 7 layers, or any predetermined number of layers, or a polymer material or intended use.

如上所述,认为本发明薄膜或组合物特别适合压缩填充、蒸煮食品包装和垂直形成/填充/密封应用。 As described above, the present invention is that the film or composition is particularly suitable compression of the packed, retort food packaging and vertical form / fill / seal applications. 压缩填充包装通常涉及首先通过吹膜技术加工塑料管。 Compression generally involves first filling and packaging blowing plastic pipe processing technology. 然后将该平折薄膜形式的管输送至填充机器中,在该填充机器中(连续操作),进行底部密封,将可压缩的物品装入管中并压缩以降低体积。 The flat film is then conveyed in the form of a tube to a filling machine, the filling machine (continuous operation), a bottom seal, compressible articles loaded tube and compressed to reduce the volume. 在物品装入管中之后,进行顶部密封由此密封包装物品。 After the items into the tube, thereby sealing the top-sealed packaging articles. 可通过压缩方式填充方式包装的物品为纺织品,例如但不限于手巾和运动护套。 Compression filled article by way of a textile package, for example but not limited to diapers and sports jacket.

蒸煮包装食品为预包装,接着蒸煮的食物。 Cooking and packaging food is pre-packaged, followed by cooking food. 这些包装和蒸煮的食品直接面向消费者、机构、或消费品零售商。 The packaging and cooking food directly to consumers, agencies, or consumer goods retailers. 用于蒸煮的包装必须在结构上能够承受暴露于蒸煮时间和温度条件下,同时包着食品。 A package for cooking must be able to withstand exposure to the cooking time and temperature conditions while the food in the package structure. 蒸煮包装食品通常用于包装火腿、火鸡、蔬菜、加工过的肉等。 Cooking food packaging commonly used for packaging ham, turkey, vegetables, processed meat. 由于本发明密封层相对高的软化点和热粘着起始温度特性,因此包括本发明密封层的多层薄膜结构特别适合蒸煮以及热填充应用。 Since the sealing layer of the present invention is relatively high softening point and the hot tack initiation temperature characteristic, the sealing layer comprising a multilayer film structure of the present invention is particularly suitable for hot fill and retort applications.

形成/填充/密封包装特别所用包装可流动的物质,如牛奶、酒、粉末等。 Form / fill / seal packaging material in particular, the packaging of flowable products such as milk, wine, powders and the like. 在形成/填充/密封包装方法中,将塑料薄膜结构片材加入形成/填充/密封机中,其中将片材通过搭接塑料薄膜并用内/外密封剂使薄膜纵向边密封在一起的方式,或通过用内/内密封剂飞边密封塑料膜的方式形成连续管。 Formed / fill / seal packaging process, the addition of plastic film sheets forming the structure / fill / seal machine, wherein the sheet by way of the plastic film and overlapped with the inner / outer sides of the longitudinal sealant films sealed together, or a continuous tube formed by fin sealing the plastic film agent sealed inner / inner manner. 接着用密封棒在一端将管横向密封形成袋子底。 The tube is then sealed transversely at the bottom end of the bag is formed by sealing bars. 然后用密封棒密封盒的顶端,并经塑料膜灼烧或用切割装置切割薄膜,由此从管中分离形成的完整盒子。 Sealing bar then seals the top of the cartridge, and the film was cut by a cutting device or burning plastic film, whereby the complete cartridge from the tube formed is separated. 用形成/填充/密封机制备盒的方法通常描述于US4,503,102和5,521,437中,因本发明密封层的低热密封和高粘着起始温度、和高热粘着强度和宽热粘着密封温度范围,因此包括本发明密封层的多层薄膜结构特别适合形成/填充/密封包装应用。 By forming / filling method / apparatus the sealing mechanism is generally described in US4,503,102 cartridge and 5,521,437, due to the low heat sealing the sealing layer of the present invention and high tack initiation temperature, heat adhesion strength and hot tack sealing temperature and a broad range, including the multilayer film structure of the present invention is particularly suitable for forming the sealing layer / fill / seal packaging applications.

热密封起始温度按照ASTMF88-85测定。 Heat sealing initiation temperature was measured in accordance ASTMF88-85. 2%正割模量按照ASTMD-882测量。 2 percent secant modulus measured according to ASTMD-882. 密度按照ASTM D-792测量并以g/cm3(g/cc)给出。 Density and given in g / cm3 (g / cc) measured according to ASTM D-792. 下面实施例中给出的测量值以及所有密度按照ASTM D-792在样品于室温下退火24小时后测量。 Measurements given in the examples, and all densities in accordance with ASTM D-792 sample was measured after annealing at room temperature for 24 hours following embodiments.

聚合物组分的密度和重量百分比可通过分析温升洗脱分级(ATREF)技术测定。 Density and weight percentage of the polymer component temperature rise elution fractionation analysis (an ATREF) technique can be determined by. 早已公开了用于ATREF技术的硬件和程序,例如Wild等人聚合物科学期刊,聚合物物理分册,20,41(1982),Hazlitt等人US4,798,081和Chum等人US5,089,321。 Already disclosed hardware and procedures for ATREF techniques, such as Wild et al., Journal of Polymer Science, Polymer Physics volumes, 20,41 (1982), Hazlitt et al US4,798,081 and Chum et al US5,089,321.

在ATREF分析中,将要分析的薄膜或组合物溶于合适的热溶剂(例如三氯苯中),并使其在含惰性载体的柱子中通过慢慢降低温度结晶。 In ATREF analysis, the film or composition to be analyzed is dissolved in a suitable hot solvent (e.g., trichlorobenzene), and allowed in a column containing an inert support by slowly reducing the temperature of crystallization. 然后通过慢慢升高洗脱溶剂(三氯苯)温度从柱子中洗脱结晶性聚合物样品的方式获得ATREF色谱曲线。 Then the solvent (trichlorobenzene) elution temperature the crystalline polymer sample from the column by way obtain ATREF chromatogram curve is raised slowly eluted. ATREF曲线通常称为短链支化分布(SCBD),原因在于它显示共聚单体(例如辛烯)如何在整个样品中均匀分布,即随着洗脱温度降低,共聚单体含量增加。 ATREF curve is usually referred to as the short chain branching distribution (SCBD), because it shows a comonomer (e.g., octene) how uniformly distributed throughout the sample in that as elution temperature decreases, comonomer content increases copolymerization.

ATREF曲线可方便地说明薄膜或组合物的几种关键结构特性,例如已知均相支化乙烯聚合物如购自The Dow Chemical Company的AFFINITYTM树脂、购自Dupont Dow Elastomer的ENGAGETM树脂、购自Mitsui Chemicali Corporation的TAFMERTM树脂和购自ExxonChemical Company的EXACTTM树脂呈现独特的对称单洗脱峰(或均相SCBD)。 ATREF curve may be conveniently described several key structural features of a film or composition, for example, known as homogeneously branched ethylene polymers available from The Dow Chemical Company's AFFINITYTM resins, available from Dupont Dow Elastomer of ENGAGETM resins, available from Mitsui TAFMERTM resin Chemicali Corporation and is available from ExxonChemical Company EXACTTM resins exhibit a unique symmetrical single elution peak (or homogeneous SCBD). 相反,已知通过常规Ziegler-Natta催化剂体系生产的乙烯聚合物(如The Dow Chemical Company出售的的DOWLEXTMLLDPE树脂)在明显不同的温度下显示具有宽和窄洗脱峰的双或非均相SCBD。 In contrast, it is known by a conventional Ziegler-Natta catalyst system produced ethylene polymers (such as sold by The Dow Chemical Company of DOWLEXTMLLDPE resin) exhibit wide and narrow elution peak dual or heterogeneous SCBD at significantly different temperatures.

