WO2006098223A1 - Film ou feuille fabrique a partir d’un copolymere sequence d'olefine - Google Patents

Film ou feuille fabrique a partir d’un copolymere sequence d'olefine Download PDF

Info

Publication number
WO2006098223A1
WO2006098223A1 PCT/JP2006/304647 JP2006304647W WO2006098223A1 WO 2006098223 A1 WO2006098223 A1 WO 2006098223A1 JP 2006304647 W JP2006304647 W JP 2006304647W WO 2006098223 A1 WO2006098223 A1 WO 2006098223A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
olefin
block copolymer
polymerization
sheet
Prior art date
Application number
PCT/JP2006/304647
Other languages
English (en)
Japanese (ja)
Inventor
Rieko Ohtani
Makoto Mitani
Terunori Fujita
Original Assignee
Mitsui Chemicals, Inc.
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 Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Publication of WO2006098223A1 publication Critical patent/WO2006098223A1/fr

Links

Classifications

    • 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
    • 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
    • C08J2323/08—Copolymers of ethene

Definitions

  • the present invention relates to a film or sheet obtained as an olefin block copolymer.
  • a block polymer in which different segments are bonded exhibits various useful physical properties, and thus is very important not only from an academic standpoint but also from an industrial standpoint.
  • the present applicant has found a transition metal compound having a salicylaldimine ligand as a new catalyst for olefin polymerization.
  • these transition metal compounds having a salicylaldimine ligand those having a specific structure are used at a high temperature that can be produced industrially, which is much higher than conventionally known living polymerization.
  • High and active living polymerization progresses, and not only homopolymerization of ethylene and propylene but also incorporation of bulky ⁇ -olefins as comonomer, that is, production of block copolymers containing bulky ⁇ -olefins I found out.
  • the present inventors have found that such a film or sheet having a block copolymer strength has physical properties superior to those of a random copolymer and a block copolymer segment having the same composition, and completed the present invention. It came to do.
  • an object of the present invention is to provide a film or sheet that exhibits various useful physical properties and is capable of obtaining an olefin block copolymer.
  • the film or sheet according to the present invention is a film or sheet having a thickness of 50 to 200 m, which is obtained by olefin block copolymer, and has a temperature of 23 ° C, a humidity of 50% and a tensile speed of 50 mmZ. It is characterized in that the breaking stress measured below is 20 MPa or more and the elongation force at break is 50% or more.
  • the olefin block copolymer which is the raw material of the film or sheet of the present invention is ( a ) an ethylene block copolymer, and (b) an ethylene block copolymer characterized by a random copolymer block obtained from ethylene and an ⁇ -olefin having 4 to 50 carbon atoms. It is characterized by that.
  • a polyolefin film or sheet excellent in both strength and elongation can be provided.
  • the film or sheet according to the present invention is a film or sheet having a thickness of 50 to 200 m obtained with an olefin block copolymer, and measured under conditions of an air temperature of 23 ° C, a humidity of 50%, and a tensile speed of 50 mmZ.
  • the yield stress is 20 MPa or more and the elongation force at yield is 50% or more.
  • the method for producing a film or sheet according to the present invention can be obtained by pressing the olefin block copolymer with a press machine heated to a melting point or higher of the olefin block copolymer. This is not the case.
  • Such films or sheets have excellent tensile strength, elongation, anti-blocking properties, transparency, cracking properties, and heat seal properties, so they can be laminated to paper and cloth, packaging materials, protective mats, books, etc. It is suitably used for applications such as protective covers.
  • the olefin block copolymer according to the present invention comprises (i) a polymer block obtained from at least one olefin force selected from olefins having 2 to 50 carbon atoms, and (ii) 2 carbon atoms.
  • Olefin linker of -50 at least one selected olefin force obtained polymer block different from the polymer block (i), and any adjacent polymer block is an olefin block copolymer different from each other is there.
  • the olefin block copolymer according to the present invention is preferably a diblock copolymer.
  • polymer block (b) it is preferable to obtain ethylene and one kind of ⁇ -olefin force selected from ⁇ -olefin linkers having 4 to 20 carbon atoms.
  • ⁇ -olefin linkers having 4 to 20 carbon atoms.
  • (B-2) an organoaluminum compound
  • M represents a titanium atom
  • m represents an integer of 1 to 2
  • R 1 represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
  • R 2 to R 5 Represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different from each other, and two or more of these may be connected to each other to form a ring.
  • n is a number satisfying the valence of M
