JP7335820B2 - 水分硬化性ワイヤおよびケーブル構造 - Google Patents
水分硬化性ワイヤおよびケーブル構造 Download PDFInfo
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- JP7335820B2 JP7335820B2 JP2019570069A JP2019570069A JP7335820B2 JP 7335820 B2 JP7335820 B2 JP 7335820B2 JP 2019570069 A JP2019570069 A JP 2019570069A JP 2019570069 A JP2019570069 A JP 2019570069A JP 7335820 B2 JP7335820 B2 JP 7335820B2
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- 238000010276 construction Methods 0.000 title description 6
- 229920000642 polymer Polymers 0.000 claims description 142
- 239000000203 mixture Substances 0.000 claims description 125
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 46
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 43
- 239000004711 α-olefin Substances 0.000 claims description 40
- 229910000077 silane Inorganic materials 0.000 claims description 35
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 23
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- 238000009833 condensation Methods 0.000 claims description 17
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 17
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 16
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 3
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- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
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- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
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- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
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- 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
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- 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
- C08K5/14—Peroxides
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- 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
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- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C08L2207/064—VLDPE
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Description
1.SIOPLAS(商標)プロセス(ケーブル押出プロセスで使用する前に別のステップで作製)、または
2.MONOSIL(商標)プロセス(ケーブル製造プロセス中にその場で作製-過酸化物、シラン、触媒を含有するエチレン性ポリマー組成物の一段階溶融ブレンド、反応、押出により)。
(A)10~99.99重量%のシラン官能基でグラフト化された非極性エチレン性ポリマー(Si-g-npPE)であって、npPEが、グラフト化前に、
(1)1,000炭素原子あたり0.2~0.7のビニル含有量、
(2)1.5~7.0デシグラム/分(dg/分)のメルトインデックス(MIまたはl2)、
(3)0.913~0.965グラム/立方センチメートル(g/cc)の密度、
(4)(≦)8以下の分子量分布(MWDまたはMw/Mn)、の特性を有する、Si-g-npPEと、
(B)0.01~20重量%のシラノール縮合触媒と、
(C)0~70重量%の難燃性添加剤と、を含む、組成物である。
一実施形態では、非極性エチレン性ポリマーは、触媒プロセス、すなわち、無触媒プロセス、例えば、高圧プロセスによって作製された低密度ポリエチレン(LDPE)とは対照的に、触媒を採用するプロセスによって作製される。一実施形態では、水分架橋性ポリマー組成物は、熱可塑性である。一実施形態では、水分架橋性ポリマー組成物は、難燃性添加剤をさらに含む。一実施形態では、難燃性添加剤は、有機難燃剤である。一実施形態では、難燃性添加剤は、無機難燃剤である。一実施形態では、難燃性添加剤は、非ハロゲン化であるかまたはハロゲンを含まない。
(A)4.00~99.67重量%の非極性エチレン性ポリマー(npPE)であって、
(1)1,000炭素原子あたり0.2~0.7のビニル含有量、
(2)1.5~7.0dg/分のI2、
(3)0.913~0.965g/ccの密度、
(4)(≦)8以下のMWD、の特性を有する、npPEと、
(B)0.3~5重量%のグラフト性シラン含有化合物、例えば、アルコキシシランと、
(C)0.01~20重量%のシラノール縮合触媒と、
(D)0.02~1.0重量%の過酸化物開始剤と、
(E)0~70重量%の難燃性添加剤と、を含む、組成物である。
一実施形態では、非極性エチレン性ポリマーは、非触媒プロセス、例えば高圧プロセスにより作製されたLDPEとは対照的に、触媒プロセスにより作製される。一実施形態では、水分架橋性ポリマー組成物は、熱可塑性である。一実施形態では、水分架橋性ポリマー組成物は、難燃性添加剤をさらに含む。一実施形態では、難燃性添加剤は、有機難燃剤である。一実施形態では、難燃性添加剤は、無機難燃剤である。一実施形態では、難燃性添加剤は、非ハロゲン化であるかまたはハロゲンを含まない。
元素周期表へのいかなる参照も、CRC Press,Inc.,1990-1991によって出版されたものへの参照である。この周期律表の元素族について記載される場合、番号順に並べた族に関する新しい表記法に依拠している。
一実施形態では、本発明の組成物は、シラングラフト化エチレン性ポリマーを含む。本発明の組成物は、反応器内でのエチレンとシラン含有化合物、例えばビニルトリメトキシシランとの共重合から作製されたエチレン性ポリマーを含まない。
本発明の実施において使用される非極性エチレン性ポリマーは、分岐、直鎖状、または実質的に直鎖状であり得、任意の重合または共重合プロセス、例えば、溶液、気相、スラリー、高圧などによって作製され得る。分岐エチレン性ポリマーの代表的なものはLDPEであり、これは典型的には、高圧気相プロセスで作製され、広範囲の長鎖分岐が特徴である。本明細書で使用される「高圧反応器」または「高圧プロセス」という用語は、少なくとも5,000ポンド/平方インチ(psi)(34.47メガパスカルまたはMPa)の圧力で動作する任意の反応器またはプロセスである。
エチレン性ポリマーは、グラフト前の分子量分布(MWDまたはMw/Mn)が、8.0以下(≦)、または≦7.5、または≦7.0、または≦6.5、または≦6.0、または≦5.5、または≦5.0、または≦4.5、または≦4.0、または≦3.5、である。一実施形態では、エチレン性ポリマーは、グラフト化前に0.1~8.0、または0.5~7.0、または1.0~6.5、または2.3~6.4のMw/Mnを有する。MWDは、実施例の試験方法に記載されているように計算または測定される。
エチレンと効果的に共重合するか、またはエチレン性ポリマーにグラフトし、したがってエチレン性ポリマーの架橋を可能にする任意のシラン(またはシラン含有化合物)が、本発明の実施で使用され得、以下の式によって記載されるものは、例示的であり、
