CN108864629A - 生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法 - Google Patents

生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法 Download PDF

Info

Publication number
CN108864629A
CN108864629A CN201810453115.4A CN201810453115A CN108864629A CN 108864629 A CN108864629 A CN 108864629A CN 201810453115 A CN201810453115 A CN 201810453115A CN 108864629 A CN108864629 A CN 108864629A
Authority
CN
China
Prior art keywords
melt
melt flow
polyvinyl acetal
plasticizer
viscosity
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.)
Granted
Application number
CN201810453115.4A
Other languages
English (en)
Other versions
CN108864629B (zh
Inventor
D.温茨利克
M.赫特
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.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
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
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of CN108864629A publication Critical patent/CN108864629A/zh
Application granted granted Critical
Publication of CN108864629B publication Critical patent/CN108864629B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
    • 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
    • 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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/72—Feedback means, i.e. part of the molten material being fed back into upstream stages of the extruder
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • C08J3/18—Plasticising macromolecular compounds
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • B29C2948/92009—Measured parameter
    • B29C2948/922—Viscosity; Melt flow index [MFI]; Molecular weight
    • 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
    • B29C2948/92323—Location or phase of measurement
    • B29C2948/92361—Extrusion unit
    • 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
    • B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
    • 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
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/92857—Extrusion unit
    • 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
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • 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
    • B29C2948/92961—Auxiliary unit, e.g. for external melt filtering, re-combining or transfer between units
    • 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
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/14—Polyvinylacetals
    • 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
    • B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
    • B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
    • 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
    • B29K2105/0038—Plasticisers
    • 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
    • B29K2829/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof, as mould material
    • B29K2829/14—Polyvinylacetals
    • 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
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明涉及在150–250°C下挤出包含至少一种聚乙烯醇缩醛和至少一种增塑剂的熔体流的方法，所述熔体流在60–170°C下具有预定的熔体粘度，所述方法特征在于：a)提供至少包含第一增塑剂和第一聚乙烯醇缩醛树脂的第一熔体流并在线测量其在60–170°C下的熔体粘度；b)将一定量的第二增塑剂和/或第二聚乙烯醇缩醛树脂添加到所述第一熔体流中以提供第二熔体流，其在60–170°C下的熔体粘度与60–170°C下的所述预定的熔体粘度具有最多20%的差异。