由于洗脱温度和ATREF曲线形状的独特性对应于聚合物密度,ATREF分析可用于指纹识别特定的聚合物。 Since the ATREF elution temperature and a curved shape corresponding to the unique polymer density, ATREF analysis can be used to fingerprint particular polymers. 特别是对于由多组分聚合物组成的组合物,通过积分ATREF曲线,可方便地测定各组分的重量分数。 Particularly for multicomponent polymer composition consisting of, by integrating the ATREF curve, the weight may be conveniently determined fraction of each component. 此外,组分聚合物的密度可由ATREF分析测定,其中组成由按照ASTM D-792的测量已知。 In addition, the density of component polymers can be measured ATREF analysis where the composition according to the measurement of ASTM D-792 are known. 例如,对于基本上线性乙烯聚合物,ATREF洗脱温度与聚合物密度的校准曲线提供通过如下等式定义的聚合物密度:ρ=0.83494+9.6133×10-4(Te)其中Te为聚合物的ATREF洗脱温度。 For example, for substantially linear ethylene polymers, calibration curves an ATREF elution temperature and polymer density provide polymer density is defined by the following equation: ρ = 0.83494 + 9.6133 × 10-4 (Te) where Te is a polymer of ATREF elution temperature. 在给定组合物的总体组成密度下,通过积分ATREF曲线的组分聚合物的重量分数和基本上线性乙烯聚合物组分的密度,可方便地计算剩余组分聚合物的密度。 In a given overall composition density of the composition, the weight fraction of the polymer component and the density of the substantially linear ethylene polymer component integral ATREF curve, can easily calculate the density of the remaining components of the polymer.

为进一步表征聚合物组合物,可使用差式粘度计。 To further characterize the polymer compositions, using a differential viscometer. 差式粘度计的输出值为粘均分子量Mv,它表示相对于洗脱体积变化的分子量变化。 Differential viscometer is the viscosity average molecular weight output Mv, which indicates a change with respect to the molecular weight of the elution volume change. Mv响应可显示哪一种组分聚合物具有较高分子量的特征,或是否聚合物组分具有基本上相等的分子量特征。 Mv response can indicate which one component is a polymer having a higher molecular weight characteristics, or whether the polymer component having a molecular weight substantially equal characteristics.

概而言之,在给定薄膜或组合物的ATREF曲线和组成密度下,可计算组分聚合物的重量分数和聚合物密度。 To sum up, in a given film or ATREF curve and composition density of the composition, the weight fraction and polymer densities of the component polymers can be calculated. 将ATREF分析与差式粘度计(ATREF/DV)结合,给出显示组分聚合物的相对分子量的信息。 The ATREF analysis with a differential viscometer (ATREF / DV) combined, is given a display of information relative molecular weight component polymers. ATREF/DV可用于指纹辨认本发明的薄膜或组合物。 ATREF / DV may be used to identify a fingerprint the film or composition of the present invention. ATREF曲线还显示给出本发明第一和第二种乙烯聚合物之间的密度差的两个区别洗脱峰,优选的实施方案将显示涉及第一种乙烯聚合物组分和分子量比第一种乙烯聚合物组分高的第二种乙烯聚合物组分的单一洗脱峰。 ATREF curve analysis also shows the difference in density between the two differences of the present invention, a first ethylene polymer and the second eluting peak, a preferred embodiment relates to the display a first ethylene polymer component and a higher molecular weight than the first single peak species high ethylene polymer component of a second ethylene polymer component.

GPC拟合技术可用于测定各乙烯聚合物组分的熔体指数。 GPC fitting techniques useful for determining the melt index for each ethylene polymer component. 在该技术中,GPC数据用上述Waters 150C高温GPC色谱获得。 In this technique, the data obtained by the above GPC Waters 150C high temperature GPC chromatogram. 在给定实验洗脱体积下,可方便地用由一系列窄分子量分布聚苯乙烯标准物获得的校准曲线计算分子量。 In a given experiment elution volume, conveniently using a calibration curve obtained by standard polystyrene molecular weight is calculated by a series of narrow molecular weight distribution. 在运行拟合程序之前,应对GPC数据归一化以确保在重量分数与log(MW)GPC曲线下的单位面积。 Before running the fitting procedure, to deal with GPC data were normalized to ensure that the basis weight fraction in the log (MW) GPC curve.

对于拟合技术,假定均相支化乙烯聚合物遵守Bamford-Tompa分子量分布,即等式[1]wi(Mi)=ln(10)MiMnexp((-Mi(1+ζ)Mn))×(2+ζζ)1/2×I1(Miζ1/2(2+ζ)1/2Mn)---[1]]]>其中wi为具有分子量Mi的聚合物重量分数,Mn为数均分子量,I1(x)为由如下等式[2]定义的第一类一阶改性Bessel函数,I1(x)=Σbx2b+122b+1b!(b+1)!---[2]]]>ζ为如下等式[3]所示的使分子量分布变宽的可调节参数MwMn=2+ζ---[3]]]>对于拟合技术,假定非均相支化乙烯聚合物(即用Ziegler-Natta催化剂体系制造的聚合物)遵守对数分布等式[4]wi(Mi)=1β(2π)0.5exp(-12(log(Mi)-log(M0)β)2)----[4]]]>其中wi为具有分子量Mi的聚合物重量分数,M0为峰分子量,β为表征分布宽度的参数,β假定为如下等式[5]所示M0的函数:β=5.70506-252383Log(M0)+0.30024(Log(M0))2[5]GPC拟合技术涉及四个拟合参数,Mn和ζ针对均相支化乙烯聚合物(通常为本 For fitting technique, homogeneously branched ethylene polymer is assumed to comply Bamford-Tompa molecular weight distribution, i.e., Equation [1] wi (Mi) = ln (10) MiMnexp ((- Mi (1 + & zeta;) Mn)) & times ; (2 + & zeta; zeta &;) 1/2 & times; I1 (Mi & zeta; 1/2 (2 + & zeta;) 1 / 2Mn) --- [1]]]> where wi is the polymer weight fraction having a molecular weight Mi, , Mn number average molecular weight, I1 (x) by the following equation [2] a first-order modified Bessel function type definition, I1 (x) = & Sigma;!! bx2b + 122b + 1b (b + 1) - - [2]]]> ζ is shown in the following equation [3] the molecular weight distribution broadening adjustable parameter MwMn = 2 + & zeta; --- [3]]]> for fitting technique, assuming a non- homogeneously branched ethylene polymers (i.e., with a Ziegler-Natta catalyst system for producing polymer) distribution compliance equation [4] wi (Mi) = 1 & beta; (2 & pi;) 0.5exp (-12 (log (Mi) -log (M0) & beta;) 2) ---- [4]]]> where wi is the weight fraction of the polymer having a molecular weight Mi, M0 is the peak molecular weight, β is a parameter characterizing the distribution width, β is assumed to be as follows, etc. formula [5] as shown in function M0: β = 5.70506-252383Log (M0) +0.30024 (Log (M0)) 2 [5] GPC fitting technique involves four parameter fit, Mn and ζ for a homogeneously branched ethylene polymers (generally known 明的第一种乙烯聚合物组分),M0针对非均相支化乙烯聚合物(优选本发明的第二种乙烯聚合物组分)和均相支化乙烯聚合物的重量分数。 Out of a first ethylene polymer component), M0 for heterogeneously branched ethylene polymer (preferably the second ethylene polymer component of the present invention) and homogeneously branched ethylene polymer weight fraction. 在Jandel Scientific提供的SigmaPlotTM内非线性曲线拟合子程序(v3.03)用于估算这些参数。 In the SigmaPlotTM Jandel Scientific Nonlinear curve fitting routines provided (v3.03) is used to estimate these parameters. 在给定的均相支化乙烯聚合物或第一种乙烯聚合物组分的数均分子量(Mn),等式[3],其I10/I2熔体流动比和其密度下,其I2熔体指数可方便地用等式[6]计算。 Given homogeneously branched ethylene polymer or the first ethylene polymer component number average molecular weight (Mn), equation [3], its I10 / I2 melt flow ratio and its density, its I2 melt index member can be easily [6] is calculated by the equation. I2FCPA=exp(62.782-3.8620Ln(Mw)-1.7095Ln((I10I2)FCPA)-16.310×ρFCPA)---[6]]]>其中FCPA表示乙烯聚合物组分。 I2FCPA = exp (62.782-3.8620Ln (Mw) -1.7095Ln ((I10I2) FCPA) -16.310 & times; & rho; FCPA) --- [6]]]> where FCPA denotes the ethylene polymer component.

实施例提供如下实施例用于说明本发明,而不用于限定本发明。 Example The following examples serve to illustrate the invention and are not intended to limit the present invention.