  • X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group , Group containing nitrogen, group containing nitrogen, group containing boron, group containing aluminum, group containing phosphorus, group containing halogen, group containing heterocyclic compound, group containing nitrogen, germanium Or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other.
  • a ring may be formed.
  • the (A) transition metal compound used in the present invention is a compound represented by the following general formula (I), and specifically includes compounds described in JP-A-2004-002640.
  • N may or may not be coordinated.
  • M is a titanium atom.
  • R 1 represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
  • R 2 to R 5 represent a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group which may be the same or different from each other
  • R 6 represents a group selected from the four basic forces of hydrogen, an aliphatic hydrocarbon group, a monocyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and two or more of these are selected. They may be connected to each other to form a ring.
  • n is a number that satisfies the valence of M
  • X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, phosphorus -Containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, a plurality of groups represented by X are the same or different from each other Or multiple groups represented by X may combine with each other to form a ring.
  • the preferred U and structure of the transition metal compound (A) used in the present invention is as follows: the general formula (I) wherein M is a titanium atom, m is 2, and R 1 has at least two fluorine substituents. Have It is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • R 1 is a difluoro process group, a trifluoro file group, a tetrafluoro file group, or a pentafluoro group
  • R 6 is a linear or branched alkyl group having 1 to 3 or 3
  • a monocyclic hydrocarbon group of ⁇ 8 or an aromatic hydrocarbon group having 6 to 30 carbon atoms is particularly preferred.
  • transition metal compound represented by the general formula (I) are shown below, but are not limited thereto.
  • Me represents a methyl group
  • Et represents an ethyl group
  • ⁇ ⁇ : represents an i-propyl group
  • 3 ⁇ 4 ⁇ represents a t-butyl group
  • Ph represents a full group.
  • a method for producing such a transition metal compound (A) is not particularly limited, and can be specifically produced as described in JP-A-2004-002640.
  • the above transition metal compounds (A) are used singly or in combination of two or more.
  • organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table described in JP-A-2004-002640 are used.
  • the (B-2) organoaluminum compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble compound as exemplified in JP-A-2-78687.
  • An organic aluminum oxide compound may be used.
  • JP-A-1-501950 is disclosed. Described in Japanese Patent Laid-Open No. 1-502036, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-207703, Japanese Patent Laid-Open No. 3-207704, USP-5321106, etc. Lewis acids, ionic compounds, borane compounds, carborane compounds, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
  • JP-A-2004-002640 ionized ionic compounds described in JP-A-2004-002640 can be mentioned.
  • transition metal compound according to the present invention when it is used in combination with an organoaluminum compound (B-2) such as methylaluminoxane as a promoter component, it has a very high polymerization activity for olefinic compounds. Indicates.
  • an ionized ionic compound (B-3) such as triphenyl carbonate tetrakis (pentafluorophenol) borate is used as a co-catalyst component, an olefin polymer having good activity and very high molecular weight can be obtained. .
  • the olefin polymerization catalyst used for the polymerization of the olefin block copolymer according to the present invention may be (A) the transition metal compound represented by (I) may be used alone,
  • (B-2) an organoaluminum compound
  • these compounds are formed in the polymerization system.
  • the bond between the metal M and Y may be covalently bonded or may be ionicly bonded.
  • Specific examples of ⁇ ⁇ , M, m, n, and X are the same as in (I).
  • Examples of Y include Chemical Review, 88–1405 (1988), Chemical Review, 93–927. (1993), WO98Z30612, page 6, weakly coordinating key-on.
  • the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A) and (B-1) Organometallic compound, (B-2) organoaluminum compound, and (B-3) ionization compound, together with at least one compound (B) to be selected as necessary
  • a carrier (C) can also be used.
  • the carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid.
  • the catalyst for olefin polymerization used for the polymerization of the olefin block copolymer according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, and (B-2) an organoaluminum oxy compound. And (B-3) at least one compound selected from ionized ionic compounds (B), optionally together with a carrier (C), and if necessary, specific organic Compound component (D) can also be included.
  • the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary.
  • organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.