Description

生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法
技术领域
本发明涉及使用回环(loop-back)在线熔体粘度控制通过挤出来生产基于增塑聚乙烯醇缩醛的膜的方法。
背景技术
早已知晓通过挤出来生产基于增塑聚乙烯醇缩醛的夹层膜的各种变体。这些挤出方法的共同点是将包含增塑聚乙烯醇缩醛(通常是增塑聚乙烯醇缩丁醛)的熔体通过薄模头挤出，以生产熔膜。随后通过在空气和/或水中冷却来固定或“冷冻”该熔膜的形状。在挤出过程中的熔体温度通常在150-250℃范围内。
为了制备玻璃层压件，将由此生产的膜置于玻璃片之间，以产生堆叠件(stack)，随后使该堆叠件经受升高的温度和压力。在层压过程中或之前，通过压力从该堆叠件中除去空气，或使空气物理溶解在PVB膜中。这种所谓的除气方法可由PVB膜赋予，所述膜在层压条件下具有过高的粘度，导致可见的气穴，尤其在层压件的边缘区域中。具有可见的气穴的玻璃层压件将不被消费者接受，并需要被丢弃。
因为聚乙烯醇缩醛树脂的化学组成(chemistry)以及由此的粘度在某些范围内变化，挤出的增塑聚乙烯醇缩醛在层压条件下的熔体粘度也变化。例如，图1显示了增塑聚乙烯醇缩醛树脂的MFR值的高斯分布，所述值使用21.6kg在100℃下测量。因此，所述膜将具有类似的机械性质分布和类似的层压性质(即，层压条件下的熔体粘度)分布。
为了调节粘度水平或使粘度分布缩窄，可行的是将具有不同摩尔质量和/或支化结构和/或不同量的增塑剂的两种等级的聚乙烯醇缩醛混合。用于调节粘度水平的实例例如在US2014/0275390中给出。此处显示了如何通过使用过氧化氢作为挤出期间的反应剂可降低重均摩尔质量并由此降低粘度。
但是，挤出期间在预定水平上的粘度调节是非常耗时的，因为人们必须测量挤出过程之前树脂的流动行为，并且基于该测量的结果，人们必须计算所添加的具有不同摩尔质量和/或支化结构的聚乙烯醇缩醛的量、增塑剂的量和/或反应剂的量。此外，例如使用振荡或动态模式的流变仪、毛细管流变仪或最简单地，使用MFR设备的细致的流变测量通常需要特定的样品制备，因为例如水分含量显著影响结果。该程序需要长的制备时间，这对于连续挤出过程来说是冗长的。
除了流变测量之外，人们可想到使用特定的挤出参数(如熔体压力)来计算一种或更多种上述组分的所需量，以便调节粘度。但是，发现层压条件下(即在60至160℃的温度范围内)的熔体粘度不能通过众所周知的时间-温度叠加原理由挤出温度下(即在150至250℃的温度范围中)的熔体粘度或由任何相关的工艺参数预测，这表明聚乙烯醇缩醛树脂显示所谓的复杂的热-流变行为。
显然，存在提供一种方法的需要，该方法在增塑聚乙烯醇缩醛在150和250℃之间、优选170和250℃之间的温度下的膜挤出过程中控制60至170℃、优选80-150℃的层压温度下的熔体粘度。
本发明的目的是提供用于增塑聚乙烯醇缩醛膜的挤出方法，其中所述膜的粘度可通过测量层压温度下的熔体的粘度进行调节。
发明内容
因此，本发明涉及在150-250℃、优选170-250℃下挤出包含至少一种聚乙烯醇缩醛和至少一种增塑剂的熔体流的方法，所述熔体流在60-170℃、优选80-150℃下具有预定的熔体粘度，所述方法特征在于：
a)提供至少包含第一增塑剂和第一聚乙烯醇缩醛树脂的第一熔体流并在线测量其在60-170℃、优选80-150℃下的熔体粘度；
b)将一定量的第二增塑剂和/或第二聚乙烯醇缩醛树脂添加到所述第一熔体流中以提供第二熔体流，其在60-170℃、优选80-150℃下的熔体粘度与80-150℃下的所述预定的熔体粘度具有最多20％、优选最多10％的差异。
例如，作为60或80℃和21.6kg下的MFR值测量的预定的熔体粘度通常在1mg/10min至500mg/10min范围内，并且在150或170℃下用10kg测量的预定的熔体粘度通常在0.1g/10min至20g/10min范围内。
80-150℃下的熔体粘度可作为熔体流动速率(MFR)、熔体体积速率(MVR)、振荡、动态或蠕变模式下的流变学或毛细管流变学来测量。在一个优选的实施方式中，所述粘度作为MFR/MVR或通过毛细管流变仪来测量。
