CN108718528A - 含火焰抑制剂的聚合物组合物 - Google Patents

含火焰抑制剂的聚合物组合物 Download PDF

Info

Publication number
CN108718528A
CN108718528A CN201780013997.6A CN201780013997A CN108718528A CN 108718528 A CN108718528 A CN 108718528A CN 201780013997 A CN201780013997 A CN 201780013997A CN 108718528 A CN108718528 A CN 108718528A
Authority
CN
China
Prior art keywords
salt
composition
mixture
acid
polymer
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.)
Pending
Application number
CN201780013997.6A
Other languages
English (en)
Inventor
F·韦斯汀
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.)
Di La Mo Stock Co
Original Assignee
Di La Mo Stock Co
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 Di La Mo Stock Co filed Critical Di La Mo Stock Co
Publication of CN108718528A publication Critical patent/CN108718528A/zh
Pending legal-status Critical Current

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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08F14/00—Homopolymers and 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 a halogen
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1078—Fire-resistant, heat-resistant materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Fireproofing Substances (AREA)

Abstract

本发明涉及一种聚合物组合物，它包括聚合物和基于a)至少一种单‑、二‑和/或三‑羧酸，b)至少一种多磷酸、焦磷酸和/或磷酸，c)碱金属或碱土金属的氢氧化物或盐的混合盐形式的火焰抑制剂，其中a)和c)形成羧酸盐，以及b)和c)形成磷酸盐，和任选地d)碱金属或碱土金属的碳酸盐。该混合盐的平均粒度范围为0.2至50μm，和结晶水含量为至少5wt％。该混合盐的存在量为全部组合物重量的5‑70％。该聚合物组合物可进一步包括一种或多种添加剂。

