CN110621474A - 用于改性和连接取向管道的方法 - Google Patents

用于改性和连接取向管道的方法 Download PDF

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CN110621474A
CN110621474A CN201880031838.3A CN201880031838A CN110621474A CN 110621474 A CN110621474 A CN 110621474A CN 201880031838 A CN201880031838 A CN 201880031838A CN 110621474 A CN110621474 A CN 110621474A
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pipe
biaxially oriented
end portion
thermoplastic polymer
tube
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CN110621474B (zh
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A·K·塔莱亚
R·克莱平格
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SABIC Global Technologies BV
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/02Thermal shrinking
    • B29C61/025Thermal shrinking for the production of hollow or tubular articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C57/00Shaping of tube ends, e.g. flanging, belling or closing; Apparatus therefor, e.g. collapsible mandrels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/22Shaping by stretching, e.g. drawing through a die; Apparatus therefor of tubes
    • B29C55/26Shaping by stretching, e.g. drawing through a die; Apparatus therefor of tubes biaxial
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/114Single butt joints
    • B29C66/1142Single butt to butt joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/50General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/52Joining tubular articles, bars or profiled elements
    • B29C66/522Joining tubular articles
    • B29C66/5221Joining tubular articles for forming coaxial connections, i.e. the tubular articles to be joined forming a zero angle relative to each other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00General aspects of processes or apparatus for joining preformed parts
