WO2018118834A1 - Copolymères à blocs d'oléfines aliphatiques/aromatiques - Google Patents

Copolymères à blocs d'oléfines aliphatiques/aromatiques Download PDF

Info

Publication number
WO2018118834A1
WO2018118834A1 PCT/US2017/067180 US2017067180W WO2018118834A1 WO 2018118834 A1 WO2018118834 A1 WO 2018118834A1 US 2017067180 W US2017067180 W US 2017067180W WO 2018118834 A1 WO2018118834 A1 WO 2018118834A1
Authority
WO
WIPO (PCT)
Prior art keywords
olefin
copolymer
olefin block
block
mole
Prior art date
Application number
PCT/US2017/067180
Other languages
English (en)
Inventor
Ranjan Tripathy
Original Assignee
Exxonmobil Chemical Patents 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 Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to KR1020197018045A priority Critical patent/KR102250766B1/ko
Priority to EP17826663.1A priority patent/EP3559063A1/fr
Priority to CN201780085457.9A priority patent/CN110248974B/zh
Priority to JP2019534349A priority patent/JP7106544B2/ja
Publication of WO2018118834A1 publication Critical patent/WO2018118834A1/fr

Links

Classifications

    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to olefin-based block copolymers including at least an aliphatic C4-C6 olefin block, at least one aromatic C8-C12 olefin block, and/or at least one cyclic C5/C10 olefin block.
  • a block copolymer is a polymer consisting of multiple sequences, or blocks, of the same or similar monomers alternating in series with other distinct monomer blocks.
  • the blocks are covalently bound to each other, such as an AAABBBAAA fashion (A and B are different types of monomers and the series of each are "blocks").
  • AAABBBAAA fashion A and B are different types of monomers and the series of each are "blocks".
  • block copolymers comes in part from their wide array of properties made possible by the existence of distinct blocks in one polymer.
  • block copolymers fill such a role.
  • Styrenic block copolymers fill such a role.
  • useful heat- activated compositions can be formed.
  • the polystyrene parts melt and allow for limited liquid- like flow.
  • the middle aliphatic section causes adhesion and after the temperature drops the strength of polystyrene is restored. This property, enhanced by the combination of the base block copolymer with other polymers, makes this styrenic block copolymers useful adhesives.
  • tackifiers are chemical compounds used in formulating adhesives to increase the tack, or the stickiness of the surface of the adhesive.
  • tackifiers are either random hydrocarbon and/or phenolic resins or synthetic random copolymers. Being random copolymers, such compounds will typically partition in the styrenic block copolymer base, and hence modify either the aliphatic or aromatic portion of the styrenic block copolymer base. Such partitioning requires the use of multiple tackifiers. It would be useful to have a tackifier that can modify the properties of both blocks of the base polymer.
  • tackifiers are made from purified aromatic monomers selected to produce a resin with an unusually high glass transition temperature and softening point. Due to these unique properties, such resins are especially suited for use as modifiers for the end-blocks of styrenic block copolymers. Resins with higher glass transition temperature and softening point than that of styrene reinforce compounds based on block copolymers, giving them higher cohesive strength and resistance to high temperatures. However, such resins associate only with the non-elastic styrenic portions of a block copolymer (i.e., they normally do not impart tack properties). Hence, there is a need for a tackifier which can modify the end block improving cohesive strength at high temperature at the same time improving tack.
  • This tackifying ability would also be useful in multilayered films, where both adhesion and flexibility are desired.
  • multilayer film technology allows two or more polymers to be combined in a layered structure to give a wide range of desirable properties.
  • the number of layers can range from two to hundreds.
  • Packaging materials typically include 3 to 7 layers of polymer material. Each layer serves a different function, such as providing mechanical strength, permeation barrier, or surface wettability.
  • the problem with such multiple layers is that the process to make such films, typically coextrusion where high shear stress is experienced by the polymer melt, often results in films having poor adhesion between the immiscible polymer layers. An additive that could affect both polymer layers of the film and improve adhesion would be desirable.