Description

含火焰抑制剂的聚合物组合物
本发明涉及一种聚合物组合物，它包括聚合物，以及基于至少一种羧酸盐和至少一种磷酸盐，碱金属或碱土金属的氢氧化物或盐，和任选地碳酸盐的混合盐形式的火焰抑制剂，和一种或多种添加剂。
在全球塑料工业中对火焰抑制剂存在显著的需求，因为聚合物树脂典型地具有非常有害的燃烧特征。它们在相对低温下，具有高的可燃性，和当暴露于火焰下时，聚合物开始滴落，滴落起到火焰蔓延的作用，从而释放大量的烟雾和有毒气体。
本领域公知，可通过掺入火焰抑制剂，降低聚合物树脂的可燃性。市场上可获得具有火焰抑制性能的许多添加剂，但遗憾地，它们中的许多释放非常有毒的气体。卤化火焰抑制剂例如具有优良的性能，但这些化学品中的许多与健康和环境问题有关。结果，若干溴化和氯化的火焰抑制剂被禁止，且好几种在环保社区受到质疑。
一些聚合物固有地为火焰抑制剂，因为它们含有诸如卤素，大量氮等之类的元素，这使得它们成为火焰抑制剂。固有地抑制火焰的聚合物的实例是聚氯乙烯，聚四氟乙烯，氯化聚乙烯，芳族聚酰胺，卤化酸酐的聚酯，和高分子量卤化芳族聚碳酸酯。
聚氯乙烯(PVC)在挠性基底组合物中广泛地用作组分。在未改性的形式中，PVC具有相对良好的火焰抑制性能，因为它具有高的氯化物含量。当PVC燃烧时，从热裂化得到的氯化氢气体减慢连续燃烧反应，并防止燃烧进展。由于PVC本身是硬质的非挠性(inflexible)热塑性材料，因此将基于PVC的挠性基底组合物采用相对大量增塑剂配制以改进最终产品的挠性。存在这些增塑剂增加最终涂层的可燃性。
由于这一原因，有时在基于PVC的挠性基底组合物中需要各种火焰抑制和烟雾抑制成分。然而，难以同时实现充分的火焰抑制和烟雾抑制效果且维持聚合物组合物的物理和机械性能二者。抑制火焰的化合物典型地引起不完全燃烧，进而增加所生成的烟雾量，同时烟雾抑制剂可通过产生较高的燃烧热更加有效地消耗可燃有机气体而起作用。三氧化锑或氢氧化铝(ATH)例如可以是有效的火焰抑制剂，但增加火焰中生成的烟雾量。因此有利的是寻找抑制火焰且没有造成烟雾生成的备选方案。
对于某些聚合物组合物来说寻找合适的火焰抑制剂是相当复杂的，采用组合物质的问题在于并非总是给出结果。存在采用磷酸酯增塑剂配制的PVC树脂以便通过各种火焰抑制试验，因为与其他类型的增塑剂相比，磷酸酯具有优越的火焰抑制特征。锑和磷之间的拮抗是公知的且论证于文献中，但迄今为止结合使用这两类物质是已知实现某些所需水平的火焰抑制的唯一方式。有利且有益的是寻找在磷酸酯增塑剂存在下有效地起作用的火焰抑制剂。然后采用较低量的火焰抑制剂，实现充分的火焰抑制。
许多现有技术参考文献描述了使用不同的火焰抑制剂，例如反应性或添加剂卤化有机化合物，无机填料，溶剂，和基于磷与铵盐的特殊配方。例如存在矿物火焰抑制剂，它们无毒(例如氢氧化铝和氢氧化镁)且通过吸热分解而起作用。这意味着在某一温度下，该化合物崩解，进而吸收热量并释放水蒸气。所形成的氧化物导致保护层，所述保护层提供烟雾抑制和氧气剥夺效果。尽管矿物火焰抑制剂具有明显的优点，但并不总是可替代卤化的火焰抑制剂。为了在需求的应用中实现可燃性标准，需要添加非常高剂量水平的矿物火焰抑制剂(最多80wt％)。这种高水平的添加剂将彻底劣化聚合物的物理性能。
聚合物树脂和火焰抑制剂之间的相互作用相当复杂。特别地对于膨胀型组合物来说，在聚合物配方中添加剂的火焰抑制性能随着基底性质变化非常大，其中保护性焦炭的快速形成高度依赖于燃烧温度和燃烧基底所形成的熔体的粘度。
本发明的目的是提供一种包括火焰抑制剂的聚合物组合物，该火焰抑制剂抑制火焰和烟雾且克服与现有技术所提及问题这二者。本发明的另一个目的是提供一种包括火焰抑制剂的聚合物组合物，其中聚合物的机械性能得到维持。本发明进一步的目的是提供一种火焰抑制剂，它还使得掺入到任何合适的聚合物树脂内和随后非常有效地配混聚合物树脂。本发明另一目的是提供在所有聚合物树脂内确保均匀且充分的火焰抑制效果的方式。
本发明因此涉及一种聚合物组合物，它包括聚合物和基于下述的混合盐形式的火焰抑制剂：
a)至少一种单-、二-和/或三-羧酸，
b)至少一种多磷酸、焦磷酸和/或磷酸，
c)碱金属或碱土金属的氢氧化物或盐，
其中a)和c)形成羧酸盐，以及b)和c)形成磷酸盐，
和任选地
d)碱金属或碱土金属的碳酸盐。
混合盐的平均粒度范围为0.2至50μm，和结晶水含量为至少5wt％。混合盐的存在量为全部组合物重量的5-70％。该聚合物组合物可进一步包括一种或多种添加剂。
在本发明的聚合物组合物内存在的混合盐量主要取决于最终聚合物组合物的火焰抑制需求，最终聚合物制品的形状，和在聚合物组合物内存在的增塑剂量。若例如最终制品具有较厚的物品(gods)，即单位体积低的比表面积，且对火焰抑制性能没有高的需求，则与其中制品单位体积具有较高比表面积，火焰抑制需求较高或者增塑剂用量较高的情况相比，混合盐的用量较低。
在本发明组合物内的聚合物优选是热塑性聚合物。在本发明的优选实施方案中，聚合物是塑化的聚卤乙烯，和增塑剂用量优选为10-50wt％，这取决于对最终聚合物组合物的需求。聚卤乙烯优选选自聚氟乙烯(PVF)，聚氯乙烯(PVC)，氯化聚氯乙烯(CPVC)，聚偏二氟乙烯(PVDF)，或聚四氟乙烯(PTFE)和最优选PVC。