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    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/735General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the extensive physical properties of the parts to be joined
    • B29C66/7352Thickness, e.g. very thin
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7371General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable
    • B29C66/73711General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable oriented
    • B29C66/73713General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable oriented bi-axially or multi-axially
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L13/00Non-disconnectible pipe-joints, e.g. soldered, adhesive or caulked joints
    • F16L13/004Shrunk pipe-joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/34Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4895Solvent bonding, i.e. the surfaces of the parts to be joined being treated with solvents, swelling or softening agents, without adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/13Single flanged joints; Fin-type joints; Single hem joints; Edge joints; Interpenetrating fingered joints; Other specific particular designs of joint cross-sections not provided for in groups B29C66/11 - B29C66/12
    • B29C66/131Single flanged joints, i.e. one of the parts to be joined being rigid and flanged in the joint area
    • B29C66/1312Single flange to flange joints, the parts to be joined being rigid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00Tubular articles
    • B29L2023/22Tubes or pipes, i.e. rigid

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  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Rigid Pipes And Flexible Pipes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

本发明涉及一种用于改性双轴取向管道的改性方法,包括:a)提供通过在轴向方向上和在圆周方向上拉伸由热塑性聚合物组合物制成的管而制成的双轴取向管道,b)将插入件置于该管道的端部中,其中该插入件横截面的外圆周基本上匹配该管道横截面的内圆周,和c)加热该端部,以使得该端部轴向收缩,同时该端部横截面的内圆周基本上得以保持,以获得具有增厚端部的经改性的双轴取向管道。