  • organic compounds described in JP-A-2004-002640 can be mentioned.
  • component (A) and component (B) are added to the polymerization vessel in any order.
  • component (B) may be added in an arbitrary order, if necessary. In this case, the components (B) may be the same or different.
  • a catalyst component may be further supported on a pre-polymerized solid catalyst component that may be polymerized.
  • the olefin block copolymer according to the present invention is an olefin polymerization catalyst as described above. In the presence, it is obtained by (a) polymerizing the resulting polymer block and then (b) copolymerizing the ethylene and the random copolymer block obtained from ⁇ -olefin linker having 4 to 50 carbon atoms. It is done.
  • the polymerization of the olefin block copolymer according to the present invention includes (b) a random copolymer block obtained from ethylene and ⁇ -olefin having 4 to 50 carbon atoms, and then (a) Ethylene power It may be carried out in the order of polymerization of the obtained polymer block, and then (b) copolymerization of ethylene and a random copolymer block from which ⁇ -olefin linker having 4 to 50 carbon atoms is also obtained.
  • the polymerization can be carried out by V or deviation of a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
  • inert hydrocarbon medium used in the liquid phase polymerization method examples include the solvents described in JP-A No. 2004-002640, and it is possible to use olefins themselves as solvents.
  • the ratio of each component, the polymerization temperature, and the polymerization pressure can be within the ranges described in JP-A-2004-002640. It is.
  • the polymerization reaction of olefin using such an olefin polymerization catalyst can also be performed in the method described in JP-A-2004-002640.
  • the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
  • the Mn (number average molecular weight) and Mw ZMn (molecular weight distribution) of the obtained (co) polymer are GPC (gel permeation chromatography), an ortho dichroic benzene solvent, Measured at 140 ° C.
  • the molecular weight of the obtained (co) polymer was converted from the polystyrene equivalent molecular weight to the polyethylene equivalent by the universal method.
  • the 1-hexene content of the obtained copolymer was determined by 1H-NMR (1, 1, 1, 2, 2-tetrachloroethane-d2 solvent, measured at 120 ° C) methyl signal ( S O. 93 ppm) Calculated from the area ratio of methylene and methine signal ( ⁇ 1.30 ppm).
  • the tensile test of the obtained copolymer and the like is based on ASTM D882-97, 23. The test was carried out under the conditions of C and 50RH% at a pulling speed of 50 mmZmin.
  • the reaction was stopped by adding a small amount of methanol, and the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a copolymer.
  • the copolymer was filtered, washed with methanol, and dried under reduced pressure at 130 ° C. for 10 hours to obtain 2.193 g of a block copolymer (2).
  • the resulting copolymer had an Mn (number average molecular weight) of 80,000, an MwZMn (molecular weight distribution) of 1.26, and a 1-hexene content of 4.3 mol% as measured by 1H-NMR. there were.
  • Mn number average molecular weight
  • MwZMn molecular weight distribution
  • a glass autoclave with an internal volume of 500 ml that had been sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently, 0.005 mmol of titanium compound (1) was added to initiate polymerization.
  • the reaction was carried out at 25 ° C for 1 minute in an atmospheric pressure ethylene gas atmosphere, and then the polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol, and the entire amount of the polymer was precipitated.
  • the obtained polyethylene (3) had a weight average molecular weight (Mw) of 75,000 and MwZMn (molecular weight distribution) of 1.16.
  • the random copolymer (4) obtained had an Mn (number average molecular weight) of 78, 000, MwZMn (molecular weight distribution) was 1.10, and the 1-hexene content measured by 1H-NMR was 7.2 mol%.
  • the random copolymer (6) obtained had an Mn (number average molecular weight) of 81,000, an MwZMn (molecular weight distribution) of 1.11, and a 1-hexene content of 5 measured by 1H-NMR. 4 mol%.
  • the block copolymer (2) obtained in Production Example 1 was converted into a film with a film pressure of 0.1 mm using a hot press machine (180 ° C, lMPa, 1 minute), and the conditions were 23 ° C and 50% RH.
  • a tensile test was conducted using a 30 mm long and 5 mm wide dumbbell-shaped punch as a test piece.
  • the elastic modulus was 119 MPa
  • the yield stress was 7.6 MPa
  • the elongation at yield was 14%
  • the breaking stress was 26 MPa
  • the elongation at break was 488%.
  • the results of the tensile test are shown in (Table 1).
  • the film or sheet of the present invention is characterized by excellent tensile strength, elongation, blocking resistance, transparency, cracking property, heat sealability and the like. Therefore, the film or sheet of the present invention makes a great industrial contribution in the field of manufacturing protective covers such as laminates, packaging materials, protective mats, and books on paper and cloth. Expected to do.