在本发明的组合物内的聚合物也可以是热塑性聚烯烃，例如聚乙烯(PE)，聚丙烯(PP)，聚甲基戊烯(PMP)或聚戊烯-1(PB-1)；聚烯烃弹性体，例如聚异丁烯(PIB)，乙烯丙烯橡胶(EPR)或乙烯丙烯二烯烃单体橡胶(EPDM橡胶)或聚苯乙烯(PS)。在本发明的组合物内的聚合物进一步可以是热塑性弹性体(TPE)，例如热塑性聚氨酯(TPU)或膨胀的热塑性聚氨酯(E-TPU)。
本发明的羧酸盐基于至少一种C2-C6单-、二-和/或三-羧酸，优选至少一种C2-C6二-羧酸和最优选至少两种C2-C6二-羧酸。在本发明的优选实施方案中，羧酸盐基于选自乙酸，乙二酸，氧代乙酸，2-羟基乙酸，丙酸，丙-2-烯酸，丙二酸，2-氧代丙酸，2-羟基丙酸，丁酸，2-甲基丙酸，丁二酸，3-氧代丁酸，丁烯二酸，氧代丁二酸，羟基丁二酸，2,3-二羟基丁二酸，丁-2-烯酸，戊酸，戊二酸，2-氧代戊二酸，己酸，己二酸，2-羟基丙烷-1,2,3-三甲酸，丙-1-烯-1,2,3-三甲酸，1-羟基丙烷-1,2,3-三甲酸，丙烷-1,2,3-三甲酸，和己-2,4-二烯酸中的至少一种单-、二-和/或三-羧酸。优选地，a)是至少一种乙酸，乙二酸，2,3-二羟基丁二酸和/或2-羟基丙烷-1,2,3-三甲酸，和最优选a)是乙二酸(也称为草酸)和/或2,3-二羟基丁二酸(也称为酒石酸)。a)中优选的羧酸被分类为强酸。
本发明的混合盐基于大于50％羧酸盐。表达本发明混合盐中不同盐比例的另一方式是，混合盐基于小于30％磷酸盐。存在羧酸盐和磷酸盐二者对于本发明组合物显著的火焰和烟雾抑制性能来说是重要的。羧酸盐和磷酸盐的这一特殊混合物使得该盐对起始的燃烧产物具有较大的反应性，和这些反应形成具有较小的可燃和有毒性能的更加所需的产物。采用本发明聚合物组合物的巨大优点是混合盐的膨胀特征，即当暴露于热量时它形成保护性炭层而不是有毒气体的能力。
本发明混合盐中c)和d)的碱金属和碱土金属选自钠，钾，钙和镁。在本发明的优选实施方案中，羧酸盐和磷酸盐中的阳离子是钙，即c)是氢氧化钙，和任选的d)是碳酸钙。本发明的混合盐优选通过酸-碱反应和自然结晶形成。形成本发明混合盐的备选方法是通过离子交换。然后分别通过a)和c)，以及b)和c)之间的离子交换，形成羧酸盐和磷酸盐，其中c)合适地为比a)中羧酸弱的羧酸的碱金属或碱土金属盐。当通过离子交换形成本发明的混合盐时，c)合适地为乙酸钙或柠檬酸钙。
当在聚合物组合物内存在混合盐中的碱金属或碱土金属碳酸盐d)时，它充当烟雾抑制剂。所述碳酸盐优选是碳酸钙，且合适地以至少3wt％混合盐的用量存在。采用本发明的聚合物组合物的主要优点是它抑制火焰和烟雾二者的能力。本发明的聚合物组合物以多种不同的方式抑制火焰。不同的成分在不同的温度下活化且抑制火焰和烟雾二者。
本发明的混合盐的pH范围优选为8-13。
采用本发明的聚合物组合物的巨大优点是混合盐小的平均粒度。在本发明的优选实施方案中，混合盐的平均粒度范围为0.5至20μm，和甚至更优选范围为1至5μm。盐晶体的粒度和形状将影响最终应用中的功能。对于单位重量来说，较小的粒子将提供较好的火焰抑制性能和对聚合物树脂的物理与机械性能较低的影响。与现有技术相比，它还改进加工性，当根据本发明注塑，吹塑和薄膜吹胀聚合物树脂时。盐形式的火焰抑制剂典型地被研磨成粉末，然后掺入到聚合物树脂内。研磨工艺产生具有尖锐边缘的晶体，它在聚合物树脂模塑工艺中可引起麻烦。采用本发明的聚合物组合物的优点是火焰抑制剂的粉末没有被研磨，即混合盐的晶体自然生长且具有均匀的形状和没有尖锐的边缘。火焰抑制剂的这些小的自然生长的晶体使得可掺入到聚合物树脂内和随后配混聚合物树脂非常有效。
采用本发明的火焰抑制剂的另一巨大优点是混合盐中不同组分的均匀分布。在每一盐晶体中代表不同的组分。若成功地掺入混合盐到聚合物树脂内，即混合盐均匀地分布在聚合物树脂内，则你可以确保火焰抑制剂的效果在所有聚合物树脂内相同。通过一起混合不同盐形成的混合盐没有显示出均匀分布的相同优点，因为在混合盐内的不同盐将具有不同的晶体形状，和在储存与处理期间因物理效应导致最终非均匀地分布。在采用其中各组分非均匀地分布的混合盐的情况下，混合盐是否成功地掺入到聚合物树脂内无关紧要，混合盐中的活性组分非均匀地分布和因此降低火焰抑制剂的效率。对于每一单位掺入的盐来说，本发明的组合物比现有技术因此提供较好的火焰抑制。通过常规的聚合物配混技术，将本发明的混合盐掺入到聚合物内。
与现有技术相比，可在具有大大地改进的光学性能的透明热塑性应用中有利地使用本发明的聚合物组合物。例如，在各种聚碳酸酯应用中存在火焰抑制剂可以是有效的。本发明组合物的令人感兴趣的应用可以是在海洋、酒店甲板和平台，展览会，商品展览，和聚会帐篷应用中的软质-乙烯基围护窗领域。本发明的聚合物组合物当然也可常规地用于不透明的热塑性用具中。
本发明的聚合物组合物也可包括选自热和UV稳定剂，烟雾抑制剂，增塑剂，增强添加剂，加工助剂，抗冲改性剂，热改性剂，颜料和填料中的一种或多种添加剂。为了它们常规地使用的目的，添加常规用量的这些添加剂。