Description

用于改性和连接取向管道的方法
本发明涉及一种用于改性双轴取向管道的改性方法。本发明进一步涉及一种所获得的经改性管道的管道连接方法。
通过取向材料来改进聚合物材料的物理和力学性能是已知的。在许多情况下,取向材料以改进在一个方向上的性能导致在垂直于该取向方向的方向上同一性能的劣化。为了在两个方向上适应该性能,可以施加材料的双轴取向。双轴取向意味着聚合物材料在两个彼此垂直的方向上取向。管道可以在轴向方向和圆周方向(环向)上取向以改进性能如拉伸强度。
由双轴取向聚合物制成的管道的端部可以通过方法如对接焊来连接。然而,当对接端熔融以用于对接焊时,管道将具有比对接焊之前更低的爆破压力,因为在对接端处失去了取向。因此,双轴取向聚合物管道通常是通过机械方法连接的,以便保存它们的取向。另一已知的用于连接管道的方式是通过使用电熔合技术,如Atkinson等,POLYM ENG SCI.,1989,第29卷,第23期,第1638-1641页。令人期望的是提供一种管道连接方法,其避免了在接头处力学性能大的下降。
本发明的一个目的在于提供一种解决了上述和/或其他问题的方法。
因此,本发明提供一种用于改性双轴取向管道的改性方法,包括:
a)提供通过在轴向方向上和在圆周方向上拉伸由热塑性聚合物组合物制成的管而制成的双轴取向管道,
b)将插入件置于该管道的端部中,其中该插入件横截面的外圆周基本上匹配该管道横截面的内圆周,和
c)加热该端部,以使得该端部轴向收缩,同时该端部横截面的内圆周基本上得以保持,以获得具有增厚端部的经改性双轴取向管道。
本发明进一步提供一种管道连接方法,包括:
I)进行根据本发明的改性方法,以获得第一经改性双轴取向管道和第二经改性双轴取向管道,和
II)将该第一双轴取向管道的增厚端部的对接端和该第二双轴取向管道的增厚端部的对接端连接。
术语“管道”和“管”在本文被理解为空心伸长的制品。横截面可以具有不同的形状例如是圆形、椭圆形、正方形、矩形或三角形。术语“直径”在本文被理解为横截面的最大尺寸。
该插入件横截面的外圆周基本上匹配该管道横截面的内圆周。这意味着该插入件横截面的外圆周和该管道横截面的内圆周具有相同的形状(即它们都是圆形或它们都是正方形等),并且该插入件横截面的外圆周的直径等于或稍小于该管道横截面的内圆周的直径,例如该插入件横截面的外圆周的直径是该管道横截面的内圆周的直径的95-100%。
根据本发明的改性方法,匹配性插入件置于双轴取向管道的一端内。将该管道的这个端部加热接近于该管道材料的熔融温度,同时该管道的其余部分不加热。加热时,该热塑性聚合物在端部处的取向度下降并且该端部在其内圆周归因于该插入件的存在而保持的同时轴向收缩。这导致具有增加厚度的端部。
这些增厚端部可以在它们的尺寸没有任何另外改变的情形下在它们的对接端处连接。该连接导致对接端处取向几乎完全失去,如常规工艺中那样。然而,根据本发明的改性方法,在连接的对接端处获得了相对高的爆破压力。虽然在连接的对接端处失去取向降低了爆破压力,但是该端部增加的厚度增加了爆破压力。因此,在连接的对接端处的爆破压力比根据常规工艺制造的连接的对接端高得多。
已经发现在增厚端部形成期间,该增厚端部中的取向度在环向上比在轴向方向上保留至更大的程度。此外,在连接步骤期间,除对接端外增厚端部中的取向得以保留到一定程度。在连接的端部中取向的保留可以进一步有利于爆破压力的保持。
制备该双轴取向管道、改性该管道端部并且连接所获得的管道可以有利地在同一装置位置进行。可替代地,管道的改性和连接可以在管道铺设位置进行。在生产位置或铺设位置进行管道的改性和连接的可能性对于管道安装效率来说是非常有利的。这通过不需要专用设备、不同于常规的机械连接方法的事实而成为可能。
步骤a)
在步骤a)中,提供了一种通过在轴向方向上和在圆周方向上拉伸由热塑性聚合物组合物制成的管而制成的双轴取向管道。优选地,拉伸已经在轴向方向上以1.1-5.0的轴向拉伸比和在圆周方向上以1.1-2.0的平均环向拉伸比进行。
优选地,步骤a)包括
a1)将热塑性聚合物组合物成形为管,和
a2)在轴向方向上以1.1-5.0的轴向拉伸比和在圆周方向上以1.1-2.0的平均环向拉伸比拉伸步骤a1)的管以获得双轴取向管道。
步骤a1)
热塑性聚合物组合物