Abstract

L’invention concerne un film ou une feuille fabriqué à partir d'un copolymère séquencé d'oléfine qui présente diverses propriétés physiques utiles. L’invention concerne spécifiquement un film ou une feuille ayant une épaisseur de 50 à 200 µm qui est fabriqué à partir d'un copolymère séquencé d'oléfine. Ce film ou cette feuille est caractérisé en ce que sa tension de rupture n’est pas inférieure à 20 MPa et son élongation à la rupture n’est pas inférieure à 450 % lorsqu’elles sont mesurées à une température de 23 °C, à un taux d’humidité de 50 % et à une vitesse de déformation de 50 mm/min.
PCT/JP2006/304647 2005-03-17 2006-03-09 Film ou feuille fabrique a partir d’un copolymere sequence d'olefine WO2006098223A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005077487 2005-03-17
JP2005-077487 2005-03-17
JP2005-088076 2005-03-25
JP2005088076A JP2006290906A (ja) 2005-03-17 2005-03-25 オレフィンブロック共重合体から得られるフィルムまたはシート

Publications (1)

Publication Number Publication Date
WO2006098223A1 true WO2006098223A1 (fr) 2006-09-21

Family

ID=36991569

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/304647 WO2006098223A1 (fr) 2005-03-17 2006-03-09 Film ou feuille fabrique a partir d’un copolymere sequence d'olefine

Country Status (2)

Country Link
JP (1) JP2006290906A (fr)
WO (1) WO2006098223A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017119426A1 (fr) * 2016-01-08 2017-07-13 コニカミノルタ株式会社 Plaque polarisante et appareil d'affichage à cristaux liquides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002640A (ja) * 2001-12-17 2004-01-08 Mitsui Chemicals Inc オレフィン重合用触媒およびオレフィンの重合方法
JP2005089497A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc オレフィンブロック共重合体、及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004002640A (ja) * 2001-12-17 2004-01-08 Mitsui Chemicals Inc オレフィン重合用触媒およびオレフィンの重合方法
JP2005089497A (ja) * 2003-09-12 2005-04-07 Mitsui Chemicals Inc オレフィンブロック共重合体、及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FURUYAMA R. ET AL.: "Ethylene/Higher alpha-Olefin Copolymerization Behavior of Fluorinated Bis(phenoxy-imine) titanium Complexes with Methylalumoxane: Synthesis of New Polyethylene-Based Block Copolymers", MACROMOLECULES, vol. 38, no. 5, 8 March 2005 (2005-03-08), pages 1550, XP003002229 *

Also Published As

Publication number Publication date
JP2006290906A (ja) 2006-10-26

Similar Documents

Publication Publication Date Title
TWI343931B (en) Polymer blends
JP5230426B2 (ja) 多中心シャトリング剤（ｍｕｌｔｉ−ｃｅｎｔｅｒｅｄｓｈｕｔｔｌｉｎｇａｇｅｎｔ）によるポリマー構造および分子量分布の制御
KR100833561B1 (ko) 에틸렌계 중합체 및 그 용도
WO2016060218A1 (fr) Procédé de production d'ionomère à base d'éthylène et ionomère à base d'éthylène
Zhang et al. Synthesis and characterization of well-controlled isotactic polypropylene ionomers containing ammonium ion groups
JP2017530201A (ja) 加工性および環境応力亀裂抵抗性に優れたエチレン／１−ヘキセンまたはエチレン／１−ブテン共重合体
JP2009518527A5 (fr)
JPWO2007034920A1 (ja) エチレン系重合体、該重合体を含む熱可塑性樹脂組成物及び成形体
KR101831418B1 (ko) 가공성 및 표면 특성이 우수한 에틸렌/알파-올레핀 공중합체
KR101910701B1 (ko) 전이금속 화합물 및 이를 포함하는 촉매 조성물
JP2016098257A (ja) ４−メチル−１−ペンテン系重合体を含む樹脂組成物からなるフィルム
Meng et al. High transparent alternate copolymer of norbornene with isoprene catalyzed by bis (phenoxy–imine) titanium complex
JP4030659B2 (ja) 二軸延伸ポリプロピレンフィルム
WO2006098223A1 (fr) Film ou feuille fabrique a partir d’un copolymere sequence d'olefine
KR20130037689A (ko) 촉매 조성물, 촉매 조성물을 사용한 노르보르넨계 공중합체의 제조 방법, 및 노르보르넨계 공중합체, 또한 그 공중합체를 사용한 내열성 필름
CN111116790A (zh) 一种丙烯聚合物及其制备方法和应用
CN103189401B (zh) 从缺电子烯烃、不含吸电子取代基的烯烃和烷氧基乙烯基硅烷形成的三元共聚物
JP3402950B2 (ja) エチレン・スチレン共重合体
JP4781623B2 (ja) オレフィンブロック共重合体、及びその製造方法
JPH0558020B2 (fr)
KR20150013498A (ko) 폴리올레핀 중합 방법, 그로부터 제조된 반-결정성 에틸렌계 중합체, 및 그러한 중합체로부터 제조된 물품
JP7130299B2 (ja) プロピレンランダム共重合体
KR20210038328A (ko) 올레핀 공중합체를 포함하는 필름
Imuta et al. Development of polyethylene copolymers manufacturing technologies and synthesis of new functionalized polyolefins with designed catalysts
CN116547265A (zh) 异己烷可溶性不饱和烷基苯铵四(全氟芳基)硼酸盐活化剂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06728864

Country of ref document: EP

Kind code of ref document: A1