附图简述
图1显示了在100℃下、用21.6kg测量的MFR值的典型分布。
图2给出了本发明方法的概览。1)至少包含第一增塑剂和第一聚乙烯醇缩醛树脂的熔体流；2)用于在80-150℃下的熔体粘度测量的测量装置；3)第二增塑剂和/或第二聚乙烯醇缩醛树脂和/或反应剂的料流；4)1)和3)的组分的混合物，产生80-150℃下具有预定粘度的熔体流。
图3显示不同量的增塑剂对于100℃下、用21.6kg测量的MFR的影响。
具体实施方案
熔体粘度可通过市售可得的在线流变仪来测量。在本发明的方法中，从主流中转移出小的侧流，并通过齿轮泵将其进料至流变仪的毛细管模头(圆环或狭缝)中。该齿轮泵使得能够获得受控且恒定的熔体流量。在毛细管模头远处的第二齿轮泵将聚合物熔体运回主流中。通过使用多于一股侧流或通过改变齿轮泵的转速，可获得各种剪切速率。这使得能够构建剪切速率依赖性粘度曲线。
在所述方法的变体中，将小的侧流加热至比挤出机中的物质温度低的温度，这使得能够进行层压温度下的粘度测量。
可使用在线流变仪测量的具体的流变学参数可为MFR、MVR、压力、剪切粘度、流量比MFR(重量1)/MFR(重量2)、流动指数。
优选在重复过程中将第二增塑剂和/或第二聚乙烯醇缩醛树脂添加到熔体流中，以达到预定的熔体粘度。
不必要使全部的第一熔体流经受60-170℃或80-150℃下的熔体粘度测量。在第一实施方案中，将第一熔体流加热至150-250℃或170-250℃的温度，并将该第一熔体流的一部分分离并冷却至60-170℃或80-150℃，以便测量其在60-170℃或80-150℃下的熔体粘度。
优选地，在分离第一熔体流的一部分之前，将第二增塑剂和/或第二聚乙烯醇缩醛树脂添加到该熔体流中。虽然有可能排出分离的熔体流，但是为了使用全部材料来进行挤出过程，可在测量分离的熔体流在60-170℃或80-150℃下的熔体粘度之后将其与第一熔体流合并。
在本发明的其它实施方案中，第二增塑剂与第一增塑剂相同和/或第二聚乙烯醇缩醛树脂与第一聚乙烯醇缩醛树脂相同。换言之，通过调节增塑剂和聚乙烯醇缩醛树脂之间的比率来调节熔体粘度。因为最终的挤出膜的机械性质很大程度取决于增塑剂含量，所以仅在基于第一熔体流±5重量％、优选±2重量％且最优选±1重量％的增塑剂含量变化范围内使用该实施方案是明智的。
图3中给出了该调整的实例。对于该实验而言，将第一聚乙烯醇缩醛树脂与26.5重量％的增塑剂一起挤出，导致100℃下、用21.6kg测量的MFR值为217mg/10min。通过添加不同量的增塑剂(在实例中为1或2重量％)，可将MFR值调节至预定粘度水平。
在又一实施方案中，通过添加第二聚乙烯醇缩醛树脂来调节熔体粘度，所述第二聚乙烯醇缩醛树脂在80-150℃下具有比所述第一聚乙烯醇缩醛树脂高或低至少5％的熔体粘度。这优选在重复过程中进行。
可在所述过程的任何点(即在挤出机上游或进入挤出机的地方，或甚至在挤出机下游)将第二增塑剂和/或第二聚乙烯醇缩醛树脂添加至第一熔体中，条件是确保各组分的充分混合。
本发明的另一目的是提供用于包含多于一层增塑聚乙烯醇缩醛的膜的挤出方法，其中至少一层的粘度可通过测量层压温度下熔体的粘度来调节。
应注意熔体流的数量不受限制，但是实际上将三、四或五层共挤出成一张最终的膜。
在本发明方法的一个实施方案中，将具有不同组成的至少两股熔体流彼此接触挤出，并且其中根据步骤a)和b)，至少一股熔体流在60-170℃下具有预定的熔体粘度。
在本发明方法的另一实施方案中，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，外部熔体流在60-170℃下具有预定的熔体粘度。
在本发明方法的另一实施方案中，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，内部熔体流在60-170℃下具有预定的熔体粘度。
在本发明方法的另一实施方案中，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，熔体流在60-170℃下具有相同或不同的预定的熔体粘度。