优选地,热塑性聚合物组合物包含选自以下的热塑性聚合物:聚乙烯、聚丙烯、聚氯乙烯、聚酯、聚碳酸酯、聚酰胺、聚缩醛、聚酰亚胺、聚偏二氟乙烯和聚醚醚酮及其组合。
热塑性聚合物的一个优选的实例是聚乙烯如高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)和低密度聚乙烯(LDPE),和特别优选高密度聚乙烯(HDPE)。热塑性聚合物的另一优选的实例是聚丙烯,优选无规聚丙烯。
聚乙烯
HDPE、LLDPE和LDPE的生产工艺由Andrew Peacock汇总在Handbook ofPolyethylene(2000;Dekker;ISBN 0824795466)第43-66页中。
HDPE
HDPE可以是乙烯均聚物或可以包含共聚单体如丁烯或己烯。
优选地,HDPE具有根据ISO1183测量的940-960kg/m3、更优选940-955kg/m3的密度。
优选地,HDPE具有根据ISO1133-1:2011(190℃/5kg)测量的0.1-4g/10min、更优选0.1-1g/10min的熔体流动速率。
在一些实施方案中,该组合物包含含HDPE和着色剂的配混料,其中该配混料具有根据ISO1183测量的947-965kg/m3的密度。该着色剂可以例如是炭黑或具有例如黑色、蓝色或橙色的颜料。该着色剂的量相对于包含HDPE和着色剂的配混料典型地是1-5wt%、更典型是2-2.5wt%,其余典型地是HDPE。
该HDPE可以是单峰、双峰或多峰。优选地,该HDPE是双峰或多峰。这样的HDPE具有适合用于生产管道的性能。
要理解的是双峰HDPE的分子量分布具有对应于聚合中的各个阶段的第一中值和第二中值的两个峰。类似要理解的是多峰HDPE的分子量分布具有对应于聚合中的各个阶段的第一中值、第二中值和一个或多个另外的中值的多个峰。
该HDPE可以通过使用低压聚合工艺来生产。例如性能类PE80和PE100的管道材料是已知的,其通常在级联设备中通过所谓的双峰或多峰法来生产。双峰HDPE的生产工艺汇总在“PE 100Pipe systems”(由Bromstrup编辑;第二版,ISBN 3-8027-2728-2)的第16-20页中。合适的低压工艺是浆料搅拌反应器级联、浆料环流反应器级联和不同工艺如浆料环流气相反应器的组合。还可以使用多峰聚乙烯、优选三峰聚乙烯作为高密度聚乙烯管道材料,如WO2007003530中所述。
性能类PE80和PE100在“PE 100 Pipe systems”(由Bromstrup编辑;第二版,ISBN3-8027-2728-2)的第35-42页中进行了讨论。质量测试方法描述在“PE 100 Pipe systems”的第51-62页。
经由低压浆料法生产双峰高密度聚乙烯(HDPE)由Alt等描述在“BimodalPolyethylene-Interplay of Catalyst and Process”(Macromol.Symp.2001,163,135-143)中。在两级级联法中,反应器可以连续进料从该方法再循环的己烷和催化剂/助催化剂、氢、单体的混合物。在反应器中,乙烯的聚合作为放热反应在例如0.5MPa(5bar)到1MPa(10bar)范围的压力下和在例如75℃到85℃范围的温度下进行。来自聚合反应的热借助于冷却水来除去。聚乙烯的特性由催化剂系统和施加的催化剂、共聚单体和氢的浓度等来确定。
两级级联法的概念由Alt等在“Bimodal Polyethylene-Interplay of Catalystand Process”(Macromol.Symp.2001,163)的第137-138页说明。该反应器以每个反应器中的不同条件(包括在第二反应器中的低氢气含量)在级联中设置。这允许生产具有双峰分子量分布并且定义了聚乙烯链中的共聚单体含量的HDPE。
HDPE优选的实例包括单峰或双峰PE80、双峰PE100和多峰HDPE树脂。PE80是MRS(在20℃下的水50年后的最低要求强度)为8MPa的PE材料,和PE100是MRS为10MPa的PE材料。该管道分级是在“PE 100Pipe systems”(由Bromstrup编辑;第二版,ISBN 3-8027-2728-2)第35页描述的。
优选地,该HDPE或包含HDPE和着色剂的配混料具有以下特性中的一种或多种,优选以下特性的全部:
-拉伸模量是500-1400MPa、优选700-1200MPa(根据ISO 527-2)
