CN102015847B - 制备高强度聚乙烯膜的方法 - Google Patents
制备高强度聚乙烯膜的方法 Download PDFInfo
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- CN102015847B CN102015847B CN200980115206.6A CN200980115206A CN102015847B CN 102015847 B CN102015847 B CN 102015847B CN 200980115206 A CN200980115206 A CN 200980115206A CN 102015847 B CN102015847 B CN 102015847B
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- 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
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/021—Heat treatment of powders
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- 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
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- 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
- B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
- B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
一种制备高强度聚乙烯膜或带的方法,包括如下步骤:提供一定量的解缠结聚乙烯;对该一定量的解缠结聚乙烯施加至少20巴的压力和介于该解缠结聚乙烯的α松弛温度和熔点Tm PE之间的温度;得到解缠结聚乙烯的块;由该解缠结聚乙烯的块削出膜或带,和通过单阶段或多阶段拉伸步骤对该膜或带在至少1∶20的总拉伸比下进行拉伸。
Description
本发明涉及一种制备高强度聚乙烯膜、丝或带的方法。
现阶段使用分子量在400000g/mol到数百万g/mol的超高分子量聚乙烯(UHMWPE)来制备高强度聚乙烯膜、丝或带。
不使用溶剂的话很难将市售的超高分子量聚乙烯(UHMWPE)加工成高强度膜、丝或带(例如,由膜纵裂形成)。加工上的难度是由超长晶体网络的缠结引起的。
由于这个原因,经常将超高分子量聚乙烯(UHMWPE)溶解在合适的溶剂中,比如十氢化萘和石蜡烃,来使网络解缠结。但在加工成膜、丝或带之后必须彻底去除溶剂。这是十分困难和昂贵的,同时也几乎从来没有达到过使溶剂含量低于0.1%。
某些不使用溶剂的开发或方法,例如,由Nippon Oil、ITS-Tensylon或DSM提出的(参见例如EP1627719),使用粉末形式的UHMWPE,将其散布在高压连续恒压(isobar)钢带压机上来制备压实的膜。该膜可在升高的温度下通过不同的步骤来拉成高强度膜或带。
散布的粉末层的厚度和均匀度,带压机上准确的压力和温度是获得关于UHMWPE产品强度和模量的全部关键因素。
另一方面,熟知的将待加工的UHMWPE加工成膜的方法是从熔结(sinter)的片或圆形(round)的块上削出薄层。这些膜通常用于抗粘表面或高抗磨表皮,比如滑橇或滑雪板的滑动面,其厚度在0.10mm至4mm之间。对于这些UHMWPE膜来说没有拉伸和伸长的需要。就这些目的而言,最终的拉伸强度和e-模量(e-modulus)不是需要的性质,只需要光滑性和抗磨性。
由于从UHMWPE块上削出的膜的缠结晶体网络,将这种削出的膜/片拉伸成高强度膜是不可能的。使用具有缠结晶体网络的UHMWPE是无法获得1∶10或更高的拉伸比λ的。但是,高强度的应用需要膜的拉伸比λ在1∶10到1∶100或甚至1∶300之间。
UHMWPE的标准的熔结粉末的最大的可能拉伸比λmax见下式:
λmax=K(Me)1/2
其中λmax为最大拉伸比,K为比例常数,Me为缠结之间的摩尔质量。
发现对于缠结的UHMWPE,最大拉伸比低于10。
因此本发明的目的是提供一种生产高强度聚乙烯膜、丝或带的方法,在该方法中现有技术的缺点至少被减少了。
该目的通过一种制备高强度聚乙烯膜或带的方法实现,该方法包括如下步骤:
-提供一定量的解缠结聚乙烯;
-对该一定量的解缠结聚乙烯施加至少20巴的压力和介于该解缠结聚乙烯的α松弛温度(αrelaxtion temperature)和熔点(Tm PE)之间的温度;得到解缠结聚乙烯的块;
-由该解缠结聚乙烯的块削出膜或带,和
-通过单阶段或多阶段拉伸步骤对该膜或带在至少1∶20的总拉伸比下进行拉伸。
高强度聚乙烯膜或带优选具有至少1200MPa的拉伸强度和至少40GPa的拉伸模量。
本发明方法使用的聚乙烯优选分子量为至少100000g/mol,,更为优选至少500000g/mol,最为优选至少1000000g/mol。该聚乙烯也可为不同分子量聚乙烯的混合物,例如,含有两种不同分子量的聚乙烯的双模聚乙烯。
定量的解缠结聚乙烯优选为粉末形式。