为评估研究各种密封材料,在Bruckner流延拉幅架BOPP薄膜生产线上制造三层(ABC)共挤出薄膜。 Evaluation of a variety of sealing materials, a three-layer (ABC) in Bruckner cast film line tenter frame BOPP coextruded film. (B)层为结构的芯或基层并保持为具有滑爽和抗静电混合添加剂的Shell KF 6100均聚物聚丙烯。 (B) a core layer or the substrate structure and remains mixed with antistatic and slip additives Shell KF 6100 homopolymer polypropylene. 该添加剂混合料通过在30MFI(在230℃用2.16kg重物测量)聚丙烯均聚物载体树脂中使用2.5wt%含15wt%抗静电和滑爽剂共混物的Ampacet 400577母料提供。 The additive mixture by 30 MFI (230 deg.] C with a 2.16kg weight at measurement) polypropylene homopolymer carrier resin using 2.5wt% Ampacet 400577 masterbatch containing 15wt% of antistatic and slip agent blend provided. Shell KF 6100均聚物聚丙烯树脂具有MFI约3(在230℃用2.16kg重物测量)。 Shell KF 6100 homopolymer polypropylene resin having a MFI of about 3 (2.16kg with a weight measured at 230 ℃).

在整个评估中用对于两层相同的密封材料生产(A)和(C)层作为可变密封表层。 In the same for the entire evaluation by two sealing materials production (A) and (C) layer as a variable sealing surface. 将含滑爽和抗结块添加剂的添加剂母料加入密封层中,提供约1250ppm芥酸酰胺和约1500ppm的SiO2。 The masterbatch containing a slip additive and an anti-caking additive is added to the sealing material layer, to provide about 1250ppm and about 1500ppm of erucamide SiO2. 实施例1和比较例2-8为该评估中研究的各种密封材料。 Example 1 and Comparative Examples 2-8 for various sealing materials evaluation studies.

在该评估中,用例如PCT专利申请94/01052中公开的现场聚合和混合方法,制备实施例1和比较例6。 In this evaluation, for example PCT Patent Application 94/01052 in the field of polymerization and mixing methods disclosed in Preparation Example 1 and Comparative Example 6. 生产的具体细节在下面给出。 Production details are given below.

通过将已知的束缚几何有机金属配合物[((CH3)4C5))-(CH3)2Si-N-(t-C4H9)]Ti(CH3)2溶于IsoparTME烃(购自Exxon ChemicalCompany)中,得到钛(Ti)浓度9.6×10-4M的透明溶液。 Bound by a known geometry organometallic complex [((CH3) 4C5)) - (CH3) 2Si-N- (t-C4H9)] Ti (CH3) 2 were dissolved in IsoparTME hydrocarbon (available from Exxon ChemicalCompany) in a clear solution 9.6 × 10-4M of titanium (Ti) concentration. 也制备活化剂配合物三(全氟苯基)硼烷的类似溶液(3×10-3M)。 Also be prepared activator complex tris (perfluorophenyl) borane similar solution (3 × 10-3M). 将已知重量甲基铝氧烷(购自Taxas Alkyls,称为MMAO)溶于正庚烷得到具有MMAO浓度1.06×10-2M的溶液。 A known weight of methylalumoxane (available from Taxas Alkyls, referred to as MMAO) was dissolved in n-heptane to obtain a solution having a concentration of 1.06 × 10-2M of MMAO. 将这些溶液独立地泵入,使刚好在加入第一个聚合反应器之前将这些溶液混合,并使束缚几何催化剂、活化剂配合物和MMAO摩尔比为1∶3.5∶7。 These solutions were separately pumped into the mixing was added just before the first of these solutions the polymerization reactor, and bound geometry catalysts, complexes and MMAO activator molar ratio 1:3.5:7.

非均相Ziegler型催化剂基本上按照US4,612,300(实施例P),通过顺序加入IsoparTME烃、无水氯化镁在IsoparTME烃中的淤浆、EtAlCl2在正己烷中的溶液和Ti(O-iPr)4在IsoparTME烃中的溶液,得到含镁浓度0.166 M和Mg/Al/Ti比例40.0∶12.5∶3.0的浆料的方式制备。 Heterogeneous Ziegler-type catalyst substantially according to US4,612,300 (Example P), by the sequential addition IsoparTME hydrocarbon IsoparTME anhydrous magnesium chloride in a hydrocarbon slurry, a solution of EtAlCl2 in n-hexane and Ti (O-iPr) 4 IsoparTME hydrocarbon solution, to give a magnesium concentration of 0.166 M was prepared and the slurry Mg / Al / Ti ratio 40.0:12.5:3.0 manner. 将一等分此浆料和Et3Al(TEA)的稀溶液独立地泵入,其中将这两种物流在刚好加入第二个聚合反应器之前混合,得到最终TEA∶Ti摩尔比6.2∶1的活性催化剂。 An aliquot of this slurry and Et3Al (TEA) are independently a dilute solution pumped, wherein these two streams mixed immediately prior to addition of the second polymerization reactor to give a final molar ratio of 6.2:1 active TEA:Ti catalyst.

在两个反应器的聚合体系中,将乙烯按照刻度速率40lb/hr(18.2kg/hr)加入第一个反应器中。 In the polymerization system of two reactors, according to the scale rate of the ethylene 40lb / hr (18.2kg / hr) added to the first reactor. 在加入第一个反应器中之前,将乙烯与包括IsoparTME烃(购自Exxon Chemical Company)和1-辛烯的稀释剂混合物合并。 Prior to joining the first reactor, the ethylene and comprises IsoparTME hydrocarbon (available from Exxon Chemical Company) and 1-octene alkylene diluent mixture combined. 对于第一个聚合反应器,1-辛烯∶乙烯比例(构成新鲜和再循环单体)为0.28∶1(摩尔百分比),稀释剂∶乙烯进料比例为8.23∶1(重量百分比)。 For the first polymerization reactor, 1-octene: ethylene ratio (constituting fresh and recycled monomer) was 0.28:1 (mole percent), the diluent: ethylene feed ratio 8.23:1 (percentage by weight). 将上面制备的均相束缚几何催化剂和助催化剂加入第一个聚合反应器中。 The homogeneous bound geometry catalysts prepared above and a cocatalyst added to the first polymerization reactor. 加入第一个聚合反应器中的催化剂、活化剂和MMAO刻度流动速率分别为1.64×10-5lb Ti/hr(7.4×10-6kg Ti/hr)、6.21×10-4lb活化剂/hr(2.82×10-4kg活化剂/hr)和6.57×10-5lb MMAO/hr(3.0×10-5kg MMAO/hr)。 Added to the first reactor a polymerization catalyst, activator, and MMAO flow rates scale were 1.64 × 10-5lb Ti / hr (7.4 × 10-6kg Ti / hr), 6.21 × 10-4lb activator /hr(2.82 × 10-4 kg activator / hr) and 6.57 × 10-5lb MMAO / hr (3.0 × 10-5kg MMAO / hr). 聚合在反应器温度70-160℃下进行。 Polymerization was carried out in a reactor at a temperature of 70-160 ℃.

将第一个聚合反应器的反应产品转移入第二个反应器中。 A reaction product of the first polymerization reactor is transferred into the second reactor. 在自第一个聚合反应器流出的物流中的乙烯浓度低于4%,如US5,272,236中所述显示存在长链支化。 Ethylene concentration in the stream from the first polymerization reactor effluent in less than 4%, as described in US5,272,236 shows the presence of long chain branching.

将乙烯按刻度速率120lb/hr(54.5kg/hr)加入第二个聚合反应器中。 The rate of ethylene calibrated to 120lb / hr (54.5kg / hr) into the second polymerization reactor. 在加入第二个聚合反应器中之前,将乙烯和氢气流与包括IsoparTME烃和1-辛烯的混合物合并。 Before the second polymerization reactor was added, ethylene and hydrogen mixture combined with the stream comprising hydrocarbons IsoparTME and 1-octene. 对于第二个聚合反应器,1-辛烯∶乙烯原料比(构成新鲜和再循环单体)为0.196∶1(摩尔百分比),稀释剂∶乙烯进料比例为5.91∶1(重量百分比),氢气∶乙烯进料比为0.24∶1(摩尔比)。 For the second polymerization reactor, 1-octene: ethylene feed ratio (constituting fresh and recycled monomer) was 0.196:1 (mole percent), the diluent: ethylene feed ratio 5.91:1 (percent by weight), hydrogen: ethylene feed ratio was 0.24:1 (molar ratio).