一実施形態では、本発明の組成物は、架橋を促進し、水分硬化を確実にするために、シラノール縮合触媒を含む。アルコキシシランポリマーを架橋するための当該技術分野において既知のシラノール縮合触媒が、本発明の組成物に用いられ得る。そのような触媒には、有機塩基、カルボン酸、および例えば、ジブチルスズジラウレート(DBTDL)、ジオクチルスズマレアート、ジブチルスズジアセテート、ジブチルスズジオクトエート、酢酸スズ、オクタン酸スズ、ナフテン酸鉛、カプリル酸亜鉛、ナフテン酸コバルト等のようなものを含む鉛、コバルト、鉄、ニッケル、亜鉛およびスズの有機チタン化合物ならびに錯体またはカルボン酸塩を含む、有機金属化合物が含まれる。カルボキシレート、特にジブチルスズジラウレートおよびジオクチルスズマレアートは、本発明の組成物にとって特に有用なシラノール縮合触媒である。シラノール縮合触媒は、組成物の総重量に基づき、0.01~20重量%、または0.025~10重量%、または0.05~5重量%、または0.1~3重量%の量で存在する。シラノール縮合触媒は、マスターバッチの形態で導入され得る。一実施形態では、シラノール縮合触媒は、0重量%超、好ましくは40重量%未満の量のマスターバッチの構成成分である。
難燃性添加剤
一実施形態では、本発明の組成物は、少なくとも1つのハロゲン化有機難燃剤を含む。有用なハロゲン化有機化合物は、単環式、二環式、または多環式環であり得る芳香環または脂環式環に結合した、少なくとも1個のハロゲン原子、好ましくは臭素または塩素を有する。臭素は、好ましいハロゲンである。ハロゲン化化合物は、組成物の加工特性または物理的特性に悪影響を及ぼさない他の官能基を含有してもよい。
一実施形態では、本発明の組成物は、火炎の生成を抑制、抑制、または遅延させることができる少なくとも1つのハロゲンを含まない難燃剤(HFFR)を含む。HFFRは、無機材料であり得る。本開示による組成物での使用に適したHFFRの例には、これらに限定されないが、金属水酸化物、赤リン、シリカ、アルミナ、酸化チタン、カーボンナノチューブ、タルク、粘土、有機変性粘土、炭酸カルシウム、ホウ酸亜鉛、三酸化アンチモン、ウォラストナイト、雲母、オクタモリブデン酸アンモニウム、フリット、中空ガラス微小球、膨張性化合物、膨張黒鉛、およびそれらの組み合わせが含まれる。一実施形態では、HFFRは、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、およびそれらの組み合わせからなる群から選択することができる。
一実施形態では、本発明の水分架橋性ポリマー組成物は、(A)シラン官能基でグラフト化された非極性エチレン性ポリマー、および(B)シラノール縮合触媒を含む。
水分架橋性ポリマー組成物の配合は、当業者に既知の標準的な手段によって達成され得る。配合装置の例は、BANBURY(商標)またはBOLLING(商標)などの内部バッチ混合機である。あるいは、FARREL(商標)連続混合機、WERNERおよびPFLEIDERER(商標)二軸スクリュー混合機、またはBUSS(商標)混錬連続押出機などの、連続単軸または二軸スクリュー混合機を使用してもよい。利用される混合機の種類および混合機の動作条件は、粘度、体積抵抗率、および押出表面の滑らかさなどの組成物の特性に影響を及ぼし、これらは、当業者に周知である。
密度をASTM D-792に従って測定する。
ρa=非晶質画分の密度(0.855g/cc)
ρc=結晶画分の密度(1.00g/cc)
(A)ベースライン較正機器。ソフトウェア較正ウィザードを使用する。まず、アルミニウムDSCパンに試料を入れずに、セルを-80°から280℃に加熱してベースラインを取得する。次いで、較正ウィザードの指示に従ってサファイア標準を使用する。標準試料を180℃に加熱し、10℃/分の冷却速度で120℃に冷却し、標準試料を120℃に等温保持することにより、1~2ミリグラム(mg)の新鮮なインジウム試料を分析し、次に標準試料を等温的に120℃で1分間保持した後、標準試料を10℃/分の加熱速度で120°から180℃に加熱する。インジウム標準試料の融解熱=28.71±0.50ジュール/グラム(J/g)および融解開始=156.6°±0.5℃であることを判定する。
(B)同じDSC機器を使用して、試験試料に対するDSC測定を実施する。160℃の温度で半結晶性エチレン性ポリマーの試験試料を薄膜に押し付ける。DSC皿に5~8mgの試験試料フィルムを秤量する。パンを蓋で閉じてクリンプし、密閉雰囲気を確保する。密閉したパンをDSCセルに入れ、30℃でセルを平衡化し、約100℃/分の速度で190℃まで加熱し、試料を190℃で3分間維持し、試料を10℃/分の速度で60℃まで冷却して冷融解熱曲線(Hf)を取得し、-60℃で3分間等温に保つ。次に、試料を再度10℃/分の速度で190℃に加熱して、第2の融解熱加熱曲線(ΔHf)を取得する。