[go: up one dir, main page]

CN1046297C - 制备交联铸塑聚合物产物的方法及设备 - Google Patents

制备交联铸塑聚合物产物的方法及设备 Download PDF

Info

Publication number
CN1046297C
CN1046297C CN94192176A CN94192176A CN1046297C CN 1046297 C CN1046297 C CN 1046297C CN 94192176 A CN94192176 A CN 94192176A CN 94192176 A CN94192176 A CN 94192176A CN 1046297 C CN1046297 C CN 1046297C
Authority
CN
China
Prior art keywords
polymer
crosslinked
fluid additive
liquid
cross
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN94192176A
Other languages
English (en)
Other versions
CN1124032A (zh
Inventor
W·科伯特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rustige Bernhard GmbH and Co KG
Original Assignee
Rustige Bernhard GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6486181&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1046297(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rustige Bernhard GmbH and Co KG filed Critical Rustige Bernhard GmbH and Co KG
Publication of CN1124032A publication Critical patent/CN1124032A/zh
Application granted granted Critical
Publication of CN1046297C publication Critical patent/CN1046297C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/565—Mixing liquids with solids by introducing liquids in solid material, e.g. to obtain slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/71—Feed mechanisms
    • B01F35/717—Feed mechanisms characterised by the means for feeding the components to the mixer
    • B01F35/7176—Feed mechanisms characterised by the means for feeding the components to the mixer using pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/94—Liquid charges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • 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
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/29—Feeding the extrusion material to the extruder in liquid form
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients

Landscapes

  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)

Abstract

本发明是一种制备交联铸塑聚合物产物的方法，其中所要交联的聚合物以颗粒或粉末形式与液体添加剂通过铸塑进行加工，其特征是：使用具有裂纹的多孔表面的聚合物颗粒或聚合物粉末。这种表面结构不规则的聚合物颗粒/聚合物粉末经输送管道输送到混合区，把至少一种用于聚合物交联的液体添加剂注入其中并在后续的连续浇铸设备中加工混合物。在加工期间会在聚合物粒子周围形成较好的液体分布、交联剂的均匀接枝并因而有交联均匀的产物。