Claims (13)

1.权利要求1的组合物，其特征在于a)是至少一种乙酸、乙二酸、2,3-二羟基丁酸和/或2-羟基丙烷-1,2,3-三甲酸。
2.权利要求1的组合物，其特征在于混合盐基于大于50％羧酸盐。
3.权利要求1的组合物，其特征在于混合盐基于小于30％磷酸盐。
4.权利要求1的组合物，其特征在于c)和d)的碱金属或碱土金属选自钠、钾、钙和镁。
5.权利要求1的组合物，其特征在于c)是盐，且通过离子交换形成羧酸盐和磷酸盐。
6.权利要求12的组合物，其特征在于c)是比a)的羧酸更弱的羧酸的盐。
7.权利要求1的组合物，其特征在于碳酸盐d)的存在量为混合盐重量的至少3％。
8.权利要求1的组合物，其特征在于混合盐的平均粒度范围为0.5至20μm。
9.权利要求1的组合物，其特征在于混合盐的平均粒度范围为1至5μm。
10.权利要求1的组合物，其特征在于混合盐的pH范围为8-13。
11.权利要求1的组合物，其特征在于混合盐具有自然生长的晶体结构。
12.权利要求1的组合物，其特征在于该组合物用于透明热塑性应用。
13.权利要求1的组合物，其特征在于任选的添加剂选自热和UV稳定剂、烟雾抑制剂、增塑剂、增强添加剂、加工助剂、抗冲改性剂、热改性剂、颜料和填料。
CN201780013997.6A 2016-02-03 2017-02-02 含火焰抑制剂的聚合物组合物 Pending CN108718528A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE1630019-6 2016-02-03
SE1630019A SE539376C2 (en) 2016-02-03 2016-02-03 A Polymer composition comprising a fire suppressant
PCT/SE2017/000007 WO2017135862A1 (en) 2016-02-03 2017-02-02 A polymer composition comprising a fire suppressant