本发明中方法的温度优选在α松弛温度和Tm PE-10℃之间,更为优选在100℃到130℃之间。
优选施加的压力为至少50巴,更为优选至少100巴,最为优选至少200巴或甚至500巴。
块是具有整齐形状的粉末——例如圆片——的压实的体积,优选厚度为至少5mm。
获得的块即使在熔点之下进行压制也是易延展的。由解缠结聚乙烯粉末在熔点下压制得到的块由于其易碎的特性无法在后续步骤中进行切削。
由块削出的膜或带厚度优选在0.1mm到10mm之间,更为优选在1mm到3mm之间。根据本发明方法获得的最终产品可具有低于1000μm的厚度,优选低于100μm,更为优选低于30μm。
膜或带的总拉伸比优选为至少1∶50,更为优选为至少1∶100,最为优选1∶150。
最近开发出了可以使用分子量在105到107g/mol范围内的聚乙烯制造无缠结或解缠结的聚乙烯粉末的方法。这种方法在聚乙烯粉末聚合时除了使用正确的聚合温度和压力外,还使用了特殊的、复杂的单位点催化剂。
所谓的解缠结或初生态的(nascent)聚乙烯几乎没有或没有各个链的缠结,并且因此轻易通过在80-90℃的α松弛温度之上拉伸材料来使得晶体展开。
不同于将UHMWPE粉末非常精确地散布在连续钢带上,本发明通过另外一种途径来获得高可拉伸性膜,其通过将现在用于滑橇/滑雪板表面的解缠结聚乙烯粉末厚块进行压制,但是温度大大低于通常即80℃-130℃之间,而不是高于150℃,经常甚至是180℃或更高的标准温度。在本发明的方法中粉末并未融化,而是在升高的温度下通过足够的压力被压实,从而避免通常在融化和熔结过程中出现的链缠结。获得的块随后可削成薄膜或带,这些薄膜和带可通过拉伸或超拉伸成高强度、高模量的膜或带。
本方法相当简便,因此相较于目前使用溶剂或双带压机的方法更加具有成本效益。双带压制法需要非常精确的加工条件。
根据本发明方法制得的削出的,且仍未缠结的聚乙烯膜可优选通过多阶段拉伸步骤进行拉伸,也就是,不同的连续拉伸阶段和温度。通过例如下述的步骤可获得良好的结果:
第一拉伸λ=6,温度136-140℃
第二拉伸λ=4,温度144-146℃
第三拉伸λ=3,温度148-150℃
第四拉伸λ=1.8,温度150-153℃
该特别设定的总拉伸比是始自由块削出的2.5mm厚的膜的根据本发明制得的原始的各向同性的解缠结的聚乙烯膜的130倍。压缩的条件为:在模具中以180巴的压力120℃的温度压10小时。
第一步骤还可以是使用压延压力辊加上其后的拉伸盘的组合过程,而不是单纯的拉伸。这样,膜的宽度上没有或只有很少的损失,最终的产品是更薄的膜,其也更容易达到正确的拉伸温度。
可以使用更多具有不同拉伸比和温度的拉伸步骤以获得总的拉伸比。起始拉伸可在低至90℃下进行。
该超拉伸膜的拉伸强度可达到1650MPa,拉伸模量可高于95GPa。
通过本发明方法制得的膜或带可用于防弹应用,以及复合应用,单独或和其他材料一起使用。
Claims (5)
1.一种制备高强度聚乙烯膜或带的方法,包括如下步骤:
-提供解缠结聚乙烯;
-对该解缠结聚乙烯施加至少20巴的压力和介于该解缠结聚乙烯的α松弛温度和熔点TmPE之间的温度;
得到解缠结聚乙烯的块;
-由该解缠结聚乙烯的块削出膜或带,和
-通过单阶段或多阶段拉伸步骤对该膜或带在至少1∶20的总拉伸比下进行拉伸。
2.如权利要求1所述的方法,其特征在于,形成解缠结聚乙烯的块的温度在α松弛温度和TmPE-10℃之间。
3.如权利要求1所述的方法,其特征在于,形成解缠结聚乙烯的块的温度在100℃和130℃之间。
4.如权利要求1所述的方法,其特征在于该高强度聚乙烯膜或带的拉伸强度为1200-1650MPa,拉伸模量为40-95GPa。
5.如权利要求1-4任一项所述方法制备的膜或带在防弹应用中的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08155406 | 2008-04-29 | ||
EP08155406.5 | 2008-04-29 | ||
PCT/EP2009/054726 WO2009132990A1 (en) | 2008-04-29 | 2009-04-21 | Process for producing high strength polyethylene film |
Publications (2)
Publication Number | Publication Date |
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CN102015847A CN102015847A (zh) | 2011-04-13 |
CN102015847B true CN102015847B (zh) | 2014-04-16 |
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CN200980115206.6A Expired - Fee Related CN102015847B (zh) | 2008-04-29 | 2009-04-21 | 制备高强度聚乙烯膜的方法 |
Country Status (7)
Country | Link |
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US (2) | US8188207B2 (zh) |