将上面制备的非均相Ziegler-Natta催化剂和助催化剂加入第二个聚合反应器中。 The heterogenous Ziegler-Natta catalyst and co-catalyst prepared above was added to a second polymerization reactor. 催化剂(Ti)和助催化剂(TEA)在第二个聚合反应器中的浓度分别为2.65×10-3和1.65×10-3摩尔。 The catalyst (Ti) and cocatalyst (TEA) concentrations in the second polymerization reactor were 2.65 × 10-3 mol and 1.65 × 10-3. 加入第二个聚合反应器中的催化剂和助催化剂刻度流动速率分别为4.49×10-4lb Ti/hr(2.04×10-4kg Ti/hr)和9.14×10-3lb TEA/hr(4.15×10-3kgTEA/hr)。 Into the second polymerization reactor scale catalyst and cocatalyst flow rates were 4.49 × 10-4lb Ti / hr (2.04 × 10-4kg Ti / hr) and 9.14 × 10-3lb TEA / hr (4.15 × 10- 3kgTEA / hr). 在第二个反应器中的聚合在反应温度150-220℃下进行。 In the second polymerization reactor at a reaction temperature of 150-220 ℃. 第一与第二个反应器之间的转化率和生产量的划分应得到表1给出的实施例1和比较例6中的“第一种乙烯聚合物组分(A)的重量百分比”。 The first division and production of conversion between the second reactor should be "the first ethylene polymer component (A) in weight percent" Example 6 and Comparative Example 1 given in Table 1 . 换言之,第一种乙烯聚合物组分(A)的重量百分比表示第一与第二个聚合反应器的生产量的划分。 In other words, a first ethylene polymer component (A) is expressed as a percentage by weight of the first and second polymerization reactors production division.

向得到的聚合物中,加入常规催化剂灭活剂(1250ppm硬脂酸钙)和抗氧剂(200ppm IRGANOXTM1010,即四(亚甲基3-(3,5-二叔丁基-4-羟苯基丙酸酯)甲烷,购自Ciba-Geigy和800ppm SANDOSTABTMPEPQ,即4,4′-联苯基亚膦酸四(2,4-二叔丁基-苯基)酯,购自SandozChemical)以稳定聚合物。 The polymer obtained, the conventional catalyst inactivating agent is added (1250 ppm Calcium Stearate) and antioxidants (200ppm IRGANOXTM1010, i.e. tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl propionate) methane, available from Ciba-Geigy and 800ppm SANDOSTABTMPEPQ, i.e. 4,4'-biphenyl phosphite tetrakis (2,4-di-tert - butylphenyl) phosphite, commercially available from SandozChemical) to stabilize the polymer.

比较例2为具有5MFI(在230℃下用2.16kg重物测量)的聚丙烯共聚物,由Solvay按牌号KS4005出售)。 Comparative Example 2 is a polypropylene copolymer having a 5 MFI (measured with a 2.16kg weight at 230 deg.] C), the grade sold by Solvay by KS4005). 比较例3为具有5MFI(在230℃下用2.16kg重物测量)的聚丙烯三元聚合物,由Solvay按牌号KS300出售。 Comparative Example 3 A polypropylene terpolymer having 5 MFI (measured with a 2.16kg weight at 230 deg.] C), and according to grades sold by Solvay KS300. 比较例4为The Dow Chemical Comapny按牌号AFFINITYTMPL 1845出售的基本上线性乙烯聚合物。 Comparative Example 4 The Dow Chemical Comapny according to grades AFFINITYTMPL 1845 substantially linear ethylene polymers sold. 比较例5为The Dow Chemical Comapny按牌号AFFINITYTMPL 1850出售的基本上线性乙烯聚合物。 Comparative Example 5 is a substantially linear ethylene polymers by The Dow Chemical Comapny designation AFFINITYTMPL 1850 sold. 比较例7为The Dow Chemical Comapny按牌号DOWLEXTM2035E出售的非均相支化线性低密度聚乙烯。 Comparative Example 7 The Dow Chemical Comapny DOWLEXTM2035E grades sold by heterogeneously branched linear low density polyethylene. 比较例8为The Dow Chemical Comapny按牌号ATTANETMSC4103出售的非均相支化超低密度聚乙烯。 Comparative Example 8 The Dow Chemical Comapny grades ATTANETMSC4103 sold by non-homogeneously branched ultra low density polyethylene.

各种密封层的热密封起始温度用常规热密封测试仪和张力计在使密封口老化24小时后测定,将达到密封强度1.8N/15mm时的温度作为密封起始温度。 Various heat sealing initiation temperature measured with a conventional sealing layer is a heat seal tester and a tension measured after the sealing port 24 hours, the temperature at which the seal strength of 1.8N / 15mm as the seal initiation temperature. 将热粘着力超过46g/cm(使用Dupont弹簧方法)的温度范围作为热粘着强度温度范围。 The thermal adhesion than 46g / cm (spring method of Dupont) temperature range as the temperature range of hot tack strength.

“足够的层间粘结”这里定义为在共挤出加工步骤期间或密封和密封试验期间观察不到分层现象。 "Sufficient interlayer adhesion" is defined herein as the observed or delamination during sealing and sealing test during coextrusion processing steps. 反之,“不良层间粘结”定义为密封期间开始分层。 Conversely, "inter-layer adhesive failure" is defined to begin delamination during sealing.

在此评估中,层厚度为(A)=1微米(μm),(B)=18μm和(C)=1μm。 In this evaluation, a layer thickness (A) = 1 micrometer (μm), (B) = 18μm and 1μm (C) =. 将相应于层(C)一面进行电晕处理至约44达因的量。 Corresponding to the layer (C) side was corona treated to about 44 dynes amount. 将这些物质在熔体温度245至275℃和骤冷辊温度25-30℃下挤出。 These materials are extruded at a melt temperature of 245 to 275 deg.] C and chill roll temperature 25-30 ℃. 纵向取向(MDO)加热辊的温度为90至125℃。 Vertical orientation (MDO) of the heating roller temperature of 90 to 125 ℃. 纵向拉伸比为5∶1,横向为8∶1。 Longitudinal stretching ratio 5:1 transverse 8:1. 拉幅架烘箱温度为180至160℃。 Tenter oven temperature of 180 to 160 ℃.

第一种乙烯聚合物组分(A)的密度和重量百分比、所得聚合物组合物的总体熔体指数、组成密度和Vicat软化点、用于制备各实施例的催化剂体系类型,以及实施例的热密封、热粘着和层间粘结性能在表1中给出。 A first ethylene polymer component (A) and the weight percent of the density of the overall melt index of the resultant polymer composition, the density and Vicat softening point of the composition, type of catalyst systems for preparing each of the embodiments, and embodiments of the heat sealing, adhesion between layers and hot tack properties are shown in table 1. 表1 Table 1

CGC表示束缚几何催化剂Z/N表示Ziegler-Natta催化剂*不是本发明的实施例,仅用于比较目的。 Bound geometry catalysts CGC represents Z / N represents a Ziegler-Natta catalyst Example * not according to the present invention, for comparison purposes only.

在另一评估中,将各种密封层物质与PP均聚物Shell KF 6100在常规流延薄膜装置上共挤出并评估其热密封和热粘着性能。 In another evaluation, the sealing layer material and the various PP homopolymer Shell KF 6100 coextrusion and evaluate the heat seal and hot tack performance over conventional cast film apparatus.

流延共挤出生产线装有76cm Johnson活模唇流延薄膜模头。 Cast coextrusion line equipped with a die lip 76cm Johnson live cast film die. 各共挤出薄膜样品的总薄膜厚度为3.0密耳(76.2μm)。 Total film thickness of each sample was coextruded film 3.0 mils (76.2μm). 两层共挤出薄膜结构由10%密封剂和90%PP均聚物Shell KF 6100组成。 Two-layer coextruded film structure from 10% sealant and 90% PP homopolymer Shell KF 6100 composition. 这些薄膜用目标生产线速度55m/min、目标聚丙烯均聚物熔融温度约277℃、目标密封剂熔融温度265℃和空气缝隙12.7cm加工。 These films with the target line speed of 55m / min, the target polypropylene homopolymer melt temperature of about 277 ℃, certain sealants deg.] C melt temperature and air gap 265 12.7cm processing.

比较例9的聚合物组合物为AFFINITYTMPL1845(The DowChemical Company提供,与上面的比较例4相同)。 Comparative Example 9 The polymer composition of AFFINITYTMPL1845 (The DowChemical Company provided, the same as in Comparative Example 4 above). AFFINITYTMPL1845为单一聚合物组分基本上线性乙烯聚合物。 AFFINITYTMPL1845 a single polymer component substantially linear ethylene polymers. 实施例11和12的聚合物组合物以及对比例10和13的聚合物组合物用两个反应器按照实施例1所述的现场聚合方法制备。 Examples 11 and 12 of the embodiment of the polymer composition and the polymer composition of Comparative Example 10 and 13 are prepared by two polymerization reactors according to the site described in Example 1. 第一种乙烯聚合物组分(A)的熔体指数通过上述GPC拟合方法测定,第一种乙烯聚合物组分(A)的密度和重量百分含量也通过上面实施例1描述的ATREF技术测定。 Determination of a first ethylene polymer component (A) has a melt index of fitting by the above GPC method described in Example 1 a first ethylene polymer component (A) and the weight percentage of the density by the above embodiment also ATREF measurement techniques.