Description

制备交联铸塑聚合物产物的方法及设备
本发明涉及一种制备交联铸塑聚合物产物的方法，以及一种实施这种方法的设备，其中所要交联的聚合物以颗粒或粉末形式与液体添加剂通过铸塑进行加工。
从DE-OS 2554525中可知一种制备交联铸塑聚合物产物的方法及设备，其中所要交联的聚合物经过挤压机给料斗输送到螺杆式挤压机并把其它的为交联所必需的组份以液体形式注入到给料斗的下部或直接注入到挤压机的颈段。
对于聚合物的完全和均匀的交联重要的是，把全部组份进行充分的混合。然而用至今已知的手段这种混合还无法令人满意地加以解决。仅仅把一定的组份注入到存在于挤压机给料斗或挤压机颈段的聚合物中只会在注入处周围形成高的添加物浓度。紧接着必须把挤压机中的反应混合物甚至在均化时还要通过一设计昂贵的挤压机螺杆进行混合。因此出现了对好的交联不利的条件并且此外需要一设计昂贵和制造费用高的挤压机螺杆。
此外表明，加工传统的塑料颗粒时，在为进行交联注入必要的添加剂时会出现颗粒表面湿润不充分，这会有很大的缺点。尽管通过在把物料送入挤压机螺杆前安装一搅拌器以便通过此种方式把颗粒充分混合和湿润，进行试验以克服此缺点。然而已表明，常用的颗粒因为其光洁表面和相对较大的体积难以湿润。由此产生了缺点，即直到物料熔融阶段液体组分同挤压机螺杆中的聚合物颗粒分离地被运送，这会引起局部液体堆积并从而出现浓度差异，这最后会严重影响由此制备的物料的均匀性。
US 4,703,093介绍了聚合物与其它物质的加工和交联的改进方法。在此碾碎和加热该聚合物以增大表面和在表面形成裂纹。通过碾碎和加热聚合物对交联物质的吸收能力得以提高。在聚合物颗粒与交联物质混合后进行冷却。
尽管混合物被加热以提高其反应能力，但在改进的方法中聚合物与添加物质或交联物质的混合还不足够达到这些物质的较好的彻底混合。
在此本发明的任务是，改进开始时提到的技术的方法和设备，从而使颗粒较好地湿润并因而较好混合直到熔融。
解决提到的任务是通过本发明的制备交联铸塑聚合物产物的方法，其中所要交联的聚合物同液体添加剂通过铸塑进行加工，其特征是，使用一种具有裂纹多孔表面的聚合物颗粒或聚合物粉末。
这时优选使用聚乙烯用于交联。使用密度为约0.89-1g/cm3的聚合物颗粒/聚合物粉末(特别是聚乙烯)是特别好的。聚合物料的粒度适宜为约10μm-2mm。
在实施本方法时所要交联的具有裂纹多孔表面的聚合物颗粒/聚合物粉末经输送装置送到混合区，混合区中至少注入一种液体添加剂用于聚合物交联，并且混合物在后续的连续浇铸设备中加工。
此外本方法的优点是，除液体添加剂外也可加入其它液体物质，如稳定剂及类似物质。
以特殊的实施形式具有裂纹的多孔表面的聚乙烯物料在添加可水解的不饱和硅烷下通过硅烷醇缩合反应进行交联。
但是这不仅存在聚乙烯物料的硅烷交联，而且根据本发明聚乙烯物料在添加过氧化物下还可进行自由基交联。
通过使用具有裂纹的多孔表面的聚合物颗粒/聚合物粉末，为加入到体系中的液体添加剂提供一个有吸收能力的、开孔的、液体能灌入的大表面，以便据此保证有最佳的混合。到目前为止使用的聚合物颗粒在有相对较大的粒度时总具有光洁的表面，很小的吸收能力并因此而难以湿润。因此在聚合物的交联反应中，在使用目前常用的具有光洁表面和相对较大的、3-4mm的粒度的颗粒的情况下甚至会出现加入到挤压机中的液体的压出，这同不利的浓度差异有关。
在本发明方法范围内使用的新型聚合物材料具有多裂纹的对液体强吸收的表面，是一种颗粒或粉末，可通过特殊的聚合过程制备。优选地该材料由聚乙烯或也可以是其它烯烃聚合物或其改性产物组成。这样的聚合物颗粒/聚合物粉末例如由Montecatini公司出售，名称是“Spherilene”。这类聚合物在使用一种具有随后除气措施的流动床气相反应器的条件下，在除去全部单体组份下进行制备，并且不经过目前常用的造粒措施(会形成光洁球形表面)的情况下使用在本发明方法中。因此该材料根据目前的概念是一种半成品(Vorpro-dukt)，然而它可直接在本方法中使用，从节省多余的工艺措施和费用上考虑，这还有其它的优点。
基于所要交联的物料的不规则的、有吸收能力的、开孔的和对液体强吸收的表面，该表面以理想的方式适合于粘合和输送液体，此外的优点是，计量加入的液体添加剂比在使用传统光洁聚合物颗粒中必需的添加剂的量少。通过本发明所使用的聚合物材料的特殊类型的表面构造可保证在颗粒中有对液体更好的吸收，因此而有更好的分布，并且不会发生液体流失。
本发明的改进在于，基于节省费用或方法技术原因不仅使用本发明的表面多孔的聚合物颗粒/聚合物粉末作为本方法的起始材料，而且使用任意混合比的根据本发明的多孔聚合物颗粒与传统的无裂纹的聚合物料的混合物。也能根据需要使用一种起始材料，该起始材料料只含有一定百分比的有裂纹的多孔聚合物料。
适合于实施本发明方法的设备是由一种聚合物材料的输送装置、一种用于至少一种添加剂的输送的装置和一种连续浇铸设备组成，其中在聚合物颗粒/聚合物粉末的输送装置3和连续浇铸设备2之间有一混合装置4，该装置4通到用于至少一种液体添加剂的输送装置5,6,7。
也可用入口套管18代替混合装置4。
下面的图形用于进一步解释本发明，其中
图1：图解一种根据第一个实施形式用于实施本发明方法的设备，
图2：图解一种根据图1设备的改进实施形式，
