JP2013523967A - ポリオレフィン組成物およびその製造方法 - Google Patents
ポリオレフィン組成物およびその製造方法 Download PDFInfo
- Publication number
- JP2013523967A JP2013523967A JP2013503118A JP2013503118A JP2013523967A JP 2013523967 A JP2013523967 A JP 2013523967A JP 2013503118 A JP2013503118 A JP 2013503118A JP 2013503118 A JP2013503118 A JP 2013503118A JP 2013523967 A JP2013523967 A JP 2013523967A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- thermoplastic elastomer
- film
- powder
- present
- 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.)
- Ceased
Links
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- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 10
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/12—Powdering or granulating
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
- D01D5/426—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
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- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
ポリオレフィン粉末またはポリオレフィンのモノマー原料を、溶媒において溶液または分散体の形態となっている熱可塑性エラストマーと組み合わせる工程と、
ポリオレフィンのモノマー原料が使用される場合においては、重合条件下でポリオレフィンのモノマー原料を重合触媒と接触させてポリオレフィンを形成する工程と、
溶媒を除去して粉末を形成する工程と
を包みし、前記ポリオレフィンと前記熱可塑性エラストマーとは同じポリマーではない、ポリオレフィン粉末の製造方法である。
本発明はまた、粒子の少なくとも80体積%が1〜3000μmの直径を有する粒度分布を有し、かつ未処理(nascent)ポリオレフィンと、ポリオレフィンおよび熱可塑性エラストマーの合計に対して0.1〜30重量%の熱可塑性エラストマーとを含む、粒状ポリオレフィン組成物に関する。
本発明のポリオレフィン組成物および方法によれば、良好な接着性と高い強度とを伴わせ持つ、熱可塑性エラストマーを含むポリオレフィンのフィルムおよび繊維の製造が可能となる。
Description
熱可塑性エラストマーは、一般的に、最大500MPa、好ましくは最大100MPa、より好ましくは最大40MPaの引張弾性率(25℃での)を有する。
a)ポリオレフィン粉末またはポリオレフィンのモノマー原料を、溶媒において溶液または分散体の形態となっている熱可塑性エラストマーと組み合わせる工程、
b)ポリオレフィンのモノマー原料が使用される場合においては、重合条件下でポリオレフィンのモノマー原料を重合触媒と接触させてポリオレフィンを形成する工程、
c)溶媒を除去して粉末を形成する工程。
最終生成物の溶媒含有量は、一般的に1重量%未満、好ましくは0.5重量%未満、さらに好ましくは0.1重量%未満である。
上述したように、重合反応が完結すると、溶媒が除去される。生成物は、同じく上記したような、最終溶媒含有量を有する。