-屈服应力是15-32MPa、优选18-28MPa(根据ISO 527-2)
-全缺口蠕变测试(FNCT):100-20000h(根据ISO 16770在80℃下/4MPa)
-在23℃下10-35℃、优选14-30℃的沙尔比(Charpy)(根据ISO1eA)。
LLDPE
适于LLDPE制造的技术包括气相流化床聚合、溶液聚合、在非常高的乙烯压力下的聚合物熔体聚合和浆料聚合。
该LLDPE包含乙烯和C3-C10α-烯烃共聚单体(乙烯-α烯烃共聚物)。合适的α-烯烃共聚单体包括1-丁烯、1-己烯、4-甲基戊烯和1-辛烯。优选的共聚单体是1-己烯。优选地,该α-烯烃共聚单体以乙烯-α烯烃共聚物的约5至约20重量%的量、更优选乙烯-α烯烃共聚物的约7至约15重量%的量存在。
优选地,该LLDPE具有根据ISO1872-2测定的900-948kg/m3、更优选915-935kg/m3、更优选920-935kg/m3的密度。
优选地,该LLDPE具有根据ISO1133-1:2011(190℃/2.16kg)测定的0.1-3.0g/10min、更优选0.3-3.0g/10min的熔体流动速率。
LDPE
该LDPE可以通过使用高压釜高压技术和通过管式反应器技术来生产。
LDPE可以是乙烯均聚物或可以包含共聚单体如丁烯或己烯。
优选地,该LDPE具有根据ISO1872-2测定的916-940kg/m3、更优选920-935kg/m3的密度。
优选地,该LLDPE具有根据ISO1133-1:2011(190℃/2.16kg)测定的0.1-3.0g/10min、更优选0.3-3.0g/10min的熔体流动速率。
聚乙烯组合物
优选地,该热塑性聚合物组合物包含HDPE。在一些实施方案中,该聚乙烯组合物包含除HDPE之外的另外的聚乙烯。该另外的聚乙烯可以例如是线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)或LLDPE和LDPE的组合。优选地,该另外的聚乙烯是LLDPE或LLDPE和LDPE的组合。更优选地,该另外的聚乙烯是LLDPE。在该另外的聚乙烯是LLDPE和LDPE的组合的情况下,LLDPE与LDPE的重量比可以例如是至少0.1,例如至少0.2或至少0.3和至多10,例如至多5或至多3。优选地,LLDPE与LDPE的重量比是至少1,例如2-10。优选地,该聚乙烯组合物中HDPE与另外的聚乙烯的重量比大于1、优选1.2-5,例如1.5-4或2-3。
在一些实施方案中,该热塑性聚合物组合物基本上不含除HDPE之外的另外的聚乙烯。该聚乙烯组合物中,HDPE在聚乙烯中的量可以是至少95wt%、至少98wt%、至少99wt%或100wt%。
优选地,该包含HDPE的热塑性聚合物组合物具有根据ISO1133-1:2011(190℃/5kg)测量的0.1-4g/10min、更优选0.1-1g/10min的熔体流动速率。
其他聚合物
该热塑性聚合物的另一优选的实例是聚丙烯、优选无规丙烯共聚物。
如本文所用,术语“无规丙烯共聚物”是含有聚合在一起以形成聚合物的丙烯单体和α-烯烃单体的共聚物,其中单个重复单元以无规或统计分布存在于聚合物链中。
添加剂
该热塑性聚合物组合物可以包含除热塑性聚合物之外的组分,例如添加剂和填料。
添加剂的实例包括成核剂;稳定剂如热稳定剂,抗氧化剂,UV稳定剂;着色剂如颜料和染料;澄清剂;表面张力改性剂;润滑剂;阻燃剂;脱模剂;流动改进剂;增塑剂;抗静电剂;外部弹性冲击改性剂;发泡剂;和/或增强聚合物和填料之间的界面结合的组分如马来酸化的聚乙烯。添加剂的量相对于总组合物典型地是0-5wt%、例如1-3wt%。
填料的实例包括玻璃纤维、滑石、云母、纳米粘土。填料的量相对于总组合物典型地是0-40wt%、例如5-30wt%或10-25wt%。
因此,在一些实施方案中,该组合物进一步包含0-5wt%的添加剂和0-40wt%的填料。
该热塑性组合物可以通过将该热塑性聚合物任选地与任何其他任选的组分熔融混合来获得。
优选地,该热塑性聚合物和任选的添加剂和任选的填料的总量相对于总热塑性聚合物组合物是100wt%。
在一些实施方案中,相对于热塑性聚合物组合物中存在的聚合物的总量,聚乙烯的总量是至少95wt%、至少98wt%、至少99wt%或100wt%。
在一些实施方案中,相对于总热塑性聚合物组合物,聚乙烯的总量是至少90wt%、至少95wt%、至少98wt%、至少99wt%或100wt%。