图3：根据现有技术的液体和颗粒的分布，
图4：根据本发明的液体和聚合物粒子的分布，和
图5：本发明的聚合物颗粒的断面放大图。
图1中简要图解本发明的挤压设备的构造：有一螺杆挤压机2，一装在挤压机2上的用于装载表面有裂纹的多孔的聚合物颗粒/聚合物粉末(优选聚乙烯)的给料斗3和一装在给料斗3和挤压机2之间的混合器4。在混合器4中还通有一个来自计量泵装置5的用于注入液体添加剂(特别是硅烷溶液)的输送管道6，该管道6经过一注入喷嘴7通到混合器4的内部。
容器4的内部装有一搅拌棒8，可通过一传动装置9进行驱动。螺杆挤压机2是塑料挤压中常用的挤压机，其螺杆总的长度直径比(长度/直径)为26∶1。所要加工的聚合物反应混合物直接由上面的搅拌器4已经最佳预混地加到螺杆挤压机2中。
图2表示一种改进的实施形式，据此从计量泵装置5经输送管道6输送的液体添加剂直接注入到装在给料斗3下面的入口套管18中。
图3表示根据现有技术存在的液体在聚合物颗粒11周围的分布情况。由此可见，相对较大的有光洁表面的颗粒粒子11隔断了液体12。颗粒的光洁表面不适合粘合液体12，因此在颗粒11的间隙里富集大量的液体并且很难湿润颗粒的表面。用这种方式可解释已知的上述的未充分混合和浓度差异的缺点。
图4表示用液体14湿润的、本发明使用的多裂纹聚合物粒子的排列。与目前使用的颗粒相比小得多的颗粒粒子或粉末粒子具有不规则的表面，这样液体14以最佳方式富集在聚合物粒子13周围，并且以这种方式液体14一方面借助于聚合物粒子13在间隙中被运载和另一方面在聚合物粒子中进行自身浸润并在此沉积。
这尤其清楚地表示在图5中，其中表示了聚合物粒子13的断面。在不规则地形成的表面以下，即也是在聚合物粒子13的内部液体形成一个液体浸润边界17。基于这种粘合液体以最佳方式沉积在表面15上并形成一个置于外部的液体表面16。因此在聚合物粒子上形成一个均匀分布的液体沉积层，该沉积层到目前为止还无法得到。
在实施本发明方法时注入到混合器4或入口套管18中的液体与来自给料斗的具有多裂纹的不规则结构的和因而较大的表面的聚合物颗粒/聚合物粉末进行混合。在粒子周围形成最佳的液体沉积层，并且混合物然后以均匀分布的形式加入到螺杆挤压机2中，在挤压机中在全部物料的高度彻底混合下进行进一步的加工。
基于本发明得到的最佳液体分布在交联反应前的加工中会导致均匀的接枝。在接枝反应中适合于交联的分子(例如硅烷分子)在聚合物基体上(例如聚乙烯)进行接枝。通过本发明的措施，由于较好的液体分布会形成均匀的接枝反应，因此下面的交联会进行得特别均匀，并且最终产物的质量大大提高。
下面对硅烷交联或过氧化物交联各举出一个实施例。但该实施例不能理解为对本发明的限制。硅烷交联：起始物料：Spherilene
      密度：0.926g/cin3
      MIFI 190℃/2.16kp=2.8g/10分钟
      堆比重：370g/l液体添加剂：乙烯基三甲氧硅烷
        过氧化二枯基(DI-CUP)
        二月桂酸二丁基锡(DBTDL)
        稳定剂混合物：98.2％ Spherilene
     1.8％液体添加剂设备：用于Spherilene和液体添加剂的重量
  测量的定量配料器，带有搅拌器。螺杆
  长度为25D的均化效果好的挤压机。加工：挤压机上的温度分布170、190、210、
  220℃；模具上的温度分布220-230℃产品：带有铜线的电缆检验结果：根据ISO R 527的抗拉强度：21.4MPa
      根据ISO R 527的撕裂伸长：526％
      根据ICE 811.2-1的热膨胀：60％/0％。过氧化物交联：起始物料：Spherilene
      密度：0.926g/cm3
      MIFI 190℃/2.16kp=2.8g/10分钟
      堆比重：370g/l液体添加剂：过氧化-叔丁基-枯基
        抗氧化剂混合物A:1.0％过氧化-叔丁基-枯基
    0.6％抗氧化剂
    98.4％ Spherilene混合物B:1.2％过氧化-叔丁基-枯基
    0.6％抗氧化剂
    98.2％ Spherilene混合物C:1.5％过氧化-叔丁基-枯基
    0.6％抗氧剂
    97.9％ Spherilene设备：布雷本登密炼机(Brabender)/压力机加工：在140℃的布雷本登密炼机(Brabender)上加工10分钟
    在120bar压力和190℃加工12分钟产品：片材检验结果 混合物A：根据ISO R 527的抗拉强度：20.3MPa；
         根据ISO R 527的撕裂伸长：566％；
         根据ICE 811.2-1的热膨胀：125％/15％检验结果 混合物B：根据ISO R 527的抗拉强度：25.2MPa；
         根据ISO R 527的撕裂伸长：562％；
         根据ICE 811.2-1的热膨胀：45％/0％检验结果 混合物C：根据ISO R 527的抗拉强度：26.0MPa；
         根据ISO R 527的撕裂伸长：575％；
         根据ICE 811.2-1的热膨胀：25％/0％