好適な繊維は、上記のようなフィルムから、例えばスリッティング等の機械的分割処理によって得ることができる。この方法により、テープを得ることもできる。テープは、例えばスリッティング等の機械的分割処理を含む、当該技術分野において公知の方法によって、繊維に加工されうる。繊維はまた、少なくとも100,000グラム/モルの重量平均分子量、最大6のMw/Mn比、および少なくとも3の200/110一面配向パラメーターを有するポリエチレンテープを、テープの全幅にわたってテープの厚さ方向に力を供する方法によっても、得ることができる。この場合において、出発テープの分子量およびMw/Mn比に関するさらなる説明および好ましい実施形態については、上述した通りである。この方法のさらなる記述については、国際公開第2010/003971号パンフレットが参照される。
本方法の1つの実施形態としては、シートは、複数の細長体からなる層を供給し、それらの細長体を、例えば細長体だけで圧縮することによって接着させて製造することができる。この実施形態としては、積層前にシート上にマトリックス材料を塗布することが望ましい。
圧縮が高温で実施される場合は、圧縮材料の冷却も、加圧下で行われるべきである。加圧下での冷却は、冷却の間、少なくとも成形品の構造がもはや大気圧下では緩和し得なくなる低い温度に達するまで、所与の最低圧力を維持することが好ましい。個々の場合に応じてこの温度を決定することは、当業者の能力の及ぶ範囲内のことである。該当する場合には、所与の最低圧力での冷却は、有機マトリックス材料の大部分をまたは有機マトリックス材料を完全に硬化または結晶化させ、かつ強化用細長体の緩和温度よりも低い温度まで、下げることが好ましい。冷却の間の圧力は、高温での圧力と同一である必要はない。冷却の間、成形品およびプレスの収縮に起因する圧力の減少を補って、適切な圧力値が維持されるように、圧力はモニタリングされるべきである。
圧密とは、シートが互いに強固に結合しているということを意味する。シートパッケージも圧縮されていると、非常に良好な結果を得ることができる。
ポリマーブレンドを、次のように製造した。
150mLの溶媒を入れた1Lビーカーグラス中に、連続的に攪拌しながら、スチレン−ブタジエン−スチレンブロックコポリマー(SBS、Styroflex 2G66(BASF))を添加した。溶解後、90gの超高分子ポリエチレン(UHMWPE、Ticona GUR 168X)を添加し、この混合物を十分に混合した。得られた混合物を、少なくとも12時間にわたって40℃の真空炉に入れた。混合物を3〜4回攪拌した。結果として、さらさらした粉末が得られた。製造および組成の詳細を、以下の表に示す。
620*30mmのキャビティを有する金型に、25gのポリマー粉末を充填し、137〜138℃で7分間、140バールで圧縮し、シートを形成した。
得られたシートを138℃で1分間余熱し、Collin Calander(ロール直径:250mm、スリット間隔:0.1mm、入口速度:0.5m/分)を用いてロール掛けした。このテープを、ロール上で直ちに延伸した(速度:2.5m/分)。
続いて、テープを、154℃の長さ50cmの油熱式ホットプレート上で、2段階で延伸した。テープは、ホットプレートの入口から20cmのところでホットプレートと接触した。
得られたテープの特性、および熱可塑性エラストマーを含有していない同じポリマーから得られたテープの特性を、以下の表に示す。
Fontijne SRB 150プレスにおいて、テープの末端を、5mmの重なりで一列をなして一緒になるように、紙およびフェルトシートの間で、120℃および25トンで5秒間プレスした。
接着力としては、材料が破断することなく支持し得る最大の力を求め、引張試験機を用いて50mm/分の速度で測定した。比力は、接着力をテープの幅で除した値として計算した。結果を次の表に示す。
ポリマーブレンドを次のように得た。
100mLの溶媒を含有する300Lビーカーグラス中に、連続的に攪拌しながら、2.70gのSBS(Styroflex 2G66(BASF))を添加した。溶解後、50gの絡み合いのないPE(University of Loughborough)を添加すると共に、200mLのトルエンを段階的に添加し、十分に混合した。得られた混合物を、およそ12時間にわたって40℃の真空炉に入れた。混合物を3〜4回攪拌した。結果として、さらさらした粉末が得られた。製造および組成の詳細を、以下の表に示す。
620*30mmのキャビティを有する金型に、25gのポリマー粉末を充填し、120℃で7分間、140バールで圧縮して、シートを形成した。