第2の加熱曲線を使用して、-20℃から(エチレンホモポリマー、エチレンと加水分解性シランモノマーのコポリマー、および0.90g/cm3以上の密度のエチレンアルファオレフィンコポリマーの場合)または-40℃から(エチレンと不飽和エステルのコポリマー、および密度が0.90g/cm3未満のエチレンアルファオレフィンコポリマーの場合)融解の終わりまで積分することにより「総」融解熱(J/g)を計算する。第2の加熱曲線を使用して、23℃(室温)から溶融終了までの23℃で垂直に降下させることにより、「室温」の融解熱(J/g)を計算する。「総結晶化度」(「総」融解熱から計算)ならびに「室温での結晶化度」(「室温」融解熱から計算)を測定して報告する。結晶化度は、試験試料の第2の加熱曲線融解熱(ΔHf)および100%結晶性ポリエチレンの融解熱に対する正規化からのポリマーの結晶化度パーセント(%)または重量パーセント(重量%)として測定および報告され、式中、%結晶化度または重量%結晶化度=(ΔHf*100%)/292J/g、式中、ΔHfは、上記で定義したものであり、*は、数学的な乗算を示し、/は数学的な除算を示し、292J/gは、100%結晶性ポリエチレンの融解熱(ΔHf)の文献値である。
Wt=CA×29.0lbf/インチ2
式中、CA=試験片の断面積である。
De=得られたベンチマーク間の距離
G=ベンチマーク間の元の距離
T2=試験後の厚さ、mm(インチ)
wi=分子量Miの材料の重量画分
およびΣni=分子の総数である。
本発明の実施例1~9A(IE1~IE9A)および比較例1~7(CE1~CE7)
(態様)
(態様1)
水分架橋性ポリマー組成物であって、前記組成物の重量に基づき重量パーセント(重量%)で、
(A)10~99.99重量%のシラン官能基でグラフト化された非極性エチレン性ポリマー(Si-g-npPE)であって、前記npPEが、グラフト化前に、
(1)1,000個の炭素原子あたり、0.2~0.7のビニル含有量、
(2)1.5~7.0デシグラム/分(dg/分)のメルトインデックス(MIまたはI 2 )、
(3)0.913~0.965グラム/立方センチメートル(g/cc)の密度、および
(4)(≦)8以下の分子量分布(MWDまたはMw/Mn)、の特性を有する、Si-g-npPEと、
(B)0.01~20重量%のシラノール縮合触媒と、
(C)0~70重量%の難燃性添加剤と、を含む、組成物。
(態様2)
非極性エチレン性ポリマーが、無触媒プロセスで作製される、態様1に記載の組成物。
(態様3)
前記Si-g-npPEの非極性エチレン性ポリマー成分が、高密度ポリエチレン(HDPE)、中密度ポリエチレン(MDPE)、直鎖状低密度ポリエチレン(LLDPE)、低密度ポリエチレン(LDPE)、超低密度ポリエチレン(VLDPE)、均一に分岐した直鎖状エチレン/α-オレフィンコポリマー、および均一に分岐した実質的に直鎖状のエチレン/α-オレフィンポリマーのうちの少なくとも1つである、態様1または2に記載の組成物。
(態様4)
シラングラフト化エチレンプラストマー/エラストマーをさらに含む、態様3に記載の組成物。
(態様5)
前記Si-g-npPEのシラン含有成分が、次式の化合物から誘導され、
(態様6)
水分架橋性ポリマー組成物であって、前記組成物の重量に基づき重量パーセントで、
(A)4.00~99.67重量%の非極性エチレン性ポリマー(npPE)であっ
て、
(1)1,000個の炭素原子あたり0.2~0.7のビニル含有量、
(2)1.5~7.0dg/分のl 2 、
(3)0.913~0.965g/ccの密度、および
(4)(≦)8以下のMWD、を有する、npPEと、
(B)0.3~5重量%のグラフト性シラン含有化合物、例えば、アルコキシシランと、
(C)0.01~20重量%のシラノール縮合触媒と、
(D)0.02~1.0重量%の過酸化物開始剤と、
(E)0~70重量%の難燃性添加剤と、を含む、組成物。
(態様7)
非極性エチレン性ポリマーが、無触媒プロセスで作製される、態様6に記載の組成物。
(態様8)
前記npPEが、高密度ポリエチレン(HDPE)、中密度ポリエチレン(MDPE)、直鎖状低密度ポリエチレン(LLDPE)、低密度ポリエチレン(LDPE)、超低密度ポリエチレン(VLDPE)、均一に分岐した直鎖状エチレン/α-オレフィンコポリマー、および均一に分岐した実質的に直鎖状のエチレン/α-オレフィンポリマーのうちの少なくとも1つである、態様6または7に記載の組成物。
(態様9)
エチレンプラストマー/エラストマーをさらに含む、態様8に記載の組成物。
(態様10)
前記シラン含有化合物が、次式のものであり、
(態様11)