Publications (1)

Publication Number Publication Date
CN108718528A true CN108718528A (zh) 2018-10-30

Family

ID=59500879

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780013997.6A Pending CN108718528A (zh) 2016-02-03 2017-02-02 含火焰抑制剂的聚合物组合物

Country Status (7)

Country Link
US (1) US20190040234A1 (zh)
EP (1) EP3411457A4 (zh)
JP (1) JP2019510867A (zh)
KR (1) KR20180107200A (zh)
CN (1) CN108718528A (zh)
SE (1) SE539376C2 (zh)
WO (1) WO2017135862A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1508190A (zh) * 2002-12-16 2004-06-30 吴荣泰 阻燃性树脂组成物
CN1681905A (zh) * 2002-08-07 2005-10-12 简斯·伯格·尼尔森 阻燃剂及其制造方法
US20070289752A1 (en) * 2004-11-24 2007-12-20 Basf Aktiengesellschaft Fire Extinguishing and/or Fire Retarding Compositions
TW200902689A (en) * 2007-04-04 2009-01-16 Trulstech Group Pty Ltd Improved environmentally safe fire retardant protein free compositions, and methods of manufacturing thereof
EP2062904A1 (de) * 2007-11-26 2009-05-27 Clariant International Ltd. Mischsalze von Diorganylphosphinsäuren und Carbonsäuren

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2905011A1 (de) * 1979-02-09 1980-08-14 Wacker Chemie Gmbh Weich-polyvinylchloridmassen und ihre verwendung
FR2553783B1 (fr) * 1983-10-21 1986-01-17 Rhone Poulenc Spec Chim Compositions a base de polyamide ignifuge
JP3563168B2 (ja) * 1995-09-01 2004-09-08 旭電化工業株式会社 塩化ビニル系樹脂組成物
JP3672368B2 (ja) * 1996-01-31 2005-07-20 旭電化工業株式会社 塩化ビニル系樹脂組成物
US6753363B1 (en) * 1999-07-16 2004-06-22 Polyplastics Co., Ltd. Polyacetal resin composition and process for production thereof
WO2001094472A1 (fr) * 2000-06-02 2001-12-13 Polyplastics Co., Ltd. Composition de resine retardatrice de flamme
JP3827562B2 (ja) * 2001-11-28 2006-09-27 株式会社Ａｄｅｋａ 塩化ビニル系樹脂組成物
DE10204765A1 (de) * 2002-02-05 2003-08-21 Mst Internat Ag Wettingen Brandschutzmittel
KR101022541B1 (ko) * 2002-06-24 2011-03-16 가부시키가이샤 아데카 난연제 조성물 및 이 조성물을 함유한 난연성 수지 조성물
US20100168295A1 (en) * 2005-08-16 2010-07-01 Christine Breiner Polycarbonate Flame Retardant Compositions
JP5363195B2 (ja) * 2009-05-25 2013-12-11 株式会社Ａｄｅｋａ 成形加工性に優れた難燃性合成樹脂組成物
TW201439287A (zh) * 2013-01-20 2014-10-16 Sekisui Chemical Co Ltd 阻燃性胺甲酸乙酯樹脂組成物
JP6328960B2 (ja) * 2014-02-27 2018-05-23 積水化学工業株式会社 繊維強化樹脂成形品
WO2016031905A1 (ja) * 2014-08-27 2016-03-03 積水化学工業株式会社 樹脂組成物
SE539377C2 (en) * 2016-02-24 2017-08-29 Deflamo Ab A process for manufacturing of fire suppressing crystals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1681905A (zh) * 2002-08-07 2005-10-12 简斯·伯格·尼尔森 阻燃剂及其制造方法
CN1508190A (zh) * 2002-12-16 2004-06-30 吴荣泰 阻燃性树脂组成物
US20070289752A1 (en) * 2004-11-24 2007-12-20 Basf Aktiengesellschaft Fire Extinguishing and/or Fire Retarding Compositions
TW200902689A (en) * 2007-04-04 2009-01-16 Trulstech Group Pty Ltd Improved environmentally safe fire retardant protein free compositions, and methods of manufacturing thereof
EP2062904A1 (de) * 2007-11-26 2009-05-27 Clariant International Ltd. Mischsalze von Diorganylphosphinsäuren und Carbonsäuren