Claims (9)

1．制备一种交联铸塑聚合物产物的方法，其中所要交联的聚合物与液体添加剂通过铸塑进行加工并且该聚合物有多裂纹的表面，其特征是：使用具有多孔表面的聚合物颗粒或聚合物粉末。
2．根据权利要求1的方法，其特征是：把聚乙烯用于交联。
3．根据权利要求1或2的方法，其特征是：把密度为0.89-1g/cm3和粒度为约10μm-2mm的聚合物材料用于交联。
4．根据权利要求1-3的方法，其特征是：所要交联的具有裂纹的多孔的表面的聚合物颗粒或聚合物粉末经输送装置送入到混合区，在混合区注入至少一种用于聚合物交联的液体添加剂并把混合物在后续的连续浇铸设备中加工。
5．根据权利要求1-4的方法，其特征是：具有裂纹的多孔的表面的聚乙烯颗粒或聚乙烯粉末在添加一种可水解的不饱和硅烷的条件下通过硅烷醇缩合反应交联。
6．根据权利要求1-4的方法，其特征是：具有裂纹的多孔的表面的聚乙烯颗粒或聚乙烯粉末在添加一种过氧化物下进行自由基交联。
7．根据权利要求1-6中的一项的方法，其特征是：聚合物颗粒/聚合物粉末输送到混合装置(4)，该混合装置位于聚合物的输送装置和连续浇铸设备(2)之间，并且在混合装置中与至少一种经输送装置(5,6,7)加入的液体添加剂进行混合。
8．根据权利要求7的方法，其特征是：聚合物颗粒/聚合物粉末与加入的液体添加剂借助于装在混合装置(4)中的搅拌装置(8)进行混合。
9．根据权利要求1-6中的一项的方法，其特征是：聚合物颗粒/聚合物粉末与至少一种经输送装置(5,6,7)加入的液体添加剂进行混合，其中液体添加剂的输送是在聚合物的输送设备和连续浇铸设备(2)之间进行。
CN94192176A 1993-04-23 1994-04-14 制备交联铸塑聚合物产物的方法及设备 Expired - Fee Related CN1046297C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4313290.1 1993-04-23
DE4313290A DE4313290A1 (de) 1993-04-23 1993-04-23 Verfahren und Vorrichtung zur Herstellung eines vernetzten extrudierten Polymerproduktes

Publications (2)

Publication Number Publication Date
CN1124032A CN1124032A (zh) 1996-06-05
CN1046297C true CN1046297C (zh) 1999-11-10

Family

ID=6486181

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94192176A Expired - Fee Related CN1046297C (zh) 1993-04-23 1994-04-14 制备交联铸塑聚合物产物的方法及设备

Country Status (13)

Country Link
US (1) US5744553A (zh)
EP (1) EP0695320B2 (zh)
JP (1) JP3266201B2 (zh)
KR (1) KR100274264B1 (zh)
CN (1) CN1046297C (zh)
AT (1) ATE154052T1 (zh)
CH (1) CH685931A5 (zh)
DE (2) DE4313290A1 (zh)
DK (1) DK0695320T4 (zh)
ES (1) ES2105692T5 (zh)
GR (1) GR3024583T3 (zh)
PL (1) PL173553B1 (zh)
WO (1) WO1994025509A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106166804A (zh) * 2016-10-14 2016-11-30 江苏华兴橡胶科技有限公司 一种再生胶用粗炼塑化系统及其粗炼方法