方法步骤
该热塑性聚合物组合物可以通过任何已知的方法如挤出或注塑来成形为管(步骤a1)。双轴伸长(步骤a2)可以通过任何已知的方法进行。
将热塑性聚合物组合物成形为管和双轴伸长该管的方法描述在US6325959中:
一种用于挤出塑料管道的常规装置包含挤出机、喷嘴、校正设备、冷却装置、牵引设备和用于切割或盘绕管道的设备。通过熔融的聚合物物质在其从挤出机穿过喷嘴和直到校正的路径上冷却和使成品管道在管道轴向方向上经历剪切和伸长等,将获得在其轴向方向上基本上单轴取向的管道。有助于该聚合物材料在材料流动方向上取向的另一原因是管道可以经历与制造相关的拉力。
为了实现双轴取向,该装置可以在牵引设备下游补充用于将管道温度控制到适于管道的双轴取向的温度的设备、取向设备、校正设备、冷却设备和将该双轴取向管道供给到切割设备或盘管的牵引设备。
双轴取向还可以在挤出后以与第一校正直接相连的方式进行,在此情况下上述补充装置在第一校正设备之后。
管道的双轴取向可以以各种方式进行,例如借助于内部心轴机械地进行,或通过内部加压流体如空气或水等进行。另一方法是借助于辊来取向管道,例如通过将管道放置在心轴上并且相对于接合该管道的一个或多个压力辊旋转心轴和管道,或经由内部排列的相对于抵靠外部排列的模具或校正设备的管道旋转的压力辊进行。
步骤a2)的条件
优选地,步骤a2)在比该热塑性聚合物组合物的熔点低1-30℃、例如比该热塑性聚合物组合物的熔点低2-20℃或3-10℃的拉制温度下进行。当针对热塑性聚合物组合物可以测量大于一个熔点时,步骤b)优选在比该热塑性聚合物组合物的最高熔点低1-30℃,例如比该热塑性聚合物组合物的最高熔点低2-20℃或3-10℃的拉制温度下进行。
在该热塑性聚合物包含HDPE的实施方案中,步骤a2)也可以在比HDPE的熔点低1-30℃、例如比HDPE的熔点低2-20℃或3-10℃的拉制温度下进行。
在一些实施方案中,步骤a2)在115-123℃的拉制温度下进行。
优选地,轴向拉伸比是1.1-5。优选地,轴向拉伸比是至少1.2、至少1.3、至少1.5或至少1.8和/或至多4.0、至多3.5、至多3.2、至多3.0、至多2.8或至多2.5。优选地,平均环向拉伸比是至少1.2或至少1.3和/或至多1.8或至多1.6。
经拉制管道的轴向拉伸比定义为起始各向同性管的横截面积与双轴取向管道(即产品)的横截面积之比,即,
OD表示外径和ID表示内径。
平均环向拉伸比可以定义为:
其中
双轴取向管道
步骤a)的双轴取向管道可以是压力管道或非压力管道。优选的管道是压力管道。
该双轴取向管道可以典型的具有0.3mm-100mm的厚度。该双轴取向管道可以典型地具有2mm-2000mm的外径。在一些实例中,该双轴取向管道具有2mm-10mm的外径和0.3mm-2mm的厚度。在一些实施例中,该双轴取向管道具有10mm-100mm的外径和1mm-3mm的厚度。在一些实施例中,该双轴取向管道具有100mm-500mm的外径和1mm-10mm的厚度。在一些实施例中,该双轴取向管道具有500mm-2000mm的外径和5mm-100mm的厚度。
在一些实施例中,该双轴取向管道具有32mm-110mm的外径和3mm-10mm的厚度。合适的步骤a)的双轴取向管道的实例具有以下外径和内径以及壁厚。
外径(mm) 内径(mm) 壁厚(mm)
110 90 10.0
90 73.6 8.2
75 61.4 6.8
63 51.4 5.8
32 26 3.0
步骤b)和步骤c)
在步骤b)中,将插入件置于该管道的端部内。
在步骤c)中,加热该端部,以使得该端部轴向收缩,同时该端部横截面的内圆周基本上得以保持。由此获得了具有增厚端部的经改性双轴取向管道。
步骤c)可以包括从该端部内部和/或外部加热该端部。已经发现从端部内部加热降低了在内表面处的轴取向度和圆周取向度,但是圆周取向度在外表面处得以大部分保持。类似地,从端部的外部加热降低了外表面处的轴取向度和圆周取向度,但是圆周取向度在内表面处得以大部分保持。
当高生产速度是重要的时候,优选从该端部的内部和外部加热该端部。
加热的位置影响取向在哪里被保持。仅从端部的内部加热或仅从端部外部加热可以用于影响取向度。当保持取向度是重要的时候,该端部优选仅从该端部的外部加热。在圆周方向上的取向度典型地在内表面处高于外表面。因此,取向度的降低对内表面的影响大于外表面。通过避免从端部的内部加热,在内表面处的圆周取向得以保持。