  • U.S. Patent No. 2,317,859 disclose a process for preparing a resin suitable for liquid coating and molding by polymerizing styrene with a piperylene component that has been previously partially polymerized catalytically using acid-acting metallic halide catalyst.
  • EP 0183448 B 1 describes a process for preparing block copolymer petroleum resins useful for hot melt pressure sensitive adhesives. Specifically, it describes a process of preparing resin from a reaction mixture using a feed of C4 or C5 that is polymerized completely in the presence of a Friedel-Crafts catalyst and adding a feed of C8 or C9 to the reaction mixture for further polymerization, to form a tackifier with a single softening point (i.e., single Tg).
  • a single softening point i.e., single Tg
  • Inventive tackifiers with two distinct glass transition temperatures (T g ), also referred to herein as a dual T g tackifier, comprising aliphatic and aromatic domains would improve chain entanglement at interfaces, thereby improving : ⁇
  • the dual T g tackifier would also improve cohesive strength at high temperature at the same time improving tack.
  • References of interest include:
  • an olefin block copolymer comprising at least one block comprising C8-C12 olefin-derived units and at least one block comprising C4-C6 olefin- derived units and/or C5/C10 cyclic, wherein each block has a number average molecular weight of at least 300 g/mole, and the copolymer has two glass transition temperatures (T g ) and an Mw/Mn value of at least 1.5.
  • Also disclosed is a method of forming the olefin block copolymer comprising combining C8-C12 olefins with a catalyst at least a first stage to form a C8-C12 olefin block, and combining C4-C6 olefins with the same or different catalyst in at least a second stage to form a C4-C6 olefin block; wherein the second stage takes place in the presence of the C8-C12 olefin block, or the first stage takes place in the presence of the C4-C6 olefin block.
  • the current invention also describes a method for producing a dual T g tackifier (i.e., a tackifier having two distinct T g ), by combining a first olefin with a catalyst at least a first stage to form a first olefin block, and combining a second olefin with the same or different catalyst in at least a second stage to form a second olefin block.
  • a dual T g tackifier i.e., a tackifier having two distinct T g
  • Fig. 1 is a DSC trace of the inventive olefin block copolymer exemplified in Example 1 where the onset, inflection point (I), and end point temperatures are indicated, where the (I) is the T g .
  • Fig. 2 is a DMTA trace of the inventive olefin block copolymer exemplified in Example 1.
  • Fig.3 is a GPC IR trace of the first stage of polymerization in Example 2, generating the C8-C12 olefin block ("C9"), and an overlay trace of the second stage of Example 1 generating the inventive olefin block copolymer.
  • Fig. 4 is an SAXS trace showing the C8-C12 homopolymer spectra ("Prod 1") and the olefin block copolymer spectra ("Prod 2").
  • Fig. 5 is a 13 C NMR spectroscopy of the reaction product (center trace) of Example 1, where the top trace is the C4-C homopolymer and the bottom trace is C8-C12 homopolymer trace.
  • Fig. 6 is a 3 ⁇ 4 NMR spectroscopy of the reaction product (center trace) of Example 1, where the top trace is the C8-C12 homopolymer and the bottom trace is C4-C6 homopolymer.
  • Fig. 7 is a 2-dimensional trace of DOSY NMR spectra of blends of C4-C6 homopolymer and C8-C12 homopolymer.
  • Fig.8 is a 2-dimensional trace of DOSY NMR spectra of the olefin block copolymer reaction product.
  • the inventive olefin block copolymers described herein comprise monomers derived from the so-called C5 stream, C5/C10 cyclic stream and C9 stream of common hydrocarbon cracking processes.
  • the "C5 stream” comprises C4 to C6 olefins and/or diolefins, and mostly comprises piperylene, and the "C9 stream” comprises C8 to C12 hydrocarbons containing at least one aromatic moiety, mostly comprising indene, vinyltoluene, and styrene.
  • the "C5/C10 cyclic stream” comprises olefins and/or diolefins and mostly cyclopentadiene, dicyclopentadiene, or derivatives thereof.