在这些实施方案中，就聚乙烯醇缩醛和增塑剂的化学性质和量而言，所述各层可具有相同或不同的组成。在优选的变体中，将三层共挤出，其中外层具有相同的组成，而内层具有与外层不同的组成。
聚乙烯醇缩醛树脂
在本发明的方法中，可使用一种或更多种化学上不同的聚乙烯醇缩醛树脂作为第一和第二聚乙烯醇缩醛树脂。此类聚乙烯醇缩醛可在聚乙烯醇含量、缩醛化程度、残留乙酸酯含量、乙烯比例、缩醛基团的醛的分子量和/或链长上有所不同。
根据本发明使用的聚乙烯醇缩醛树脂通过至少一种聚乙烯醇与一种或更多种含有2至10个碳原子、具有一个或更多个羰基官能的脂族或芳族、支化或非支化的化合物(例如醛和酮)的反应产生。为了这个目的，优选使用正丁醛或异丁醛来获得优选用于本发明的正-和/或异-聚乙烯醇缩丁醛。
所述第一和/或第二聚乙烯醇缩醛树脂可具有0.1至20mol％、优选0.5至3mol％或5至8mol％的聚乙酸乙烯酯基团含量。
所使用的聚乙烯醇缩醛的聚乙烯醇含量可在14-26重量％之间、16-24重量％之间、17-23重量％之间并优选18和21重量％之间。
添加剂
所述第一和/或第二熔体可含有碱金属离子和/或碱土金属离子，以便调节它们对于玻璃的粘合水平(所谓的防粘添加剂)。以下给出的浓度基于最终的膜。
基于夹层膜的重量，碱金属盐的总量可低至0.005重量％。碱金属盐的优选范围为0.01％-0.1％；0.02-0.08％；0.03-0.06％，各重量％基于膜的重量。
增塑剂
根据本发明使用的熔体的增塑剂含量不是特别重要，并且可针对最终膜的机械性质根据需要进行调节。正如本领域技术人员所知晓的，此类膜的增塑剂含量通常在0至80重量％的宽范围内调节。
但是，根据本发明使用的熔体的优选增塑剂含量对于增塑剂减少的膜而言将落入0-16重量％，更优选在0和8重量％之间的范围内；对于标准膜而言，将落入14.0-45.0重量％，优选15.0-32.0重量％且特别是26.0-30.0重量％的范围内，并且对于完全潮湿的膜而言，将落入25-80重量％，优选25-60重量％且特别是30至45重量％的范围内。
作为增塑剂，可使用选自以下组的一种或更多种化合物：
-多价脂族或芳族酸的酯，例如己二酸二烷基酯，例如己二酸二己酯、己二酸二辛酯、己二酸己酯环己酯、己二酸庚酯和乙二酸壬酯的混合物、己二酸二异壬酯、己二酸庚酯壬酯，以及己二酸与环脂族酯醇或含有酯醇的醚化合物的酯，癸二酸二烷基酯，例如癸二酸二丁酯，以及还有癸二酸与环脂族酯醇或含有酯醇的醚化合物的酯，邻苯二甲酸的酯，例如邻苯二甲酸丁酯苄酯或邻苯二甲酸双-2-丁氧基乙酯。
-多价脂族或芳族醇的酯或醚或具有一种或更多种非支化或支化脂族或芳族取代基的低聚醚甘醇，例如甘油、二甘醇、三甘醇或四甘醇与直链或支链脂族或脂环族羧酸的酯；后一组的实例包括二甘醇-双-(2-乙基己酸酯)、三甘醇-双-(2-乙基己酸酯)、三甘醇-双-(2-乙基丁酸酯)、四甘醇-双-正庚酸酯、三甘醇-双-正庚酸酯、三甘醇-双-正己酸酯、四甘醇二甲基醚和/或一缩二丙二醇苯甲酸酯。
-脂族或芳族酯醇的磷酸酯，例如磷酸三(2-乙基己基)酯(TOF)、磷酸三乙酯、磷酸二苯基-2-乙基己酯和/或磷酸三甲酚酯。
-柠檬酸、琥珀酸和/或富马酸的酯。
优选1，2-环己烷二羧酸二异壬酯(DINCH)或三甘醇-双-2-乙基己酸酯(3GO或3G8)用作增塑剂。
另外，所述熔体可进一步含有添加剂，例如残余量的水、UV吸收剂、抗氧化剂、粘附调节剂、荧光增白剂或荧光添加剂、稳定剂、着色剂、加工助剂、无机或有机纳米颗粒、热解法硅酸和/或表面活性物质。
根据本发明的方法可用于生产用于层压玻璃的夹层膜和/或用于光伏模块的粘附膜。
层压方法
使用本发明的方法生产的膜用作夹层来生产玻璃层压件。
层压方法是本领域技术人员已知的。例如，在大约10至15巴的升高的压力和100至150℃的温度下，在大约2小时期间进行所谓的高压釜方法。例如根据EP 1 235 683 B1的真空袋或真空环方法(在某种意义上不需要后续的高压釜处理)在大约200毫巴和130至145℃下起作用。
真空层压机还可用于层压方法。这些包括可被加热和排空的腔室，其中层压玻璃可在30-60分钟内被层压。0.01至300毫巴的减压和100至200℃、特别是130-160℃的温度已证明其在实践中的价值。