EP (1) | EP2274365A1 (zh) |
JP (1) | JP5349585B2 (zh) |
KR (1) | KR20110007156A (zh) |
CN (1) | CN102015847B (zh) |
RU (1) | RU2489453C2 (zh) |
WO (1) | WO2009132990A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US7976932B1 (en) * | 2007-04-13 | 2011-07-12 | BAE Systems Tensylon H.P.M, Inc. | Ballistic-resistant panel including high modulus ultra high molecular weight polyethylene tape |
US8771569B2 (en) * | 2009-01-09 | 2014-07-08 | Teijin Aramid B.V. | Polyethylene film and method for the manufacture thereof |
US8579325B2 (en) | 2010-11-09 | 2013-11-12 | Salflex Polymers Ltd. | Active bolster |
WO2012109122A1 (en) | 2011-02-07 | 2012-08-16 | Salflex Polymers Limited | Active bolster assembly |
US10005256B2 (en) | 2012-06-14 | 2018-06-26 | The Boeing Company | Selectively weakened stretched films |
US20170373360A1 (en) * | 2016-06-27 | 2017-12-28 | Ei Du Pont De Nemours And Company | Articles containing a heat source and a heat spreader |
US12011868B2 (en) | 2021-09-14 | 2024-06-18 | Case Western Reserve University | High elastomeric modulus and strength polymer constructs and methods of forming |
Citations (2)
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US4769433A (en) * | 1985-11-25 | 1988-09-06 | E. I. Du Pont De Nemours And Company | High strength polyolefins |
US7348053B1 (en) * | 2001-11-27 | 2008-03-25 | Bae Systems Tensylon H.P. Material, Inc | Ultra high molecular weight polyethylene ballistic structures |
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JPS57148627A (en) * | 1981-03-11 | 1982-09-14 | Nitto Electric Ind Co Ltd | Manufacture of transparent and nonstatic sliding sheet |
IN170335B (zh) * | 1986-10-31 | 1992-03-14 | Dyneema Vof | |
DE69018332T2 (de) * | 1989-07-28 | 1995-10-26 | Nippon Oil Co Ltd | Verfahren zur kontinuierlichen Herstellung eines Polyethylenmaterials mit hoher Festigkeit und hohem Modul. |
NL9001857A (nl) * | 1990-08-23 | 1992-03-16 | Stamicarbon | Werkwijze voor het vervaardigen van voorwerpen uit etheenpolymeer met een intrinsieke viscositeit van ten minste 4 dg/l. |
NL9100279A (nl) * | 1991-02-18 | 1992-09-16 | Stamicarbon | Microporeuze folie uit polyetheen en werkwijze voor de vervaardiging daarvan. |
JPH07251462A (ja) * | 1994-01-31 | 1995-10-03 | Somar Corp | 高分子シート、高分子シートの製造方法及び滑走材 |