  • Random C5/C9 olefin copolymers are known and prepared by polymerizing pre-mixed streams of C5/C9 using an appropriate catalyst. However, the inventor has found that sequential monomer addition, forming blocks comprising similar monomer-derived units, is preferred for the synthesis of blocky olefin copolymers with at least two glass transition temperatures. At the selected condition of catalyst and temperature, the "C9 stream” polymerizes in a controlled fashion keeping the chain ends active.
  • the C5 or C5/C10 cyclic monomer stream is introduced and the polymer chain continues to grow. The order can be reversed as well.
  • “monomer-derived units” or simply “units” are “mer” groups in the polymer backbone derived from a polymerizable monomer. Monomers are reacted with one another to form a polymer comprising monomer-derived units. A polymer may be referred to as having or comprising monomers, meaning that the polymer comprises those monomer- derived units.
  • Such an olefin block copolymer is a useful tackifying resin in adhesive compositions and/or a component of a film, either as its own layer or a component of a layer in a multi-layered film or sheet.
  • the inventive aliphatic/aromatic olefin block copolymer (or simply "olefin block copolymer") contains at least one aliphatic or "C4-C6 block” (mostly piperylene with other C4-C6 aliphatic olefins) or " C5/C10 block” (mostly dicyclopentadine with other derivatives of cyclopentadiene) and at least one aromatic or "C8-C12 block” (C6- C8 olefins comprising at least one aromatic moiety) which are attached covalently, thus forming micro phase domains.
  • C4-C6 block mostly piperylene with other C4-C6 aliphatic olefins
  • Each individual domain selectively interacts at the interface with appropriate styrenic-based hot melt adhesive or with immiscible multilayer films, thus improving inter-layer adhesion as well as tackifying each block to produce useful adhesives.
  • the use of cyclic C5/C10 stream can also act as a reinforcing and increasing the cohesive strength at high temperature of styrenic-based hot melt adhesives.
  • a unique approach is disclosed to prepare the olefin block copolymer with two glass transition temperatures using sequential monomer addition.
  • the olefin block copolymer may be referred to as including at least the two blocks, a C4-C6 olefin block (or “C5 block”), C5/C10 cyclic and a C8-C12 olefin block (or “C9 block”), all of which are covalently bound to one another.
  • the separate C4-C6 polymer may be referred to as a "homopolymer", and the separate C5/C10 cyclic polymer, C8- C12 polymer likewise.
  • AAABBB type block copolymer Thus produced is at least an AAABBB type block copolymer.
  • the "a” and “b” integers may range independently from 1, or 2, or 5 to 10, or 20 or more. Note that the reactants (styrene, indene, piperylene) shown here are not exclusive and there may be other reactants, and likewise the identity of each block may vary depending on the amount and/or type of reactants.
  • the C8-C12 olefin block(s) described herein comprises units derived from C8-C12 aromatic-containing olefins, wherein at least one of the C8-C12 aromatic-containing olefins comprise at least one aromatic moiety, (A) in the above reaction.
  • An "aromatic-containing olefin” is an olefin comprising at least one aromatic moiety such as indene, methylindene, vinyltoluene, methylstyrene, dicyclopentadiene, naphthalene, and/or styrene.
  • the C8-C12 olefin block comprises units derived from indene, styrene and combinations thereof. In any embodiment, the C8-C12 olefin block comprises units derived from indene, methylindene, vinyltoluene, methylstyrene, dicyclopentadiene, naphthalene, or styrene, and combinations thereof.
  • the C4-C6 olefin block(s) described herein comprises units derived from linear and/or cyclic aliphatic C4-C6 olefins and/or diolefins, (B) in the above reaction.
  • the C4-C6 olefin block comprises units derived from piperylene.
  • the C5/C10 cyclic olefin block comprises units derived from cyclopentadiene, dicyclopentadiene, or cyclopentene, and combinations thereof.
  • At least 80, or 85, or 90, or 95, or 98 wt% by weight of all units in the C4-C6 olefin block are C4 to C6 olefin- and/or diolefin-derived units; and there may be a minor amount (20, or 15, or 10, or 5, or 2 wt% or less) of units derived from lower (C3 and lower) or higher (C7 and above) olefins and/or diolefins.