当该端部是至少从端部内部加热的时候,步骤c)优选包括加热该插入件的至少部分。
在一些实施方案中,该插入件包含热传导部分和隔热部分。在这种情况下,步骤b)包括将插入件置于该管道中,以使得热传导部分比隔热部分更靠近该管道端部的对接端。这可以典型地通过放置该插入件以使得热传导部分的端部与该管道端部的对接端齐平来进行。步骤c)包括仅加热该插入件的热传导部分。该隔热部分可以合适地由金属如钢制成。该隔热部分可以例如由尼龙制成。
优选地,在步骤c)中,该端部的热传导部分在处于或高于拉制温度的温度下加热。步骤c)中的加热温度可以例如最多比拉制温度高5℃。
优选地,该增厚端部的厚度是该端部初始厚度的110-250%。
优选地,该增厚端部具有通过ASTM D2290测量的初始管道的端部的最小极限拉伸载荷的至少80%、优选至少90%、更优选至少100%的最小极限拉伸载荷。
经改性的管道
本发明还涉及通过根据本发明的改性方法可获得或获得的经改性双轴取向管道。
管道连接方法
本发明提供一种管道连接方法。在步骤I)中,进行根据本发明的改性方法以获得第一经改性双轴取向管道和第二经改性双轴取向管道。在步骤II)中,将该第一双轴取向管道的增厚端部的对接端和该第二双轴取向管道的增厚端部的对接端连接。这可以包括对接焊、溶剂连接或电熔合。
对接焊包括将管道的端部加热到高于管道材料的熔点并且连接对接端,随后冷却。
在溶剂粘接中,施用可以在室温下暂时溶解聚合物的溶剂。连接溶解的对接端。给定足够的时间,溶剂将渗透穿过该聚合物并且渗出进入环境中,以使得链失去其移动性。
电熔合描述在Atkinson等,POLYM ENG SCI.,1989,第29卷,第23期,第1638-1641页中。
经连接的管道
本发明还涉及通过根据本发明的管道连接方法可获得或获得的经连接的管道。
本发明还涉及一种经连接的管道,其包含两个双轴取向管道和在这两个双轴取向管道之间的接头部分,其中该双轴取向管道具有2mm-2000mm的外径和0.3mm-100mm的厚度,并且通过以1.1-5.0的轴向伸比和1.1-2.0的环向拉伸比拉制由热塑性聚合物组合物制成的管来获得,
其中该接头部分由与该管相同的热塑性聚合物组合物制成,
其中该两个双轴取向管道和接头部分具有相同的内径,和
该接头部分具有比双轴取向管道更大的厚度。
优选地,该接头部分的厚度是该双轴取向管道厚度的110-250%。
优选地,该接头部分具有根据ASTM D2290测量的双轴取向管道的最小极限拉伸载荷的至少80%、优选至少90%、更优选至少100%的最小极限拉伸载荷。
用途
本发明还涉及根据本发明的经连接的管道用于压力管道的用途,该压力管道用于气体、水和工业应用或建筑和施工应用如脚手架和屋顶支架。
要注意的是本发明涉及本文所述特征的所有可能的组合、特别优选的是权利要求中所提出的特征的组合的那些。因此将理解本文描述了与根据本发明组合物有关的特征的所有组合;与根据本发明方法有关的特征的所有组合以及与根据本发明组合物有关的特征和与根据本发明方法有关的特征的所有组合。
进一步要注意的是术语“包含(包括)”不排除存在其他元素。然而,还要理解的是对于包含某些组分的产品/组合物的描述还公开了由这些组分组成的产品/组合物。由这些组分组成的产品/组合物可以是有利的,这在于其提供了更简单、更经济的方法以制备该产品/组合物。类似地,还要理解的是对于包含某些步骤的方法的描述还公开了由这些步骤组成的方法。由这些步骤组成的方法可以是有利地,这在于其提供了更简单、更经济的方法。
当针对参数的下限和上限提及值时,由下限值和上限值组合而成的范围也理解为被公开了。
本发明现在借助于以下实施例来说明,但是不限于此。
实施例
制备口模拉制的管道
将外径60mm和内径25mm的圆形HDPE管熔融挤出。这些厚各向同性管在出口直径59mm的锥形心轴上在120℃的温度下拉制。
双轴取向管道使用分批口模拉制设施生产。一系列的外径64.9(±0.8)mm和内径56.6(±0.3)mm的双轴取向管道通过以约3.5的轴向拉伸比和约1.4的平均环向拉伸比拉制来制备。
制备增厚端部
将外径与经取向的管道内径相同的圆柱形插入件置于双轴取向管道的一端内部。该插入件由连接在一起的钢制圆柱和尼龙制圆柱来制造。将该插入件插入经取向的管道中,以使得该钢柱的端部与对接端平齐。将该钢柱加热到130-140℃,接近于HDPE管道材料的熔融温度,同时在钢柱附近的管道的其余部分在尼龙柱上方保持远低于该温度。这种设置显示在图1和2中。图1和2示出了分别在时刻t=0和t=10分钟时用于制备管道端部的加热工具。