在该评估中,无一样品在共挤出或热密封操作和密封试验期间表现出密封层与聚丙烯层分层的迹象。 In this evaluation, a sample exhibited no signs of delamination sealing layer and the polypropylene layer during co-extrusion or heat sealing operation and sealing test.

在该评估中热密封起始温度定义为获得1lb/in(2N/15mm)密封强度时的最低温度。 In this evaluation, the heat seal initiation temperature is defined as obtaining 1lb / in (2N / 15mm) the lowest temperature at which the seal strength. 热密封试验在Topwave热粘着测试仪上使用0.5秒停留时间和40psi(0.275Mpa)密封棒压力进行。 Heat sealing test using a residence time of 0.5 seconds and 40psi (0.275Mpa) sealing bar pressure on Topwave hot tack tester. 密封口按5℃递增通过将密封薄膜向上折叠并使其本身密封的方式形成。 5 ℃ ascending sealing ports by the sealing film folded upwardly and sealed to itself in a manner that it is formed. 将如此形成的密封口在制成至少24小时后用Instron张力仪在10in/min十字头速率下拉动。 The sealing ports thus formed is pulled at least 24 hours after preparation using an Instron tensile tester at 10in / min crosshead speed.

同样在此评估中,极限热粘着定义为在通常试验范围即60-120℃内获得的最大热粘着强度。 Also in this evaluation, the ultimate hot tack is defined as the maximum heat i.e. typically 60-120 deg.] C obtained in the adhesion strength test range. 热粘着试验同样用Topwave热粘着测试仪在0.5秒停留时间、0.2秒延迟时间和40psi(0.275Mpa)密封棒压力下进行。 Hot tack tester with the adhesive tested in the same heat Topwave 0.2 second delay time and 40psi (0.275Mpa) sealing bar under pressure at a residence time of 0.5 seconds. 热粘着密封口按5℃递增通过将密封层向上折叠并使其本身热粘着密封的方式形成。 Ascending hot tack sealing ports 5 ℃ folded upwardly by the sealing layer and hot tack sealing it to itself, is formed. 施于如此形成的热粘着密封口上的剥离速率为150mm/sec。 The hot tack peel rate applied to the sealing port thus formed is 150mm / sec. 设定测试仪程序以在0.2秒延迟后立即拉动密封口。 Tester program set at 0.2 seconds after a delay immediately pull the sealing ports.

表2概列出用3.0密耳(0.08mm)流延薄膜共挤出获得的热密封和热粘着数据。 Table 2 lists the approximate heat seal and hot tack data obtained using 3.0 mil (0.08mm) co-extrusion cast film. 表2 Table 2

表2中的数据(和如图3所示)说明,在恒定总体熔体指数下为达到最高热粘着强度存在第一种乙烯聚合物组分(A)最佳分子量或熔体指数。 The data in Table 2 (and shown in FIG. 3) described in order to achieve a constant melt index of the overall presence of a first ethylene polymer component (A) the optimum molecular weight or melt index maximum hot tack strength. 从这些数据可以看出,具有I2熔体指数大于0.14g/10min至低于0.68g/10min的第一种乙烯聚合物组分(A)提供最佳热粘着强度。 From these data, having a first ethylene polymer component (A) I2 melt index of greater than 0.14g / 10min to less than 0.68g / 10min to provide optimum hot tack strength. 比较例10和13显示,对于用作流延BOPP薄膜以及垂直形式填充和密封(VFFS)领域,如快餐食品包装和谷物制食品包装领域的密封层,比较例10和13的热粘着强度不足。 Comparative Examples 10 and 13 show, for use as a cast film and BOPP vertical form fill and seal (the VFFS) art, such as fast food packaging and sealing layer cereal food packaging field, insufficient hot tack strength of Comparative Examples 10 and 13.

在研究各种密封材料的评估中,制备由采用束缚几何催化剂体系生产的基本上线性乙烯共聚体和用Ziegler-Natta催化剂体系生产的非均相支化乙烯共聚体构成的组合物的熔体共混物。 In Study assessments various sealing materials, prepared by a melt geometry catalyst systems produced using the bound composition and substantially linear ethylene interpolymers with Ziegler-Natta catalyst systems produce heterogeneous branched ethylene interpolymer composed of a total of mix. 该熔体共混物包括实施例14、15、17、18、20和21以及比较例16、19和22-25。 The melt blend comprising Example 14,15,17,18,20 and 21 and Comparative Examples 16, 19 and 22-25. 通过称取合适量的各组分聚合物并翻滚掺混该混合物,然后用常规单螺杆配混挤出机在约350°F(177℃)熔体温度下熔体挤出该混合物,制备熔体掺混物。 By weighing appropriate amounts of each component and the polymer mixture was tumble blended with a normal single-screw compounding extruder and the mixture was melt extruded at a melt temperature of about 350 ° F (177 ℃), prepared melt body blend. 对比例26和27通过使用诸如PCT专利申请94/01052中描述的方法和程序现场聚合制备。 Comparative Examples 26 and 27 by using methods described in PCT Patent Application 94/01052 and polymerization procedures such as site.

实施例的热密封起始温度通过测量密封层在由0.5密耳PET/1密耳LDPE 5004/2密耳密封层组成的挤出层压结构上(实施例14、15、17、18、20和21和对比例16、19和22-27)或在由1密耳(0.025mm)尼龙6/1密耳(0.025mm)PRIMACOR 1410/1.5密耳(0.038mm)密封层组成的三层共挤出吹膜结构上(比较例28)的性能确定。 Example heat sealing initiation temperature by measuring the sealing layer by the extrusion lamination structure 0.5 mil PET / 1 mil LDPE 5004/2 mils sealing layers (Examples 14,15,17,18,20 and 16, 19 and 21 and the ratio of 22-27) or by the three 1 mil (0.025mm) nylon 6/1 mil (0.025mm) PRIMACOR 1410 / 1.5 mil (0.038mm) a sealing layer composed of a total of extrusion blown film structure (Comparative Example 28) the properties determined. 这些实施例的热密封起始温度定义为获得11b/in(2N/15mm)密封强度时的最低温度。 The heat sealing initiation temperature is defined as those obtained in Example 11b / in (2N / 15mm) the lowest temperature at which the seal strength. 热密封试验在Topwave热粘着测试仪上使用0.5秒停留时间和40psi(0.275Mpa)密封棒压力进行。 Heat sealing test using a residence time of 0.5 seconds and 40psi (0.275Mpa) sealing bar pressure on Topwave hot tack tester. 密封口按5℃递增通过将密封薄膜向上折叠并使其本身密封的方式形成。 5 ℃ ascending sealing ports by the sealing film folded upwardly and sealed to itself in a manner that it is formed. 将如此形成的密封口在形成至少24小时后用Instron张力仪在10in/min(250mm/min)十字头速率下拉动。 The sealing ports thus formed pulling 10in / min under (250mm / min) crosshead rate of at least 24 hours after formation of an Instron tensile tester. 在研究中对下表3中列出的实施例评估其密封层。 Example assess the sealing layer in the study are listed in Table 3 in. 尼龙6由Allied-Signal Company出售。 Nylon 6 sold by Allied-Signal Company. 聚酯薄膜HOSTAPHAN 2DEF由American Hoechst Corporation出售。 HOSTAPHAN 2DEF polyester film sold by American Hoechst Corporation. PRIMACOR1410粘合剂聚合物和LDPE 5004树脂由The Dow Chemical Company出售。 PRIMACOR1410 binder polymer and LDPE 5004 resin sold by The Dow Chemical Company.

共挤出薄膜在装有直径2、2.5和2.5in.(5.1、6.4和6.4cm)的三个挤出机的Gluocester吹膜装置上加工。 Coextruded blown film processing apparatus in Gluocester three extruders with diameters of 2, 2.5 and 2.5in. (5.1,6.4 and 6.4cm) of. 模头为设定70密耳(1.8mm)模头缝隙的8in.(20.3cm)共挤出模头。 The die 70 is set mils (1.8mm) die gap 8in. (20.3cm) coextrusion die. 在所有共挤出中吸胀比保持为2∶1。 In all imbibed coextrusion 2:1 ratio maintained. 比出料速率为6lb/hr/in.(6.9kg/hr/cm)模头,熔体温度为400至420°F(204至216℃)。 Than the feed rate was 6lb / hr / in. (6.9kg / hr / cm) die and a melt temperature of 400 to 420 ° F (204 to 216 ℃).