  • At least 80, or 85, or 90, or 95, or 98 wt% by weight of all units in the C8-C12 olefin block are C8 to C12 aromatic-containing olefin-derived units and there may be a minor amount (20, or 15, or 10, or 5, or 2 wt% or less) of units derived from lower (C7 and lower) or higher (CI 3 and higher) olefins, diolefins and/or aromatic-containing olefin-derived units.
  • any embodiment is a copolymer comprising (or consisting essentially of, or consisting of) at least one block comprising C8-C12 olefin-derived units and at least one block comprising C4-C6 olefin-derived units, wherein each block has a number average molecular weight (Mn) of at least 300, or 400, or 600 g/mole and two glass transition temperatures (T g ).
  • Mn number average molecular weight
  • T g glass transition temperatures
  • the at least two glass transition temperatures comprise a first Tgi and a second T g 2 as determined by DSC described herein, wherein T g 2 is greater than Tgi by at least 5, or 10, or 20°C, or within a range from 5, or 10, or 20°C to 30, or 50, or 60°C.
  • T g i is within a range from -30, or -20°C to 40, or 60°C
  • T g 2 is within a range from -10, or 0, or 10°C to 60, or 80, or 120°C.
  • values of Tg were determined by the DSC method described herein to a value of +0.5°C.
  • the inventive copolymer has certain molecular weight features elucidated by Gel Permeation Chromatograph (GPC).
  • the at least one C8-C12 olefin block has a number average molecular weight (Mn) within the range from 300, or 400, or 600 g/mole to 1,000, or 2,000, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000 g/mole.
  • the at least one C8-C 12 olefin block has a weight average molecular weight (Mw) within the range from 600, or 800, or 1,000 g/mole to 2,200, or 2,600, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000, or 40,000 g/mole.
  • Mw weight average molecular weight
  • the at least one C4-C6 olefin block has an Mn within the range from 300, or 400, or 600 g/mole to 1,000, or 2,000, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000 g/mole. In any embodiment, the at least one C4-C6 olefin block has a Mw within the range from 600, or 800, or 1,000 g/mole to 2,200, or 2,600, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000, or 40,000 g/mole.
  • the at least one C5/C10 cyclic olefin block has an Mn within the range from 300, or 400, or 600 g/mole to 1,000, or 2,000, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000 g/mole. In any embodiment, the at least one C5/C10 cyclic olefin block has a Mw within the range from 600, or 800, or 1,000 g/mole to 2,200, or 2,600, or 3,000, or 4,000, or 6,000, or 10,000, or 20,000, or 40,000 g/mole.
  • the copolymer itself has an Mn within the range from 500, or 800, or 1,000 g/mole to 2,000, or 4,000, or 6,000, or 10,000, or 20,000, or 40,000 g/mole. In any embodiment, the copolymer itself has an Mw within the range from 1,000, or 2,000, or 2,500, or 5,000 g/mole to 6,000, or 8,000, or 10,000, or 30,000, or 40,000, or 60,000, or 80,000 g/mole.
  • the copolymer as a z-average molecular weight (Mz) within the range from 3,000, or 4,000 g/mole to 16,000, or 20,000, or 40,000, or 60,000, or 80,000, or 100,000 g/mole.
  • the Mz/Mw value of the copolymer is at least 2.0, or 2.2, or 2.4, or 2.8, or 3.0, or within a range from 2.0, or 2.2, or 2.4, or 2.8, or 3.0 to 5, or 6, or 7, or 8, or 10.
  • the Mw/Mn value of the copolymer in any embodiment is at least 1.5, or 1.6, or 1.7, or 1.8; or Mw/Mn is within a range from 1.5, or 1.6, or 1.7, or 1.8 to 2.5, or 3, or 4, or 6, or 8, or 10.
  • copolymer can also be elucidated by Atomic Force Microscopy (AFM) and other means described herein as having "nano-scale" structures or segregation.