Claims (14)

1.在150-250℃下挤出包含至少一种聚乙烯醇缩醛和至少一种增塑剂的熔体流的方法，所述熔体流在60-170℃下具有预定的熔体粘度，所述方法特征在于：
a)提供至少包含第一增塑剂和第一聚乙烯醇缩醛树脂的第一熔体流并在线测量其在60-170℃下的熔体粘度；
b)将一定量的第二增塑剂和/或第二聚乙烯醇缩醛树脂添加到所述第一熔体流中以提供第二熔体流，其在60-170℃下的熔体粘度与60-170℃下的所述预定的熔体粘度具有最多20％的差异。
2.根据权利要求1所述的方法，其特征在于，在60-170℃下的所述熔体粘度作为熔体流动速率MFR、熔体体积速率MVR、压力、剪切粘度、流量比MFR(重量1)/MFR(重量2)或流动指数测量。
3.根据权利要求1或2所述的方法，其特征在于，在进行步骤a)的位置的上游将所述第二增塑剂和/或第二聚乙烯醇缩醛树脂添加至所述第一熔体流中。
4.根据权利要求1至3中任一项所述的方法，其特征在于，将所述第一熔体流加热至150-250℃的温度，并将所述第一熔体流的一部分分离并冷却至60-170℃，以便测量其在60-170℃下的熔体粘度。
5.根据权利要求4所述的方法，其特征在于，在分离所述第一熔体流的一部分之前将所述第二增塑剂和/或第二聚乙烯醇缩醛树脂添加至所述第一熔体流中。
6.根据权利要求4或5所述的方法，其特征在于，在测量分离的熔体流在60-170℃下的熔体粘度之后将其与所述第一熔体流合并。
7.根据权利要求1至5中任一项所述的方法，其特征在于，所述第二增塑剂与所述第一增塑剂相同。
8.根据权利要求1至7中任一项所述的方法，其特征在于，所述第二聚乙烯醇缩醛树脂与所述第一聚乙烯醇缩醛树脂相同。
9.根据权利要求1至7中任一项所述的方法，其特征在于，所述第二聚乙烯醇缩醛树脂在60-170℃下具有比所述第一聚乙烯醇缩醛树脂高或低至少5％的熔体粘度。
10.根据权利要求1至9中任一项所述的方法，其特征在于，将所述第二增塑剂和/或第二聚乙烯醇缩醛树脂添加至在150-250℃的温度下的所述第一熔体流中。
11.根据权利要求1至10中任一项所述的方法，其特征在于，将具有不同组成的至少两股熔体流彼此接触挤出，并且其中根据步骤a)和b)，至少一股熔体流在60-170℃下具有预定的熔体粘度。
12.根据权利要求11所述的方法，其特征在于，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，外部熔体流在60-170℃下具有预定的熔体粘度。
13.根据权利要求11所述的方法，其特征在于，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，内部熔体流在60-170℃下具有预定的熔体粘度。
14.根据权利要求11所述的方法，其特征在于，将三股熔体流彼此接触挤出，其中根据步骤a)和b)，所述熔体流在60-170℃下具有相同或不同的预定的熔体粘度。
CN201810453115.4A 2017-05-12 2018-05-11 生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法 Expired - Fee Related CN108864629B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17170927.2 2017-05-12
EP17170927 2017-05-12

Publications (2)

Publication Number Publication Date
CN108864629A true CN108864629A (zh) 2018-11-23
CN108864629B CN108864629B (zh) 2021-04-16

Family

ID=58709322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810453115.4A Expired - Fee Related CN108864629B (zh) 2017-05-12 2018-05-11 生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法

Country Status (5)