用装有2.5in.(6.4cm),30∶1 L/D挤出机的Black-Clawson挤出贴面装置加工挤出层压结构。 Equipped with a 2.5in. (6.4cm), 30:1 L / D extruder Black-Clawson extrusion coating apparatus for processing a surface extrusion laminated structure. 挤出层压在熔体温度约550-600°F(288-316℃)和贴面速率约440英寸/min.(134m/min.)下进行。 Extrusion lamination conducted at a melt temperature of about 550-600 ° F (288-316 ℃) and a rate of about 440 inches veneer /min.(134m/min.) Lower. 为进行挤出层压,将LDPE 5004树脂挤出贴面于0.5密耳(0.013mm)聚酯薄膜上,并将2-密耳(0.051-mm)密封材料单层吹膜在挤出夹辊处滑移压片于LDPE树脂上。 For extrusion lamination, extrusion coating LDPE 5004 resin 0.5 mil (of 0.013 mm) on a polyester film, and 2- mil (0.051-mm) blown monolayer sealing material in the extrusion nip roll slip on the tableting LDPE resins. 将该层压结构用骤冷辊冷却并收集,随后测定其热密封起始温度。 The laminate structure was cooled chill roll and collected by subsequently measured heat sealing initiation temperature.

实施例的2%纵向(MD)模量通过2密耳(0.051mm)单层吹膜测量。 2% of the longitudinal (MD) modulus by Example 2 mil (0.051 mm) blown monolayer measured. 用于物理试验的单层薄膜(以及在上述挤出层压中用作滑移压片密封材料的2密耳(0.051mm)单层吹膜)在装有2.5in(6.4cm)直径、24∶1 L/d挤出机(使用单螺线双混合聚乙烯螺杆、设定70密耳(1.8mm)模头间隙的6in.(15.2cm)模头)的Gloucester吹膜装置上加工。 Single-layer film (2 mils and tabletting slip as the sealing material in the above extrusion lamination (0.051 mm) blown monolayer) for physical testing (6.4cm) in diameter with 2.5in, 24 :1 L / d extruder (single-screw spiral double mixed polyethylene, set 70 mils (1.8mm) 6in die gap. (15.2 cm) die) on a Gloucester blown film processing apparatus. 所有实施例保持吸胀比2.5∶1,由此加工2密耳(0.051mm)薄膜,并将熔体温度设定为450°F(232℃)以达到比出料速率61b./hr/in.(6.9kg/hr/cm)模头。 Holding all embodiments imbibition than 2.5, whereby the processing 2 mil (0.051 mm) film, and the melt temperature set at 450 ° F (232 ℃) than the feed rate to achieve 61b./hr/in . (6.9kg / hr / cm) die. 下表3提供各种实施例组合物的性能数据以及DOWLEX LLDPE树脂2045(比较例28)、DOWLEX LLDPE树脂2049(比较例29)、DOWLEX LLDPE树脂2038(比较例30)的性能数据。 Table 3 provides various properties of the composition in Example data and DOWLEX LLDPE 2045 resin (Comparative Example 28) embodiment, DOWLEX LLDPE 2049 resin (Comparative Example 29), DOWLEX LLDPE 2038 resin (Comparative Example 30) the performance data. 所有DOWLEX树脂为The Dow Chemical Company出售的非均相支化乙烯共聚体。 Not all DOWLEX resins sold by The Dow Chemical Company homogeneously branched ethylene interpolymer. 表3 table 3

SLEP表示使用束缚几何催化剂体系制备的基本上线性乙烯聚合物。 SLEP indicates substantially linear ethylene polymers used to be bound geometry catalyst system was prepared. Z/N表示用Ziegler-Natta催化剂体系制备的非均相乙烯聚合物。 Z / N represents a heterogeneous ethylene polymers prepared using Ziegler-Natta catalyst system. N/A表示不适用。 N / A means not applicable. N/D表示未测量。 N / D means not measured. *不是本发明的实施例,仅用于对比目的由表3中给出的数据绘制多张图。 * Not an embodiment of the present invention, given only for comparative purposes by the data in Table 3 plots the various figures. 图4为作为均相支化乙烯聚合物组分(C)重量百分比的函数的本发明和对比薄膜实施例的热密封起始温度图。 FIG 4 is a thin film of the present invention and as a function of comparative homogeneously branched ethylene polymer component (C) weight percent of the heat sealing initiation temperature the embodiment of FIG. 令人吃惊的是,图4说明,对于约20至约60wt%的基本上线性乙烯聚合物作为第一种乙烯聚合物组分(C),实施例14、15、17、18、20和21与由密度大于0.89g/cc的均相支化乙烯聚合物构成的薄膜比较例相比呈现较低的密封起始温度。 Surprisingly, Figure 4 illustrates, for from about 20 to about 60wt% of substantially linear ethylene polymers as a first ethylene polymer component (C), Example 14,15,17,18,20 and 21 homogeneous with a density greater than 0.89g / cc branched ethylene polymer constituting the film of Comparative Example exhibit lower compared seal initiation temperature. 对于百分比大于或等于35wt%(按制备薄膜的双组分组合物总重量计),实施例的密封起始温度尤其低于可比拟的比较例。 Percentage is greater than or equal to 35wt% (film was prepared by a two-component composition total weight), a seal initiation temperature lower than the particular embodiment of the Comparative Example can be compared.

更令人吃惊的是,图5说明实施例的密封起始温度显著低于相同组成密度的比较例的密封起始温度。 More surprising is that in FIG. 5 illustrates an embodiment of a seal initiation temperature is significantly lower than the seal initiation temperature of Comparative Example having the same composition density. 图6说明与薄膜比较例相比实施例在相同的薄膜模量下呈现较低密封起始温度。 6 illustrates a thin film in comparison with Comparative Examples exhibits a low seal initiation temperature under the same modulus of the film. 换言之,当比较例呈现较高的薄膜模量和较高的密封起始温度时,本发明实施例在给定薄膜模量下具有较低的密封起始温度。 In other words, when Comparative Example films exhibit higher modulus and higher seal initiation temperature, embodiments of the present invention with a given lower seal initiation temperature lower film modulus.

最后,图7说明,尽管本发明实施例对于给定薄膜模量呈现较低的密封起始温度,当在给定组成密度下其薄膜模量令人吃惊地高于相同密度的单组分非均相支化乙烯聚合物的薄膜模量。 Finally, Figure 7 illustrates, for a given single component non-film exhibits a low modulus, seal initiation temperature, at a given composition when the densities of film modulus surprisingly higher than the same density although the embodiments of the present invention homogeneously branched ethylene polymer film modulus. 因此,概而言之,图4-7说明,本发明实施例呈现与较低密度乙烯聚合物相等的密封起始温度,同时保持中等至较高的密度乙烯聚合物的薄膜模量。 Thus, summary, FIG. 4-7 shows that the present embodiment is equal to the lower density ethylene polymer of the present invention, the sealing initiation temperature, while keeping the modulus of the film medium to high density ethylene polymer. 因此,这些数据证明,本发明令人吃惊且意想不到地克服了热密封性能与薄膜劲度之间传统上的相互抵消。 Thus, these data demonstrate that the present invention surprisingly and unexpectedly overcome the traditional offset each other between the heat sealing properties of the film stiffness.