得られたシートを118℃で1分間余熱し、Collin Calander(ロール直径:250mm、入口速度:0.5m/分、125°)を用い、それぞれ0.3mm、0.2mm、および0.15mmのスリット間隔で、3回ロール掛けした。このテープを、0.15mmのスリット間隔で、ロール上で直ちに延伸した(速度2.5m/分)。続いて、テープを、136℃の長さ50cmの油熱式ホットプレート上で、2段階で延伸した。テープは、ホットプレートの入口から20cmのところでホットプレートと接触した。
得られたテープの特性、および熱可塑性エラストマーを含有していない同じポリマーから得られたテープの特性を、次の表に示す。
Fontijne SRB 150プレスにおいて、テープの末端を、5mmの重なりで一列をなして一緒になるように、紙およびフェルトシートの間で20秒間、135℃、25トンでプレスした。温度は、熱電対(K型)を備えたFluke 54II温度計を用いて測定した。
接着力としては、材料が破断することなく支持し得る最大の力を求め、引張試験機を用いて50mm/分の速度で測定した。比力は、接着力をテープの幅で除した値として計算した。結果を次の表に示す。
Claims (10)
- 熱可塑性エラストマーを含むポリオレフィン粉末を製造する方法であって、
ポリオレフィン粉末またはポリオレフィンのモノマー原料を、溶媒において溶液または分散体の形態となっている熱可塑性エラストマーと組み合わせる工程と、
ポリオレフィンのモノマー原料が使用される場合においては、重合条件下でポリオレフィンのモノマー原料を重合触媒と接触させてポリオレフィンを形成する工程と、
前記溶媒を除去して粉末を形成する工程と、
を含み、前記ポリオレフィンと前記熱可塑性エラストマーとは同じポリマーではない、ポリオレフィン粉末の製造方法。 - 熱可塑性エラストマーを含むポリオレフィンフィルムを製造する方法であって、
熱可塑性エラストマーを含有するポリオレフィン粉末を、加工の間の如何なる時点においても、その温度が前記ポリオレフィンの融点よりも高い値とならない条件下で、圧縮工程および延伸工程に供する工程を包含する、ポリオレフィンフィルムの製造方法。 - 熱可塑性エラストマーを含むポリオレフィン繊維を製造する方法であって、
熱可塑性エラストマーを含むポリオレフィンフィルムを、機械的分割処理に供する工程を包含する、ポリオレフィン繊維の製造方法。 - 前記ポリオレフィン粉末が、未処理ポリオレフィン粉末である、請求項1〜3いずれかに記載の方法。
- 前記ポリオレフィンが、少なくとも100,000グラム/モル、特には少なくとも300,000グラム/モル、さらには少なくとも500,000グラム/モルの分子量を有するポリエチレンを含む、請求項1〜4いずれかに記載の方法。
- 粒子の少なくとも80体積%が1〜3000μmの直径を有する粒度分布を有し、かつ未処理ポリオレフィンと、ポリオレフィンおよび熱可塑性エラストマーの合計に対して0.1〜30重量%の熱可塑性エラストマーとを含む、粒状ポリオレフィン組成物。
- 請求項6に記載のポリオレフィンと熱可塑性エラストマーとを含む粒状ポリオレフィン組成物から得られるポリオレフィンフィルムであって、
前記熱可塑性エラストマーが、当該ポリオレフィンフィルム内に存在する、ポリオレフィンフィルム。 - 請求項6に記載のポリオレフィンと熱可塑性エラストマーとを含む粒状ポリオレフィン組成物から得られるポリオレフィン繊維であって、
前記熱可塑性エラストマーが、当該ポリオレフィン繊維内に存在する、ポリオレフィン繊維。 - シートの圧縮積層体を含む耐弾性成形品であって、
各シートは強化細長体を含み、前記圧縮積層体内の前記細長体の方向は一方向ではなく、前記細長体は請求項7に記載のポリオレフィンフィルム、請求項8に記載のポリオレフィン繊維、請求項2に記載の方法によって製造されたポリオレフィンフィルム、請求項3に記載の方法によって製造されたポリオレフィン繊維、またはその組み合わせである、耐弾性成形品。 - フィルムまたは繊維の製造における、請求項6に記載の粒状ポリオレフィン組成物の使用。
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WO2014201652A1 (zh) * | 2013-06-20 | 2014-12-24 | 郑州中远防务材料有限公司 | 单纱、单纱制品及其制备方法 |
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US20130025444A1 (en) | 2013-01-31 |
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