Country Link
US (1) US10899059B2 (zh)
EP (1) EP3401077B1 (zh)
JP (1) JP2018192795A (zh)
KR (1) KR20180124752A (zh)
CN (1) CN108864629B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944173A (zh) * 2020-08-24 2020-11-17 安徽皖维皕盛新材料有限责任公司 一种改善pvb胶片粘度调节剂分散性的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3650488A1 (en) * 2018-11-09 2020-05-13 Kuraray Europe GmbH Method for producing films based on plasticized polyvinyl acetal having a predefined viscosity by molar mass adjustment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040020272A1 (en) * 2002-07-31 2004-02-05 Ye-Gang Lin In-line rheometer device and method
WO2008040943A2 (en) * 2006-10-02 2008-04-10 The Queen's University Of Belfast Improvements relating to the measurement of viscosity
CN102822250A (zh) * 2010-03-31 2012-12-12 可乐丽股份有限公司 聚乙烯醇缩醛膜及其用途
US20160159043A1 (en) * 2014-12-08 2016-06-09 Solutia Inc. High tg monolithic poly(vinyl acetal) sheet

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904844A (en) * 1956-02-10 1959-09-22 Du Pont Process for embossing polyvinyl acetal sheets
DE2751225C3 (de) * 1977-11-16 1981-08-13 Werner & Pfleiderer, 7000 Stuttgart Vorrichtung mit einer nach dem Siebpaket eines Schneckenextruders angeordneten Schmelzindex-Meßeinrichtung und Verfahren zum Regeln der Viskosität von aufgeschmolzenem und auszuformendem Kunststoff
US4448736A (en) * 1982-05-24 1984-05-15 Standard Oil Company (Indiana) Continuous in-line melt flow rate control system
US4468953A (en) * 1982-07-22 1984-09-04 Rheometrics, Inc. Viscosity and elasticity of a fluid
US4817416A (en) * 1988-06-13 1989-04-04 Rheometrics, Inc. On-line rheological measurements
US4992487A (en) * 1990-01-09 1991-02-12 E. I. Du Pont De Nemours And Company Method for determining flow behavior index and using index to control polymer rheology and physical properties
US5078007A (en) * 1990-06-27 1992-01-07 E. I. Du Pont De Nemours And Company In-line polymer melt rheometer
US5014545A (en) * 1990-09-19 1991-05-14 E. I. Du Pont De Nemours And Company Apparatus for determining flow behavior index
US5347852A (en) * 1993-03-11 1994-09-20 Rheometrics, Inc. On-line rheological measurements for process control
US5959195A (en) * 1995-09-13 1999-09-28 Gottfert Werkstoff-Prufmaschinen Gmbh Process for determining and evaluating melt flow index values
US5708197A (en) * 1996-05-07 1998-01-13 Polymer Processing Institute Helical barrel rheometer
US5974866A (en) * 1997-08-29 1999-11-02 General Electric Company On-line rheometer device
DE19741674A1 (de) * 1997-09-22 1999-03-25 Haake Gmbh Geb Mischer insbesondere für viskoelastische Materialien
US6182503B1 (en) * 1999-07-01 2001-02-06 Rheometric Scientific, Inc. On-line rheological measurement for process control
DE19951444A1 (de) 1999-10-25 2001-04-26 Huels Troisdorf Verfahren und Folie zur Herstellung von Verbundsicherheitsscheiben
GB0002192D0 (en) * 2000-01-31 2000-03-22 Borealis Polymers Oy Rheometry
US6691561B2 (en) * 2002-04-15 2004-02-17 Gerneral Electric Company Rheological measurement process
DE102004013201A1 (de) 2004-03-17 2005-10-06 Kuraray Specialities Europe Gmbh Verfahren zur Coextrusion von Schmelzeströmen unterschiedlicher Zusammensetzung
US8460588B2 (en) 2007-07-30 2013-06-11 Kimberly-Clark Worldwide, Inc. Cross directional zoned bicomponent films, film laminates, and systems and methods for manufacture of the same
DE102007000817A1 (de) 2007-10-05 2009-04-09 Kuraray Europe Gmbh Weichmacherhaltige Folien auf Basis von Polyvinylacetal mit erhöhter Glasübergangstemperatur und verbessertem Fließverhalten
EP2153989B1 (de) * 2008-08-01 2021-09-29 Kuraray Europe GmbH Mehrschichtfolien aus weichmacherhaltigem Polyvinylacetal mit schalldämpfenden Eigenschaften
EP2732968A1 (de) * 2012-11-16 2014-05-21 Kuraray Europe GmbH Penetrationsfeste Mehrschichtfolien aus weichmacherhaltigem Polyvinylacetal mit schalldämpfenden Eigenschaften
US9346947B2 (en) * 2013-03-14 2016-05-24 Solutia Inc. Hydrogen peroxide as a reactive extrusion additive for poly(vinyl butyral)
EP3006202A1 (en) * 2014-10-08 2016-04-13 Kuraray Europe GmbH Multilayer films of plasticizer-containing polyvinyl acetal with photochromic properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040020272A1 (en) * 2002-07-31 2004-02-05 Ye-Gang Lin In-line rheometer device and method
WO2008040943A2 (en) * 2006-10-02 2008-04-10 The Queen's University Of Belfast Improvements relating to the measurement of viscosity
CN102822250A (zh) * 2010-03-31 2012-12-12 可乐丽股份有限公司 聚乙烯醇缩醛膜及其用途
US20160159043A1 (en) * 2014-12-08 2016-06-09 Solutia Inc. High tg monolithic poly(vinyl acetal) sheet
CN107001758A (zh) * 2014-12-08 2017-08-01 首诺公司 高Tg的整体聚(乙烯醇缩醛)片材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944173A (zh) * 2020-08-24 2020-11-17 安徽皖维皕盛新材料有限责任公司 一种改善pvb胶片粘度调节剂分散性的方法