前記難燃性添加剤が、ペルクロロペンタシクロデカン、無水マレイン酸を有するヘキサクロロシクロペンタジエンのディールスアルダー付加物、ヘキサブロモベンゼン、ペンタブロモエチルベンゼン2,4,6-トリブロモフェノール、トリブロモフェニルアリルエーテル、エチレン-1,2-ビス(ペンタブロモフェニル)、オクタオブロモジフェニル、ポリ(ペンタブロモベンジル)アクリレート、ペンタブロモジフェニルエーテル、オクタブロモジフェニルエーテル、デカブロモジフェニルエーテル、テトラクロロビスフェノールA、テトラブロモビスフェノールA、テトラブロモビスフェノールAのビス(ジブロモプロピル)エーテル、テトラクロロフタル酸無水物、テトラブロモフタル酸無水物、
ヘキサクロロエンドメチレンテトラヒドロフタル酸、エチレン-ビス(テトラブロモフタトミド)、およびヘキサブロモシクロドデカン、のうちの少なくとも1つのハロゲン化難燃剤である、態様5または10に記載の組成物。
(態様12)
無機アンチモン難燃剤をさらに含む、態様11に記載の組成物。
(態様13)
前記難燃性添加剤が、ハロゲンを含まない、態様5または10に記載の組成物。
(態様14)
前記シラノール縮合触媒が、有機チタネート、および鉛、コバルト、鉄、ニッケル、亜鉛およびスズの錯体またはカルボキシレートのうちの少なくとも1つである、態様1~13のいずれかに記載の組成物。
(態様15)
態様1~14のいずれかに記載の組成物から作製された物品であって、UL2556第7.14節、版番号:4、版日付:2015年12月15日、「斜め衝撃試験」で測定される、斜め衝撃後のACBD値が20%以上である、態様1~14のいずれかに記載の組成物から作製された物品。
(態様16)
態様1~12の組成物のうちの1つから作製されたコーティングを含むワイヤまたはケーブルとしての、態様13に記載の物品。
Claims (8)
- 水分架橋性ポリマー組成物であって、前記組成物の重量に基づき重量パーセント(重量%)で、
(A)10~99.99重量%のシラン官能基でグラフト化された非極性エチレン性ポリマー(Si-g-npPE)であって、前記npPEが、グラフト化前に、
(1)1,000個の炭素原子あたり、0.2~0.7のビニル含有量、
(2)1.5~7.0デシグラム/分(dg/分)のメルトインデックス(MIまたはI2)、
(3)0.913~0.965グラム/立方センチメートル(g/cc)の密度、および
(4)(≦)8以下の分子量分布(MWDまたはMw/Mn)、の特性を有する、Si-g-npPEと、
(B)0.01~20重量%のシラノール縮合触媒と、
(C)0~70重量%の難燃性添加剤と、を含む、組成物であって、
前記メルトインデックス(MIまたはI2)は、ASTM D-1238、条件Eで決定され、190℃および2.16kgで測定される、組成物。 - 前記Si-g-npPEの非極性エチレン性ポリマー成分が、高密度ポリエチレン(HDPE)、中密度ポリエチレン(MDPE)、直鎖状低密度ポリエチレン(LLDPE)、低密度ポリエチレン(LDPE)、超低密度ポリエチレン(VLDPE)、分岐した直鎖状エチレン/α-オレフィンコポリマー、および分岐した実質的に直鎖状のエチレン/α-オレフィンポリマーのうちの少なくとも1つである、請求項1に記載の組成物。
- シラングラフト化エチレンプラストマー/エラストマーをさらに含む、請求項2に記載の組成物。
- 前記Si-g-npPEのシラン含有成分が、次式の化合物から誘導され、
- 水分架橋性ポリマー組成物であって、前記組成物の重量に基づき重量パーセントで、
(A)4.00~99.67重量%の非極性エチレン性ポリマー(npPE)であって、
(1)1,000個の炭素原子あたり、0.2~0.7のビニル含有量、
(2)1.5~7.0dg/分のI2、
(3)0.913~0.965g/ccの密度、
(4)(≦)8以下のMWD、を有する、npPEと、
(B)0.3~5重量%のグラフト性シラン含有化合物と、
(C)0.01~20重量%のシラノール縮合触媒と、
(D)0.02~1.0重量%の過酸化物開始剤と、
(E)0~70重量%の難燃性添加剤と、を含む、組成物であって、
前記I2は、ASTM D-1238、条件Eで決定され、190℃および2.16kgで測定される、組成物。 - 前記npPEが、高密度ポリエチレン(HDPE)、中密度ポリエチレン(MDPE)、直鎖状低密度ポリエチレン(LLDPE)、低密度ポリエチレン(LDPE)、超低密度ポリエチレン(VLDPE)、分岐した直鎖状エチレン/α-オレフィンコポリマー、および分岐した実質的に直鎖状のエチレン/α-オレフィンポリマーのうちの少なくとも1つである、請求項5に記載の組成物。
- エチレンプラストマー/エラストマーをさらに含む、請求項6に記載の組成物。
- 前記シラン含有化合物が、次式のものであり、
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