  • AFM Atomic Force Microscopy
  • the copolymer has discontinuous domains of at least 0.5, or 1, or 2 ⁇ in size, or within a range from 0.5, or 1, or 2 ⁇ to 3, or 4, or 6 ⁇ .
  • Also disclosed in any embodiment is a method of forming the copolymer described herein comprising (or consisting essentially of, or consisting of) combining C8-C12 olefins with a catalyst in at least a first stage to form a C8-C12 olefin block, and combining C5/C10 cyclic olefins or C4-C6 olefins with the same or different catalyst in at least a second stage to form a C5/C10 cyclic olefins or C4-C6 olefin block; wherein the C5/C10 or C4-C6 olefin block forming stage takes place in the presence of the C8-C12 olefin block, or the C8-C12 olefin block forming stage takes place in the presence of the C5/C10 or C4-C6 olefin block.
  • the second stage takes place in the presence of the at least one C8-C12 olefin block, or the first stage takes place in the presence of the at least one C5/C10 or C4-C6 olefin block.
  • the polymerization can take place starting either with the C8-C12 olefin block or the C5/C10 cyclic or C4-C6 olefin block, and preferably takes place in a serial fashion such that the first block(s) to be made are present when the next block is produced, thus forming a series of covalently linked blocks.
  • the catalyst is a Lewis Acid catalyst and the components are combined at a temperature within the range from -10, or 0, or 10°C to 20, or 30, or 40, or 50°C.
  • Categories of useful Lewis acids include those comprising Al 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Ti 2+ , Sn 2+ , and the like, electron deficient compounds including BF3, AIF3, AlCb, and the like, acids having a central atom having more than 8 valence shell electrons, such as SiBr 4 , SiF 4 , and the like, and/or compounds having multiple bonds between two atoms of different electronegativities, such as CO2, SO2, and the like.
  • the reaction can be a living polymerization reaction, but may also be variants of such reactions.
  • the reaction may be a so-called "controlled block copolymerization" or a Friedel-Crafts-type reaction, the reaction may also be a controlled anionic polymerization that can be catalyzed by such agents as n-butyl lithium, or controlled cationic polymerization reaction.
  • the reaction is preferably a continuous polymerization process.
  • the reaction preferably takes place in an aprotic medium, and most preferably in an aliphatic and/or aromatic solvent, such as hexanes and/or toluene. Preferably, there is some residual water moisture present to facilitate the catalytic reaction.
  • a catalyst is combined with olefins comprising indene and/or styrene in one step to form an aromatic C8-C12 olefin block, and in a sequential step the same or different catalyst in the presence of the C8-C12 olefin block (or, at this point, C8- C12 homopolymer) is combined with olefins comprising piperylene to form an aliphatic, or C4-C6 olefin block covalently bonded to the C8-C12 block to form the olefin block copolymer.
  • This can be repeated to increase the number of blocks, for instance, as an AAABBBAAA, or AAABBBAAABBB, etc., block copolymer.
  • a catalyst is combined with olefins comprising piperylene in one step to form an aliphatic C4-C6 olefin block, and in a sequential step the same or different catalyst in the presence of the C4-C6 olefin block (or, at this point, C4-C6 homopolymer) is combined with olefins comprising indene and/or styrene to form an aromatic, or C8-C12 olefin block covalently bonded to the C4-C6 block to form the olefin block copolymer.
  • This can be repeated to increase the number of blocks for instance, as a BBBAAABBB, or BBBAAABBBAAA, etc. block copolymer.
  • a catalyst is combined with cyclic olefins comprising cyclopentadiene or dicyclopentadiene in one step to form an C5/C10 olefin block, and in a sequential step the same or different catalyst in the presence of the C5/C10 olefin block (or, at this point, C5/C10 homopolymer) is combined with olefins comprising indene and/or styrene to form an aromatic, or C8-C12 olefin block covalently bonded to the C5/C10 block to form the olefin block copolymer.
  • This can be repeated to increase the number of blocks for instance, as a CCCAAACCC, or CCCAAACCCAAA, etc. block copolymer, where "C" is a C5/C10 cyclic component.