Claims (18)

1.一种密封薄膜组合物,其特征在于包括并由如下组分制备:按组合物总重量计,5至95wt%的至少一第一种乙烯聚合物,其为均相支化的基本上线性乙烯聚合物或均相支化的线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i.熔体流动比例I10/I2≥5.63ii. I2熔体指数0.001g/10min至2g/10min,按照ASTMD-1238条件190℃/2.16kg测定,iii.密度0.85至0.92g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和按组合物总重量计,5至95wt%的至少一第二种乙烯聚合物,其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度低于0.97g/cc,其中组合物的特征是具有组成密度0.89g/cc至0.95g/cc,按照ASTM D-792测量,和至少一第一种乙烯聚合物的I2熔体指数低 1. A sealing film composition, characterized by the following composition was prepared comprising: by weight of the total composition, 5 to 95wt% of at least one first ethylene polymer which is a homogeneously branched substantially line ethylene polymer or homogeneously branched linear ethylene polymer, wherein the first ethylene polymer is characterized by having:.. i melt flow ratio I10 / I2≥5.63ii I2 melt index of 0.001g / 10min to 2g / 10min, in accordance with 190 ℃ / 2.16kg measured ASTMD-1238 condition, iii. a density of 0.85 to 0.92g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn is less than 3.5, as measured by gel permeation chromatography, iv. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and the total weight of the composition, 5 to 95wt% of at least one second ethylene polymer which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer characterized as having a density less than 0.97g / cc, wherein the composition is characterized by having a composition density of 0.89g / cc to 0.95g / cc, measured according to ASTM D-792, and I2 melt index of at least a first ethylene polymer is low 至少一第二种乙烯聚合物的I2熔体指数。 I2 melt index of at least a second ethylene polymer.
2.一种包括聚丙烯层和密封层的多层结构,所述密封层具有平衡性能,包括与聚丙烯的极好层间粘结性能,其特征在于包括并由如下组分制备:(A)按密封层的总重量计,5至95wt%的至少一第一种乙烯聚合物,其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数大于0.14g/10min至低于0.67g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度0.85至0.92g/cc,按照ASTM D-792测量,iii. I10/I2熔体流动比6至12,按照ASTM D-1238条件190℃/2.16kg和条件190℃/10kg测定,iv.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,v.在-30至150℃之间的单一差示扫描量热DSC熔化峰,vi.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(B)按密封层总重量计,5至95wt%的至少一第二种乙烯聚合物,其为均相支化乙烯聚合物或非 A multilayer structure comprising a polypropylene layer and a sealing layer, said sealing layer having a balance of properties, including excellent inter-layer adhesion properties to polypropylene, characterized by comprising the following ingredients was prepared: (A ) by total weight of the sealing layer, 5 to 95wt% of at least one first ethylene polymer which is a homogeneously branched substantially linear ethylene polymers or homogeneously branched linear ethylene polymer, wherein the first ethylene characterized in that the polymer has:.. i I2 melt index of greater than 0.14g / 10min to less than 0.67g / 10min, in accordance with 190 ℃ / 2.16kg measured ASTM D-1238 conditions, ii density of 0.85 to 0.92g / cc, according to ASTM D-792 measurement, iii. I10 / I2 melt flow ratio of from 6 to 12, according to ASTM D-1238 condition 190 ℃ / 2.16kg and conditions of 190 ℃ / 10kg measured, iv. a molecular weight distribution Mw / Mn is less than 3.5, according to gel permeation chromatography, v. a single difference between the -30 deg.] C to 150 scanning calorimetry DSC melting peak, vi. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and (B) by the total weight of the sealing layer, 5 to 95wt% of at least one second ethylene polymer which is a homogeneously branched ethylene polymer or 相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.89g/cc至0.965g/cc,其中密封层的特征是具有组成密度0.89g/cc至0.93g/cc,按照ASTMD-792测量,和I2熔体指数1g/10min至5g/10min,按照ASTM D-1238条件190℃/2.16kg测定,和其中至少一第一种乙烯聚合物(A)的分子量高于至少一第二种乙烯聚合物(B)的分子量。 Branched linear ethylene polymer phase, wherein the second ethylene polymer is characterized in having a density of 0.89g / cc to 0.965g / cc, wherein the sealing layer is characterized in having a composition density of 0.89g / cc to 0.93g / cc, according to ASTMD-792 measurement, and I2 melt index of 1g / 10min to 5g / 10min, measured according to ASTM D-1238 condition 190 ℃ / 2.16kg, wherein the molecular weight and the at least one first ethylene polymer (a) is higher than at least a molecular weight of the second ethylene polymer (B) is.
3.一种具有改进模量和组成密度的薄膜或薄膜层,所述薄膜或薄膜层的特征在于包括并由如下组分制备:(C)按薄膜或薄膜层的总重量计,20至60wt%的至少一第一种乙烯聚合物,其为均相支化基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTMD-1238条件190℃/2.16kg测定,ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(D)按薄膜或薄膜层总重量计,40至80wt%的至少一第二种乙烯聚合物,其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTM D-792测量,其中至少一第一种乙烯聚合物组分(C)的I2熔体指数等于或 3. An improved modulus, density and composition of the film or film layer having the feature that the film or film layer comprising the following composition was prepared by: (C) the film or film layer by total weight, 20 to 60wt % of at least one first ethylene polymer which is a homogeneously branched substantially linear ethylene polymers or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having:. i I2 melt index 0.001g / 10min to 2g / 10min, in accordance with 190 ℃ / 2.16kg measured ASTMD-1238 condition, ii. a density less than 0.89g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn below 3.5, measured according to gel permeation chromatography, iv. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and (D) the film or film layer by total weight, 40 to 80wt% of at least one of the second ethylene polymer is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc, according to ASTM D-792 measurement, wherein the at least one first ethylene polymer component (C) is equal to a melt index or I2 于至少一第二种乙烯聚合物组分(D)的I2熔体指数,和薄膜或薄膜层的特征是具有组成密度0.915g/cc至0.95g/cc,按照ASTM D-792测量。 Wherein at least one second ethylene polymer component (D) is I2 melt index, and a film or film layer has a composition density of 0.915g / cc to 0.95g / cc, measured according to ASTM D-792.
4.一种制备具有改进模量的密封薄膜的方法,该薄膜的特征在于包括至少一薄膜层,该方法的特征在于包括如下步骤:提供由如下组分构成或制备的聚合物组合物(C)按薄膜的总重量计,20至60wt%的至少一第一种乙烯聚合物,其为基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTMD-1238条件190℃/2.16kg测定,ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(D)按薄膜总重量计,40至80wt%的至少一第二种乙烯聚合物,其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTMD-792测量,其中至少一第一种乙烯聚合 An improved method for preparing a modulus of the sealing film, wherein the film comprises at least one film layer, characterized in that the method comprises the steps of: providing a polymer composition composed of the following ingredients was prepared or (C ) by total weight of the film, 20 to 60wt% of at least one of a first ethylene polymer wherein a first polymer of ethylene is characterized as a substantially linear ethylene polymer or homogeneously branched linear ethylene polymers, with:.. i I2 melt index of 0.001g / 10min to 2g / 10min, in accordance with 190 ℃ / 2.16kg measured ASTMD-1238 condition, ii density of less than 0.89g / cc, measured according to ASTM D-792, iii molecular weight distribution. Mw / Mn is less than 3.5, measured according to gel permeation chromatography, iv. short chain branching distribution index (The SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and (D) by the total weight of the film, 40 to 80wt % of at least one second ethylene polymer which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc, measured in accordance with ASTMD-792, wherein at least one of a first ethylene polymerization 组分(C)的I2熔体指数等于或低于至少一第二种乙烯聚合物组分(D)的I2熔体指数,和薄膜的特征是具有组成密度0.915g/cc至0.95g/cc,按照ASTM D-792测量;挤出该聚合物组合物形成至少一薄膜层的薄膜;和收集包括至少一薄膜层的薄膜。 Component (C) has a melt index I2 of less than or equal to at least a second ethylene polymer component (D) is I2 melt index, and wherein the film composition having a density of 0.915g / cc to 0.95g / cc , measured according to ASTM D-792; extruding the polymer composition to form a film of at least one film layer; and at least one thin film comprising a collection layer.