Also Published As

Publication number Publication date
EP3401077A1 (en) 2018-11-14
CN108864629B (zh) 2021-04-16
JP2018192795A (ja) 2018-12-06
EP3401077B1 (en) 2019-12-11
US10899059B2 (en) 2021-01-26
KR20180124752A (ko) 2018-11-21
US20180326638A1 (en) 2018-11-15

Similar Documents

Publication Publication Date Title
JP6714066B2 (ja) ２種類以上の樹脂のブレンドを含むポリマー中間層
US10889087B2 (en) High Tg monolithic poly(vinyl acetal) sheet
US10717796B2 (en) Ethylene vinyl alcohol copolymer pellet, method for extrusion of the pellet and extrusion molded film produced thereby
CN108864629A (zh) 生产基于具有预定粘度的增塑聚乙烯醇缩醛的膜方法
EP2173805A1 (en) Polyethylene films with improved bubble stability
JP2020520829A (ja) 環状オレフィンコポリマーコアを含むシュリンクフィルム
US10696018B2 (en) Multilayer interlayers having high Tg and high modulus
EP3650488A1 (en) Method for producing films based on plasticized polyvinyl acetal having a predefined viscosity by molar mass adjustment
CN105860200A (zh) 一种高粘性自粘保护膜及其制备方法
US9994002B2 (en) Polymer composition for high clarity laminate, process of manufacture and applications thereof
CN105111629A (zh) 高抗pvc合金型材及其制备方法
EP1584459B1 (en) Multilayer tube of thermoplastic and method of its obtaining
CN114181339B (zh) 一种流延用线性低密度聚乙烯树脂及其制备方法
JP2007510016A (ja) フィルム製造物の密着性能を改善するための方法
CN106633325A (zh) 一种聚乙烯组合物以及耐久性薄膜
Stránskáa et al. Effect of processing agents on production of ion exchange membranes
CN106633323A (zh) 一种聚乙烯组合物以及耐久性薄膜
CN116254064A (zh) 聚合物膜
KR100750946B1 (ko) 초고속 압출코팅용 에틸렌비닐아세테이트 수지
KR20180020908A (ko) 폴리카보네이트 시트를 라미네이팅시키기 위한 가소제-비함유 폴리비닐아세탈의 용도
CN106633324A (zh) 一种聚乙烯组合物以及耐久性薄膜

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210416

CF01 Termination of patent right due to non-payment of annual fee