在加热管道端时,该管道端开始轴向收缩,同时内径归因于受插入件约束而保持。该端部的外径和内径从值64.9(±0.8)mm和56.6(±0.3)mm变化到70.6(±0.4)mm和54.5(±0.5)mm。该方法最终导致端部壁厚从4.1mm显著增加到8mm。
爆破压力
管道的爆破压力可以经由Lame关系来计算:
其中P表示爆破压力,S是管道材料的最小极限拉伸强度,D是外管道直径和d是内管道直径。管道材料的最小极限拉伸强度以使用分离盘(split disk)法ASTM D2290测量的管道环向拉伸强度来测量。表1显示了针对不同的管道尺寸值计算的爆破压力的变化,以示出管壁厚的影响。
表1
1)取向部分失去
2)在接头处的取向完全失去
这些计算证明具有高壁厚的接头具有高爆破压力,这将补偿取向的失去。
与加热有关的结晶形态改变
一系列的极图图表来源于对每个样品进行的WAXD实验,样品从该管道横截面内的不同位置制得。
已经发现加热导致在靠近内管道表面的非常窄的区域内取向失去和熔融。在外管道表面处的取向得以保持到较大程度。在轴向方向上比在环向方向上存在更多的取向度下降。

Claims (15)

1.一种用于改性双轴取向管道的改性方法,包括:
a)提供通过在轴向方向上和在圆周方向上拉伸由热塑性聚合物组合物制成的管而制成的双轴取向管道,
b)将插入件置于该管道的端部内,其中该插入件横截面的外圆周基本上匹配该管道横截面的内圆周,和
c)加热该端部,以使得该端部轴向收缩,同时该端部横截面的内圆周基本上得以保持,以获得具有增厚端部的经改性双轴取向管道。
2.根据权利要求1的方法,其中步骤a)包括:
a1)将热塑性聚合物组合物成形为管,和
a2)在轴向方向上以1.1-5.0的轴向拉伸比和在圆周方向上以1.1-2.0的平均环向拉伸比拉伸步骤a1)的该管以获得该双轴取向管道。
3.根据权利要求2的方法,其中步骤a2)包括在比该热塑性聚合物组合物的熔点低1-30℃的拉制温度下拉制该管。
4.根据权利要求3的方法,其中步骤c)包括在处于或高于该拉制温度的温度下加热该端部。
5.根据前述权利要求中任一项的方法,其中从该端部的内部和/或外部加热该端部。
6.根据前述权利要求中任一项的方法,其中该插入件包含热传导部分和隔热部分,其中步骤b)包括将该插入件置于该管道中,以使得该热传导部分比该隔热部分更靠近该管道端部的对接端,和步骤c)包括加热该插入件的热传导部分。
7.根据前述权利要求中任一项的方法,其中该热塑性聚合物选自聚乙烯、聚丙烯、聚氯乙烯、聚酯、聚碳酸酯、聚酰胺、聚缩醛、聚酰亚胺、聚偏二氟乙烯和聚醚醚酮及其组合。
8.根据前述权利要求中任一项的方法,其中该热塑性聚合物包含高密度聚乙烯或无规聚丙烯。
9.根据前述权利要求中任一项的方法,其中该增厚端部具有的厚度是该端部的初始厚度的110-250%。
10.根据前述权利要求中任一项的方法,其中该端部的初始厚度是0.3mm-100mm。
11.根据前述权利要求中任一项的方法,其中该增厚端部具有根据ASTM D2290测量的初始管道端部的最小极限拉伸载荷的至少80%、优选至少90%、更优选至少100%的最小极限拉伸载荷。
12.一种管道连接方法,包括:
I)进行根据权利要求1-11中任一项的改性方法,以获得第一经改性双轴取向管道和第二经改性双轴取向管道,和
II)将该第一双轴取向管道的增厚端部的对接端和该第二双轴取向管道的增厚端部的对接端连接。
13.根据权利要求12的管道连接方法,其中步骤II)包括焊接、溶剂连接或电熔合。
14.一种经连接的管道,其包含两个双轴取向管道和在该两个双轴取向管道之间的接头部分,其中该双轴取向管道具有2mm-2000mm的外径和0.3mm-100mm的厚度,并且通过以1.1-5.0的轴向拉伸比和1.1-2.0的环向拉伸比拉伸由热塑性聚合物组合物制成的管来获得,
其中该接头部分由与该管相同的热塑性聚合物组合物制成,
其中该两个双轴取向管道和该接头部分具有相同的内径,和
该接头部分比该双轴取向管道具有更大的厚度。
15.根据权利要求14的经连接的管道作为压力管道的用途,该压力管道用于气体、水和/或工业应用或建筑和施工应用如脚手架和屋顶支架。
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