  • the copolymer described herein is useful in any number of applications and articles such as in single layered films, multi-layered films and as part of an adhesive composition, or tire tread and/or tire sidewall compositions. As applied in tires, the inventive copolymer could independently change the two important parameters of tread: rolling resistance (RR) and wet traction (WT).
  • RR rolling resistance
  • WT wet traction
  • the inventive tackifier can also be used for improving the cohesive strength at high temperature at the same time improving the tack.
  • the copolymer may desirably include just the olefin block copolymer, but may also include other components from the reaction used to make it, such as side products of C4-C6 homopolymers and/or C5/C10 and/or C8-C12 homopolymers that did not form a block.
  • a composition comprising (or consisting essentially of, or consisting of) the copolymer described herein and a C4-C6 homopolymer, a C8-C12 homopolymer, a C5-C10 homopolymer or combination thereof.
  • compositions comprising the copolymer as described herein.
  • preferred compositions are those that comprise the olefin block copolymer with ethylene-vinyl-acetate (EVA), styrene- butadiene rubber (SBR), styrene-isoprene-styrene (SIS) copolymers, and/or styrene-butadiene- styrene copolymers (SBS), and hydrogenated versions of any of these.
  • EVA ethylene-vinyl-acetate
  • SBR styrene-butadiene rubber
  • SIS styrene-isoprene-styrene copolymers
  • SBS styrene-butadiene- styrene copolymers
  • the olefin block copolymer is preferably present in these compositions to within a range of 0.5, or 1, or 5 wt% to 10, or 20, or 30
  • inventive olefin block copolymers can be combined with other descriptive elements and numerical ranges to describe the invention(s); further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein, including the examples in jurisdictions that allow such combinations.
  • DSC Measurements The following DSC procedure was used to determine the glass transition temperatures (T g ) of the dual Tg tackifier. Approximately 6 mg of material was placed in a microliter aluminum sample pan. Due to the amorphous nature of the copolymers and homopolymers described herein, the samples were not annealed. The sample was placed in a differential scanning calorimeter (Perkin Elmer or TA Instrument Thermal Analysis System) and was heated from 23°C to 120°C at 10°C/minute and held at 120°C for 5 minutes. Afterward, the sample was cooled down to -50°C at 10°C/minute.
  • T g glass transition temperatures
  • the sample was held at - 50°C for 5 minutes and then heated from -50°C to 210°C at 10°C/minute for a second heating cycle.
  • the T g was determined in the TA Universal Analysis on the second heating cycle.
  • the "Glass Transition" menu item on the TA Universal Analysis equipment is used to calculate the onset, end, inflection, and signal change of T g in the DSC.
  • the program enables the determination of the onset, which is the intersection of the first and second tangents, where the inflection is the portion of the curve between the first and third tangents with the steepest slope, and the end is the intersection of the second and third tangents.
  • the polymer mixture was filtered through a 0.45 ⁇ Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate was 1.0 mL/min and the nominal injection volume is 200 ⁇ .
  • the molecular weight analysis was performed with EcoSEC software.
  • the mass recovery was calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight was determined by using a polystyrene calibration relationship with the column calibration which is performed with a series of mono- dispersed polystyrene (PS) standards ranging from 400 to 35,000 kg/mole.
  • PS mono- dispersed polystyrene
  • NMR Measurements 500 MHz NMR instrument in TCE-d2 or CDC1 3 solvent at 25 °C and 120 scans. NMR data of the olefin block copolymer were measured by dissolving 20 + 1 mg of sample in 0.7 ml of d- solvents. The samples are dissolved in TCE-d2 in 5 mm NMR tube at 25 °C until the sample was dissolved. There is no standard used. The TCE-d2/ CDCI3 presents as a peak at 5.98 or 7.24 ppm and used as the reference peak for the samples.