5.一种提供改进薄膜模量的可热密封组合物,该组合物的特征在于包括并由如下组分制备:(C)按组合物总重量计,20至60wt%的至少一第一种乙烯聚合物,其为基本上线性乙烯聚合物或均相支化线性乙烯聚合物,其中第一种乙烯聚合物的特征在于具有:i. I2熔体指数0.001g/10min至2g/10min,按照ASTM D-1238条件190℃/2.16kg测定,ii.密度低于0.89g/cc,按照ASTM D-792测量,iii.分子量分布Mw/Mn低于3.5,按照凝胶渗透色谱测定,iv.短链支化分布指数(SCBDI)大于50%,用温升洗脱分级测量,和(D)按组合物重量计,40至80wt%的至少一第二种乙烯聚合物,其为均相支化乙烯聚合物或非均相支化线性乙烯聚合物,其中第二种乙烯聚合物的特征是具有密度0.94g/cc至0.97g/cc,按照ASTMD-792测量,其中至少一第一种乙烯聚合物组分(C)的I2熔体指数等于或低于至少一第二种乙烯聚合物组分(D)的I2 5. A method of providing improved film modulus heat seal composition, wherein the composition is characterized by comprising the following components was prepared: (C) by the total weight of the composition, of at least a first one of 20 to 60wt% ethylene polymer which is a substantially linear ethylene polymer or homogeneously branched linear ethylene polymers, wherein a first polymer of ethylene is characterized by having:. i I2 melt index of 0.001g / 10min to 2g / 10min, according to ASTM D-1238 condition 190 ℃ / 2.16kg measured, ii. a density less than 0.89g / cc, measured according to ASTM D-792, iii. a molecular weight distribution Mw / Mn is less than 3.5, as measured by gel permeation chromatography, iv. short chain branching distribution index (the SCBDI) greater than 50%, with a temperature rise elution fractionation measurement, and (D) by weight of the composition, 40 to 80wt% of at least one second ethylene polymer which is a homogeneously branched ethylene polymer or homogeneously branched linear ethylene polymer, wherein the second ethylene polymer is characterized in having a density of 0.94g / cc to 0.97g / cc, measured in accordance with ASTMD-792, wherein at least one of a first ethylene polymerization composition component (C) is less than or equal to I2 melt index I2 of at least one second ethylene polymer component (D), 体指数,和组合物的特征是具有组成密度0.915g/cc至0.95g/cc,按照ASTM D-792测量。 Wherein the index member, and compositions having a composition density of 0.915g / cc to 0.95g / cc, measured according to ASTM D-792.
6.权利要求1-3任何一项的的组合物、结构、薄膜或薄膜层,其中至少一第一种乙烯聚合物为具有如下特征的基本上线性乙烯聚合物:i.通过凝胶渗透色谱测定,分子量分布Mw/Mn由如下方程定义:(Mw/Mn)≤(I10/I2)-4.63ii.使基本上线性乙烯聚合物表面熔体破裂开始时的临界剪切速率比线性乙烯聚合物表面熔体破裂开始时的临界剪切速率大至少50%的气体挤出流变性能,其中基本上线性乙烯聚合物和线性乙烯聚合物包括相同的共聚单体,线性乙烯聚合物具有的I2、Mw/Mn和密度值在基本上线性乙烯聚合物的上下10%范围内,和其中基本上线性乙烯聚合物和线性乙烯聚合物的相应临界剪切速率在相同的熔体温度下使用气体挤出流变仪测定。 6. A composition according to any one of claims 1-3 of the structure, film or film layer, wherein the at least one first ethylene polymer is characterized as having substantially linear ethylene polymers:. I by gel permeation chromatography Determination of the molecular weight distribution Mw / Mn defined by the equation: (Mw / Mn) ≤ (I10 / I2) -4.63ii substantially linear ethylene polymers to make the surface melt fracture critical shear rate at the beginning than the linear ethylene polymer. surface melt fracture critical shear rate at the start of at least 50% of the gas extrusion rheological properties, wherein a substantially linear ethylene polymer and the linear ethylene polymer comprise the same comonomer, linear ethylene polymers having I2, Mw / Mn and density values ​​in the range of substantially linear ethylene polymers and down 10%, and wherein the respective critical shear rates substantially linear ethylene polymers and linear ethylene polymers extruded using a gas at the same melt temperature Determination rheometer.
7.权利要求6的组合物、结构、薄膜或薄膜层,其中基本上线性乙烯聚合物具有0.01至3个长支链/1000个碳原子。 The composition, structure, film or film layer of claim 6, wherein the substantially linear ethylene polymer having 0.01 to 3 long chain branches / 1000 carbon atoms.
8.权利要求1-3任何一项的组合物、结构、薄膜或薄膜层,其中第二种乙烯聚合物为非均相支化线性乙烯聚合物。 4. The composition, structure, film or film layer according to any one of claim 1, wherein the second ethylene polymer is non homogeneously branched linear ethylene polymers.
9.权利要求1-3任何一项的组合物、结构、薄膜或薄膜层,其中至少一第一种乙烯聚合物或第二种乙烯聚合物为乙烯与至少一种选自1-丙烯、1-丁烯、1-异丁烯、1-己烯、4-甲基-1-戊烯、1-戊烯、1-庚烯和1-辛烯的α-烯烃的共聚体。 9. 4. The composition, structure, film or film layer according to any one of claims, wherein the at least one first ethylene polymer is a second ethylene polymer or ethylene and at least one compound selected from 1-propenyl, 1 - butene, 1-isobutylene, 1-hexene, 4-methyl-1-pentene, α- olefin interpolymer 1-pentene, 1-heptene and 1-octene.
10.权利要求1-3任何一项的组合物、结构、薄膜或薄膜层,其中至少一第一种乙烯聚合物或第二种乙烯聚合物为乙烯与1-辛烯的共聚物。 1-3 10. The composition, structure, film or film layer according to any one of claims, wherein the at least one first ethylene polymer is a second ethylene polymer or an ethylene copolymer with 1-octene.
11.权利要求1-3任何一项的组合物、结构、薄膜或薄膜层,其中聚合物组合物或层通过将第一种乙烯聚合物与第二种乙烯聚合物由至少一种选自熔体挤出、干混、顺序操作至少两个聚合反应器和平行操作至少两个聚合反应器的方法混合制备。 1-3 11. The composition, structure, film or film layer according to any one of claims, wherein the polymer composition or the first layer of an ethylene polymer and second ethylene polymer is selected from at least one melt extruded, dry blending, sequential operation of the method at least two polymerization reactors and parallel operation of the reactor is prepared by mixing at least two polymerization.
12.权利要求11的组合物、结构、薄膜或薄膜层,其中至少两个聚合反应器为再循环环路反应器。 The composition, structure, film or film layer of claim 11, wherein the at least two reactors is a recirculating loop polymerization reactor.
13.权利要求2的多层薄膜结构,其中该结构为蒸煮包装物、热填充包装物、可流动物质包装盒、压缩填充包装物、收缩薄膜或阻挡收缩薄膜。 13. A multilayer film structure as claimed in claim 2, wherein the structure is a retort packaging material, the hot fill packaging material, a flowable material package, filling the package compressed, shrink film or barrier shrink film.
14.权利要求2的多层薄膜结构,其中该结构包括双轴取向聚乙烯薄膜层。 14. A multilayer film structure as claimed in claim 2, wherein the structure comprises a biaxially oriented polyethylene film layer.
15.权利要求2的多层薄膜结构,其中该结构还包括阻挡材料或层。 15. A multilayer film structure as claimed in claim 2, wherein the structure further comprises a barrier material or layer.
16.权利要求15的多层薄膜结构,其中阻挡材料或层为聚偏二氯乙烯共聚物、聚酯、聚酰胺、双轴取向聚丙烯或铝箔。 16. A multilayer film structure as claimed in claim 15, wherein the barrier material or layer is a polyvinylidene chloride copolymer, polyester, polyamide, or biaxially oriented polypropylene foil.
17.权利要求4的方法,其中挤出通过吹膜工艺完成。 17. The method as claimed in claim 4, wherein the blown film extrusion process is done by.
18.权利要求4的方法,其中挤出步骤包括将该层与至少另一层在形成该层的同时结合,或在形成该层后结合。 18. The method as claimed in claim 4, wherein the extruding step comprises the binding layer while at least another layer in the layer is formed or after formation of the binding layer.
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CN1806004B (en) * 2003-06-10 2010-06-16 陶氏环球技术公司 Film layers made from ethylene polymer blends
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CN102802946A (en) * 2009-04-10 2012-11-28 陶氏环球技术有限责任公司 High performance sealable coextruded biaxially oriented polypropylene film
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CN101287598B (en) * 2005-10-12 2016-08-03 金达胶片美国有限责任公司 Plural layers, preparation method and goods prepared therefrom
CN102802946A (en) * 2009-04-10 2012-11-28 陶氏环球技术有限责任公司 High performance sealable coextruded biaxially oriented polypropylene film
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CN104640920A (en) * 2012-06-28 2015-05-20 陶氏环球技术有限责任公司 Crosslinked foams having high hardness and low compression set
CN106163800A (en) * 2014-04-01 2016-11-23 陶氏环球技术有限责任公司 Multilayer film and the goods prepared by it
CN106163800B (en) * 2014-04-01 2019-12-06 陶氏环球技术有限责任公司 Multilayer films and articles made therefrom
WO2018045559A1 (en) * 2016-09-09 2018-03-15 Dow Global Technologies Llc Multilayer films and laminates and articles comprising the same

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