JPH10180864A (ja) * | 1996-12-25 | 1998-07-07 | Sekisui Chem Co Ltd | ポリオレフィン成形体の製造方法 |
JP4475699B2 (ja) * | 1999-04-28 | 2010-06-09 | 三井化学株式会社 | 透明性に優れる高強度高分子量ポリオレフィンフィルムおよびその製造方法 |
JP2003096229A (ja) * | 2001-09-20 | 2003-04-03 | Mitsui Chemicals Inc | 多孔質(共)重合体フィルムの製造方法およびそれにより得られる多孔質(共)重合体フィルム |
JP4945442B2 (ja) * | 2004-07-02 | 2012-06-06 | ディーエスエム アイピー アセッツ ビー.ブイ. | 可撓性耐弾性アセンブリ |
IL224437A (en) * | 2004-08-16 | 2014-05-28 | Yuval Fuchs | Durable ballistic penetration item containing multiple polyethylene and ballistic fiber layers |
EP2014445A1 (en) * | 2007-07-09 | 2009-01-14 | Teijin Aramid B.V. | Polyethylene film with high tensile strength and high tensile energy to break |
CN101881582B (zh) * | 2009-12-09 | 2015-03-25 | 湖南中泰特种装备有限责任公司 | 一种防刺防弹材料及制备方法 |
-
2009
- 2009-04-21 US US12/935,352 patent/US8188207B2/en not_active Expired - Fee Related
- 2009-04-21 CN CN200980115206.6A patent/CN102015847B/zh not_active Expired - Fee Related
- 2009-04-21 EP EP09738034A patent/EP2274365A1/en not_active Withdrawn
- 2009-04-21 WO PCT/EP2009/054726 patent/WO2009132990A1/en active Application Filing
- 2009-04-21 KR KR1020107024300A patent/KR20110007156A/ko active IP Right Grant
- 2009-04-21 RU RU2010148415/05A patent/RU2489453C2/ru not_active IP Right Cessation
- 2009-04-21 JP JP2011506656A patent/JP5349585B2/ja not_active Expired - Fee Related
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2012
- 2012-03-14 US US13/420,521 patent/US8273839B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4769433A (en) * | 1985-11-25 | 1988-09-06 | E. I. Du Pont De Nemours And Company | High strength polyolefins |
US7348053B1 (en) * | 2001-11-27 | 2008-03-25 | Bae Systems Tensylon H.P. Material, Inc | Ultra high molecular weight polyethylene ballistic structures |
Also Published As
Publication number | Publication date |
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EP2274365A1 (en) | 2011-01-19 |
JP2011518933A (ja) | 2011-06-30 |
US20110028671A1 (en) | 2011-02-03 |
RU2489453C2 (ru) | 2013-08-10 |
CN102015847A (zh) | 2011-04-13 |
US8273839B2 (en) | 2012-09-25 |
US20120172565A1 (en) | 2012-07-05 |
KR20110007156A (ko) | 2011-01-21 |
JP5349585B2 (ja) | 2013-11-20 |
RU2010148415A (ru) | 2012-06-10 |
US8188207B2 (en) | 2012-05-29 |
WO2009132990A1 (en) | 2009-11-05 |
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