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19724317C1 (de) * 1997-06-10 1998-08-27 Pcd Polymere Ag Segmentierte Polyolefine
US5972267A (en) * 1998-03-30 1999-10-26 Union Carbide Chemicals & Plastics Technology Corporation Process for the production of a thermosetting composition
DE19824958B4 (de) * 1998-06-03 2004-02-05 Werner Kempter Verfahren zur Herstellung eines vernetzten, extrudierten Polymerproduktes
AU744802B2 (en) 1998-06-22 2002-03-07 General Electric Company Silane vulcanized thermoplastic elastomers
DK1148518T3 (da) * 2000-04-17 2004-02-23 Nexans Fremgangsmåde til fremstilling af tværbundne polyethylencoatede ledningstråde
EP1319050A2 (en) * 2000-09-14 2003-06-18 The Lubrizol Corporation Liquid additive spray injection to polymeric powders
US20040028808A1 (en) * 2001-09-13 2004-02-12 Williams Charles F. Liquid additive spray injection to polymeric powders
US7064163B2 (en) * 2002-09-04 2006-06-20 Msi Technology Llc Polyolefin-based adhesive resins and method of making adhesive resins
US7202309B2 (en) * 2003-09-12 2007-04-10 Momentive Performance Materials Inc. Process for crosslinking thermoplastic polymers with silanes employing peroxide blends and the resulting crosslinked thermoplastic polymers
ES2247910B2 (es) * 2004-02-04 2007-02-01 Govoni Iberica, S.A. Procedimiento para la produccion de granza basicamente de polietileno reticulable, directamente extrudible, e instalacion para la realizacion del mismo.
DK1771500T3 (da) * 2004-07-30 2008-06-02 Silon S R O Plana Nad Lu Znici Fremgangsmåde til blanding af et kunststofgranulat med et additiv samt blandeanordning til udförelse af fremgangsmåden og indretning med blandeanordningen
US7326753B2 (en) * 2005-02-08 2008-02-05 Momentive Performance Materials Inc. Process for the production of crosslinked polymer employing low VOC-producing silane crosslinker and resulting crosslinked polymer
US7810986B2 (en) * 2005-11-21 2010-10-12 Process Control Corporation Systems and methods for liquid dosing of material in a blender system
EP2069424A2 (de) * 2006-10-04 2009-06-17 Silon s.r.o. Planá nad Lu'znici Verfahren zur herstellung eines vorzugsweise vernetzten, extrudierten polymerproduktes
US20080114134A1 (en) * 2006-11-14 2008-05-15 General Electric Company Process for crosslinking thermoplastic polymers with silanes employing peroxide blends, the resulting crosslinked thermoplastic polymer composition and articles made therefrom
AT504709B1 (de) 2006-11-23 2008-09-15 Erema Verfahren und vorrichtung zur einbringung von zusatzstoffen

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB863732A (en) * 1958-04-18 1961-03-22 Phillips Petroleum Co Method of dispersing additives in solid polymers
DE2411141A1 (de) * 1974-03-08 1975-09-18 Kabel Metallwerke Ghh Verfahren zur herstellung von umhuellungen aus in anwesenheit von fluessigkeit vernetzbaren thermoplasten fuer langgestrecktes gut
DE3035709A1 (de) † 1978-07-21 1982-04-29 Kabel- und Metallwerke Gutehoffnungshütte AG, 3000 Hannover Verfahren zur herstellung von extrudierbaren und feuchtigkeitsvernetzbaren mischungen
IT1099761B (it) * 1978-10-05 1985-09-28 Montedison Spa Procedimento per ottenere composizioni omogenee di polimeri olefinici in forma granulare e di additivi vari
DE2856381A1 (de) * 1978-12-27 1980-07-10 Kabel Metallwerke Ghh Verfahren zur aufbereitung gefuellter und vernetzbarer polymerer werkstoffe
US4564349A (en) * 1983-06-01 1986-01-14 Union Carbide Corporation Extruder assembly for extruding water-curable silane modified polymers
US4703093A (en) * 1985-01-16 1987-10-27 Colonial Rubber Works, Inc. Method of preparing a polymer for cross-link rotational molding and a polymer prepared by said method
DE3506164A1 (de) * 1985-02-22 1986-08-28 kabelmetal electro GmbH, 3000 Hannover Verfahren zur herstellung von vernetzbaren mischungen
GB8919895D0 (en) † 1989-09-04 1989-10-18 Du Pont Canada Moisture cross-linking of polymers
US5112919A (en) † 1989-10-30 1992-05-12 Union Carbide Chemicals & Plastics Technology Corporation Solid feeding of silane crosslinking agents into extruder
US5076988A (en) † 1990-03-09 1991-12-31 Union Carbide Chemicals And Plastics Technology Corporation Process for the extrusion of low density polyethylene
NL9000840A (nl) * 1990-04-10 1991-11-01 Wavin Bv Werkwijze en installatie voor het vervaardigen van kunststofvoortbrengsels met behulp van een warm mengsel van pvc-poeder en additieven, alsmede een voor toepassing bij deze werkwijze geschikte warmmenger.
DE4103602A1 (de) * 1991-02-07 1992-08-13 Wacker Chemie Gmbh Verfahren zur kontinuierlichen herstellung von htv-siliconmassen
US5238635A (en) * 1992-04-16 1993-08-24 Himont Incorporated Process for treatment of particulate olefin polymer, resulting treated particles and method for using treating particles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106166804A (zh) * 2016-10-14 2016-11-30 江苏华兴橡胶科技有限公司 一种再生胶用粗炼塑化系统及其粗炼方法
CN106166804B (zh) * 2016-10-14 2019-01-08 江苏华兴橡胶科技有限公司 一种再生胶用粗炼塑化系统及其粗炼方法