Also Published As

Publication number Publication date
EP3411457A4 (en) 2019-11-13
WO2017135862A1 (en) 2017-08-10
US20190040234A1 (en) 2019-02-07
JP2019510867A (ja) 2019-04-18
EP3411457A1 (en) 2018-12-12
SE1630019A1 (en) 2017-08-04
KR20180107200A (ko) 2018-10-01
SE539376C2 (en) 2017-08-29

Similar Documents

Publication Publication Date Title
KR101205126B1 (ko) 난연성 중합체 조성물
US9790349B2 (en) Flame retardant wood plastic composite
ES2628890T3 (es) Composición polimérica ignífuga
CN104693485A (zh) 一种无卤膨胀型复配阻燃剂及其在高密度聚乙烯中的应用
ES2760551T3 (es) Sistema de expansión para espumas de aislamiento flexibles
Weil et al. Flame and smoke retardants in vinyl chloride polymers–commercial usage and current developments
JP3320575B2 (ja) 高難燃性樹脂発泡体
CN108718528A (zh) 含火焰抑制剂的聚合物组合物
CN105683223A (zh) 热稳定的聚偏二氟乙烯聚合物组合物
KR20210149115A (ko) 불연성 하이포포스파이트 금속염 분말 및 난연 성분으로서의 용도
JPS62937B2 (zh)
JP6404594B2 (ja) 難燃性プロピレン系樹脂組成物の製造方法
Al-Mosawi et al. Increasing inhibition flame resistance for PVC composite by using 2ZnO. 3B2O3. 3.5 H2O-Sb2O3 mixture
Reyes et al. Flame Retardants for Enhanced Properties in Polyolefins
JPH1121392A (ja) 難燃性ポリオレフィン樹脂成形体
JP3310710B2 (ja) 難燃性シート
KR101443780B1 (ko) 연소시 유독가스의 발생량이 적은 고분자 난연수지조성물
JPS62167338A (ja) 難燃性ポリオレフイン組成物
IL95673A (en) Thermoplastic resin composition containing suppressed smoke emission and a method of suppressing the tendency to smoke emission of thermoplastic resin preparations in fire situations
JP2013139499A (ja) 難燃性合成樹脂フィルム及びその製造方法
JP2018090697A (ja) 樹脂組成物及び成形体
PL434718A1 (pl) Kompozycja stabilizująco - uniepalniająca do zawierających chlorowiec polimerów winylowych, sposób jej otrzymywania oraz zawierająca chlorowiec stabilizowana kompozycja polimerowa o obniżonej palności
Douibi et al. Effect of PVC resin and its additives on the decomposition temperature of a chemical blowing agent (azobisformamide)
TWI440702B (zh) 阻燃聚烯烴組成物
PL429508A1 (pl) Bezhalogenowe kompozycje polietylenu oraz kopolimeru etylenu i octanu winylu o ograniczonej palności

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20181030

WD01 Invention patent application deemed withdrawn after publication