  • SAXS/MAXS/WAXS Measurements All small- and wide-angle X-ray scattering (SAXS/WAXS) were performed using an SAXSLAB Ganesha 300XL+ instrument. The samples were sandwiched in between two kepton films and mounted on a multi-sample stage holder. All sample data were collected at sample-to-detector positions of 91 mm (WAXS) and 1041 mm (SAXS) and were held in a vacuum to minimize air scatter. The SAXS and WAXS were recorded using a Dectris Pilatus. Sample to detector distance was calibrated using a silver behenate standard. A 0-360° integration was performed on the 2D scattering patterns to yield a ID I(q) versus q scattering profile.
  • Atomic Force Microscopy is a morphological imaging technique carried out using an Asylum Research Cypher Atomic Force Microscope. Samples were cryo-microtomed prior to scanning in order to create a smooth surface at -120°C. After microtoming, the samples were purged under N2 in a desiccator before evaluation. Imaging was conducted according to the following: The instrument was tuned to the fundamental (1st) mode of the cantilever, setting the amplitude at 1.0 V and the drive frequency to about 5% below the free-air resonance frequency of the cantilever.
  • a higher mode (2nd, 3rd, or 4th, depending on cantilever and holder) was selected, setting the amplitude to 100 mV and the drive frequency on resonance.
  • the setpoint was set to 640 mV, the scan rate to 1 Hz, and the scan angle to 90°.
  • An Asylum Research reference standard (10 microns x 10 microns pitch grating x 200 nm deep pits) was used for the AFM SQC and X, Y, and Z calibration. The instrument was calibrated to be accurate to within 2% or better of true value for X-Y and within 5% or better for Z. Representative scan sizes were 10x10 ⁇ , 5x5 ⁇ , lxl ⁇ and 500x500 nm.
  • Example 1 (C5 stream first, followed by C9 stream).
  • the synthesis of a first olefin block copolymer by sequential monomer addition is as follows.
  • the C8-C12 and C4-C6 feeds were dried in molecular sieve before polymerization.
  • the C4-C6 stream was first introduced into the continuous stirred tank reactor (CSTR).
  • the C4-C6 cationic polymerization was initiated in conjunction with residual moisture present in the system and Lewis Acid (AICI3).
  • AICI3 Lewis Acid
  • the olefin block copolymer thus produced was characterized by GPC for molecular weight, 3 ⁇ 4 and 13 C NMR spectroscopy for structural characterization. DSC and DMTA were measured for thermal analysis of the olefin block copolymer. Small angle X-ray scattering and atomic force microscopy was measured to analyze the morphology of the olefin block copolymer.
  • the resulting product, the olefin block copolymer had an Mn of 1165 g/mole, a Mw of 2078 g/mole, and an Mz of 4148 g/mole, thus having an Mz/Mw of 2.0, and an Mw/Mn of 1.79.
  • the cross-over frequencies of 13 C resonate at a ⁇ of 45 ppm which is buried under the signals of the homopolymer.
  • the presence of the next carbon resonance at a ⁇ of 53 ppm suggests cross-over and thus the existence of the block copolymer.
  • Example 1 The 3 ⁇ 4 NMR spectroscopic results for Example 1 are shown in Fig. 6 with traces of a C8-C12 homopolymer (top), a C4-C6 homopolymer (bottom), and the olefin block copolymer poly(C9-b-C5) (middle). From the overall integration of 3 ⁇ 4 NMR spectroscopy, it is suggested that the composition of the block contains 57 wt% of aliphatic and 43 wt% of aromatic composition. All of the olefinic composition is from the aliphatic C4-C6 monomer units.
  • Example 2 (C9 stream first, followed by C5 stream).
  • the synthesis of a second olefin block copolymer by sequential monomer addition is as follows.
  • the C8-C12 and C4-C6 olefins were dried by passing through molecular sieve before the reactions.
  • the C8-C12 olefin stream was introduced as the first monomer into a CSTR and the polymerization was initiated with the addition of Lewis Acid (AlCb).
  • AlCb Lewis Acid
  • the reaction temperature and catalyst concentration was kept at 10°C and 0.2 wt% of catalyst, for minimizing chain transfer and cyclization.
  • the C4-C6 olefins were introduced as the 2 nd monomer into the same reactor containing the polymerized C8-C12 olefins.
  • the first polymerizable fraction (aliquot) was withdrawn for analysis of the first block.
