CN1137166C - 交联聚合物产品的生产方法 - Google Patents

交联聚合物产品的生产方法 Download PDF

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CN1137166C
CN1137166C CNB008052298A CN00805229A CN1137166C CN 1137166 C CN1137166 C CN 1137166C CN B008052298 A CNB008052298 A CN B008052298A CN 00805229 A CN00805229 A CN 00805229A CN 1137166 C CN1137166 C CN 1137166C
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A·哈霖
M·海文萨罗
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Naiksetorom Holding S A
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92609—Dimensions
    • B29C2948/92657—Volume or quantity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92714—Degree of crosslinking, solidification, crystallinity or homogeneity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
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    • B29K2301/10—Thermosetting resins

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  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

本发明涉及一种制备由硅烷交联的聚合物产品的方法，其中将聚合物、接枝剂、引发剂和交联催化剂以及可能的添加剂加入挤压机中并挤压，然后得到的接枝材料用水和催化剂进行交联得到交联的聚合物产品。根据该方法，用在线的方法测量接枝材料的接枝度，基于得到的结果连续调节进入挤压机的成分的用量以获得希望的接枝度。

Description

交联聚合物产品的生产方法
本发明涉及生产通过硅烷交联的聚合物产品的方法。
本领域已知诸如聚乙烯和其它聚烯烃的聚合物的性质可通过交联改进。例如，如US 3 646 155和US 4 117 195所述，可通过使用过氧化物引发剂、水解硅烷化合物和缩合催化剂交联聚乙烯。所述的方法可通过将聚乙烯、例如过氧化二枯基的过氧化物、例如乙烯基三甲氧基硅烷或乙烯基三乙氧基硅烷的硅烷化合物和例如二月桂酸二丁基锡的缩合催化剂注入挤压机中并挤压，从而得到接枝的产物，其随后有水或水蒸汽存在的缩合条件下处理得到交联的产物。
当追求产品的均匀性时，现有技术的交联方法经常伴有一些缺点。这些问题特别是在连续工艺中出现。例如，当用连续交联工艺生产电缆和导体绝缘层时，生产线很长，得到的产品可能由于质量变化而不能使用。在这种情况下经济损失会是非常可观的。当生产电缆和导体绝缘层时得到性能均一的产品是非常重要的。在使用连续工艺和长生产线生产其它诸如管道的产品时显然也是如此。
当涉及电缆和导体绝缘层时，交联度是特别重要的，因为其直接影响到产品的电学和热变形性质以及长期耐用性能。主要影响交联度的是进入挤压机的成分的量、特定的交联条件、压力和温度以及挤压机的尺寸。例如，当如上述美国专利公开所示通过交联聚乙烯绝缘导体或电缆时，过氧化物引发剂、硅烷化合物和缩合催化剂的量影响交联度。通过改变所述的量可影响绝缘性能。迄今交联度是在实验室中通过在缩合处理后从得到的交联产品取样分析人工确定的。如果交联度不令人满意，就重新调整起始成分的进料以得到需要的产品。然而，问题是在连续生产的反应条件中经常发生不希望的变化，这对最终产品的性能有不利的影响。由于人工分析速度慢，会生成大量低质量的产品，从而导致经济损失。例如，当使电缆和导体绝缘时，生产线很长，如果根据最终产品人工分析得到的结果调整成分的进料，次品量可能非常大。
还应当指出的是游离的硅烷特别对于铝导体有腐蚀性。而过氧化物残余物削弱了塑料的长期稳定性。从而，将这两种所述物质的残留减至最低可提高电缆的长期耐久性能。
现已发现，如果在交联之前的一个更早的步骤对聚合物的接枝度进行测定并由此调整工艺进料的物质的用量，上述缺点可以避免。在交联工艺中作为中间产物得到的接枝聚合物的接枝度必须足够高以获得交联度足够高(大于60％)的最终产物。使用在线方法而不干扰生产过程确定接枝度并基于获得的结果连续调节起始成分的量，可确保制备的产品的性质并降低次品的量。
本发明涉及一种通过硅烷交联的聚合物产品的制备方法，其中将聚合物、硅烷、引发剂和交联催化剂以及可能的添加剂加入挤压机中并挤压，然后用水和催化剂交联得到的接枝物质以得到交联的聚合物产品。该方法的特征在于接枝物质的接枝度用在线方法测定，并且基于得到的结果连续调节加入挤压机中的成分的量从而得到需要的接枝度。
适当地通过测定在接枝产物中游离的和接枝的硅烷的含量确定接枝度。其优选用IR分光光度计采用让物流通过比色杯的方式进行。测定在硅烷的IR光谱中810cm-1处吸收峰面积确定游离硅烷含量，类似地测定1080cm-1处吸收峰确定接枝的硅烷的含量。在校正中使用已知的接枝聚乙烯硅烷混合物，其硅烷含量和相应的接枝物质的硅烷含量通过例如NMR光谱定义。因为在反应中消耗的过氧化物在聚合物硅烷接枝中用作引发剂，过氧化物的量必须适当，起始量约0.1重量％，以使用量约0.8-2重量％的硅烷被有效地接枝，从而在没有硅烷时不发生直接交联干扰接枝。在接枝好的物质中残留的过氧化物的量非常低，几乎不能测出。
此外，通过IR光谱测定1155cm-1处的吸收峰面积可控制过氧化物的含量。用在硅烷的情况下相同的方法进行校正。因为用连续的在线测量方法测定接枝度，可迅速地获得结果，如果需要，还可以迅速地对起始成分的进料给予控制。基于测定的结果，可如下所述用计算机自动地调节起始成分的进料。
调节例如可基于模糊逻辑形的算法。当硅烷/过氧化物混合物进料时和当硅烷和过氧化物分别进料时，测量和调节的例子如下所示。
实施例1  加入已经混合的硅烷/过氧化物混合物
测量(量)   控制(量)
接枝的硅烷   游离的硅烷   游离的过氧化物   加入硅烷/过氧化物混合物
低低低低高高高高高   低低高高低低低高高   低高低高低高高低高   加稍加稍加停止好稍减稍减稍减减
实施例2  分别加入硅烷和过氧化物
测量(量) 控制(量)
接枝的硅烷   游离的硅烷   游离的过氧化物   加入硅烷   加入过氧化物
低低低低高高高高   低低高高低低高高   低高低高低高低高   加加好停止好好减减   加-加停止好减好减
通常交联的、其接枝度可用本发明方法调节的聚合物是聚烯烃，优选聚乙烯和聚丙烯。交联的产品优选是电缆或导体绝缘层、塑料管或型材。交联催化剂优选二月桂酸二丁基锡。水解的硅烷化合物，优选乙烯基三甲氧基硅烷用作接枝剂，引发剂通常为过氧化物，优选过氧化二枯基。常规的添加剂包括抗氧化剂和着色剂。
接枝后用水和催化剂交联物质。在聚合物产品充分冷却后立即在运行中再次测定交联度，例如通过使用热力学分析仪测定材料的弹性。当进行测定时，薄测试头以恒定的负载压在交联的材料上，取决于聚合物的交联度、温度和测定头上荷载的弹性偏离的大小被记录下来。将记录的偏离值与在相同温度下测定的相应物质的校准曲线比较，从而得出与偏离相应的交联度。将由交联度测定和接枝度测定值以及其它测定的操作参数得到的信息结合起来得出对与最终产物质量相关的生产工艺的反馈。对与最终产品质量相关的生产工艺的反馈使其能更早地发现正确的不同原料的操作参数并能实现生产线的自动质量控制。
以最简单的方式，热力学分析仪可由两个置于电缆或另一聚合物产品相对两侧运行的两个轮子构成，它们对同一样品加压，一个轮子用已知压力加压，测量产品中由于轮子加压产生的偏离，热力学分析仪还包括记录偏离和材料温度的记录装置。仪器的例子仅用于说明一种在运行期间在线测定产品弹性的方法，这个例子不对本发明的范围构成限制。