Also Published As

Publication number Publication date
US5744553A (en) 1998-04-28
PL173553B1 (pl) 1998-03-31
CN1124032A (zh) 1996-06-05
ES2105692T5 (es) 2002-07-01
WO1994025509A1 (de) 1994-11-10
CH685931A5 (de) 1995-11-15
KR100274264B1 (ko) 2000-12-15
DK0695320T4 (da) 2002-03-11
DK0695320T3 (da) 1997-12-22
DE59403038D1 (de) 1997-07-10
EP0695320B1 (de) 1997-06-04
JP3266201B2 (ja) 2002-03-18
KR960701926A (ko) 1996-03-28
PL311229A1 (en) 1996-02-05
EP0695320A1 (de) 1996-02-07
GR3024583T3 (en) 1997-12-31
DE4313290A1 (de) 1994-10-27
ATE154052T1 (de) 1997-06-15
ES2105692T3 (es) 1997-10-16
JPH08509262A (ja) 1996-10-01
EP0695320B2 (de) 2001-12-12

Similar Documents

Publication Publication Date Title
CN1046297C (zh) 制备交联铸塑聚合物产物的方法及设备
US3931094A (en) Filled thermoplastic containing fibrous dispersion aid
CN1097605C (zh) 官能化α－烯烃的均聚物和共聚物的方法
CN1102883C (zh) 聚合物原料及其制法、pva基塑料制品的制法
US20090130443A1 (en) Fiber pellets, method of making, and use in making fiber reinforced polypropylene composites
US5332308A (en) Process and apparatus for production of plastics containing additives
CN103258610B (zh) 一种磁性塑胶复合材料及其制备方法
CN1549761A (zh) 填充热塑性聚合物的生产方法和装置
CN101423589A (zh) 聚乙烯/马来酸酐熔融接枝高浓缩预混合母料的制备方法
US4015039A (en) Fibrous dispersion aid for thermoplastics
FR2714326A1 (fr) Procédé de traitement d'une poudre de talc en vue de l'incorporer dans une matière, en particulier matière thermoplastique.
WO1994025509B1 (de) Verfahren und vorrichtung zur herstellung eines vernetzten extrudierten polymerproduktes
JPH07164434A (ja) 重合α−オレフィン樹脂を配合する方法
DE60105008T2 (de) Verfahren und vorrichtung zur bereitstellung eines granulatgemisches, und granulatgemisch
CN1256377C (zh) 一种利用高分子废弃物生产的复合材料
CA2149847A1 (en) Process for the production of a filled reaction
US20060073319A1 (en) Method and apparatus for making products from polymer wood fiber composite
CN1629217A (zh) 聚合物——秸杆复合材料管道的生产方法
US4145227A (en) Fibrous dispersion aid for thermoplastics
JP3509750B2 (ja) 植物質食品加工残さ複合成形材料の製造方法及びその複合成形材料を用いた成形方法
US4153762A (en) Process for working additive into polymers, particularly polymers which can be foamed
CA1104282A (en) Fibrous dispersion aid for thermoplastics
CN218659977U (zh) 一种改性塑胶粒挤出设备
JP3327020B2 (ja) ポリオレフィン乳化物の連続製造方法
CN217072987U (zh) 高填充材料生产设备

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 19991110

Termination date: 20100414