Claims (12)

1.一种制备由硅烷交联的聚合物产品的方法，其中将聚合物、接枝剂、引发剂和交联催化剂以及可能的添加剂加入挤压机中并挤压，然后得到的接枝材料用水和催化剂进行交联得到交联的聚合物产品，其中用在线的方法控制接枝材料的接枝度，该方法的特征在于在接枝后测定流程中影响接枝度的成分的浓度，基于得到的结果连续调节进入挤压机的成分的用量以获得希望的接枝度。
2.根据权利要求1的方法，其特征在于用IR光谱测定法测定浓度。
3.根据权利要求1或2的方法，其特征在于还测定交联聚合物产品的交联度。
4.根据权利要求1-3中任一项的方法，其特征在于用热力学分析仪测定交联度。
5.根据权利要求1-4中任一项的方法，其特征在于使用聚合物是聚乙烯。
6.根据权利要求1-4中任一项的方法，其特征在于使用接枝剂是硅烷化合物。
7.根据权利要求6的方法，其特征在于使用硅烷化合物是乙烯基三甲氧基硅烷。
8.根据权利要求1-7中任一项的方法，其特征在于使用引发剂是过氧化物。
9.根据权利要求8的方法，其特征在于使用过氧化二枯基作为引发剂。
10.根据权利要求1-8中任一项的方法，其特征在于使用二月桂酸二丁基锡作为交联催化剂。
11.根据权利要求1-10中任一项的方法，其中接枝产品是电缆或导体绝缘层。
12.根据权利要求1-11中任一项的方法，其中接枝产品是管子。
CNB008052298A 1999-03-18 2000-03-17 交联聚合物产品的生产方法 Expired - Fee Related CN1137166C (zh)

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EP1541601A1 (en) * 2003-12-09 2005-06-15 SOLVAY (Société Anonyme) Improved process for producing silane crosslinked polyethylene
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DE102007026751A1 (de) * 2007-06-09 2008-12-11 Inoex Gmbh Verfahren zur Herstellung von peroxidvernetzten Polyethylen-Rohren in einer Extrusionslinie
CN105440215A (zh) * 2014-08-25 2016-03-30 蒋小华 一种硅烷交联聚乙烯电缆料的制备工艺
EP3339366A1 (en) 2016-12-22 2018-06-27 Borealis AG A crosslinkable polyolefin composition
EP3409701A1 (en) 2017-05-31 2018-12-05 Borealis AG A crosslinkable propylene polymer composition
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