  • the temperature and the catalyst concentration were kept constant.
  • the reaction was maintained for 2 hours until all the C4-C6 olefins had reacted.
  • the polymerization was quenched with isopropanol.
  • the olefin block copolymer was distilled under nitrogen at 250°C to remove unreacted hydrocarbons.
  • the amount of C8-C12 and C4-C6 olefins were adjusted in a way that results in 50% of aliphatic and 50% of aromatic composition in the final olefin block copolymer.
  • the olefin block copolymer thus produced was characterized by GPC for molecular weight, and 3 ⁇ 4 and 13 C NMR spectroscopy for structural characterization. DSC and DMTA techniques were used for thermal analysis of the reaction products. The NMR characterization of the olefin block copolymer in Example 2 was consistent with that of Example 1.
  • the number average molecular weight (Mn) of the C8-C12 olefin block from Example 1 was 760 g/mole, and its weight average molecular weight (Mw) was 1820 g/mole, and an Mz of 3400 g/mole.
  • the final olefin block copolymer had a Mn of 953 g/mole, and an Mw of 4611 g/mole, and an Mz of 12,000 g/mole, thus having an Mz/Mw of 2.6, and an Mw/Mn of 4.8.
  • GPC traces in Fig. 3 are of the precursor (C8-C12 homopolymer) as well as the olefin block copolymer product in Example 2. Both the refractive index (RI) (shown) and the UV (not shown) signals were used to characterize the resin.
  • the first block which is C8-C12 ("C9"), was UV detectable, whereas the C4-C6 ("C5") was not UV-detectable.
  • the shift in RI- signal with the addition of the 2nd block clearly evidences the change in molecular weight, which is due to the formation of block copolymer.
  • the UV signal there was no change even after the addition of 2nd block, which demonstrates that the numbers of chains with C8-C12 molecules are constant.
  • the C4-C6 olefin block was adding to the already initiated chains from C8-C12, thus forming block copolymers.
  • the volume of the UV trace was increasing which further suggests addition of C4-C12 molecules to the already initiated C8-C12 chains.
  • a small hump in the GPC RI trace was observed, which was present after the addition of C4-C12 monomers, which is interpreted as being due to the presence of homopolymer of C4-C12.
  • the GPC analysis provides evidence for a block copolymer of block-C9-C9-C9-block-C5-C5-C5 and some homopolymer of C4-C12.
  • Example 2 DSC and DMTA studies for Example 2 were also conducted, including the C8-C12 homopolymer and of the resulting olefin block copolymer reaction product.
  • the DMTA plots of just the C8-12 homopolymer present one big transition in the tan ⁇ peak at 40°C, which correlates with the DSC measurement.
  • the 2 nd DMTA plot is of the product from the reaction in Example 2 and presents multiple transitions: one at lower temperature, -22°C (C4-C6 olefin block) and the other at higher temperature 12°C (C8-C12 olefin block). Both of these transitions are consistent with the DSC measurements of the same reaction product, showing multiple glass transition temperatures.
  • SAXS measurements provide evidence that the reaction products of both Examples yield an olefin block copolymer.
  • the scattering patterns were normalized to the primary beam intensity and corrected for background scattering.
  • SAXS from Example 2 (Fig. 4) reaction products display a slope of -4 in the low-q regime, which indicates presence of domains larger than 0.5 microns.
  • the AFM image height of the Example 2 reaction product evidences the presence of bi-continuous domains of about 50 nm, which correlates with the scattering peak (or shoulder) correspond to the characteristic distance of that structure.
  • the AFM image is consistent with a blocky copolymer composition exhibiting distinct micro phase domains at a molecular level of at least 0.5 ⁇ .
  • the AFM image and SAXS supports formation of block copolymers.
  • One way to view the block copolymers are as different polymers connected via a covalent bond such that they do not mix, thus the blocks repulse each other and form segregated domains of "nano- scale" structures depending upon molecular weight and chemical nature of each block. In the above case such similar domains are observed in SAXS.
  • 2D-DOSY NMR is a valuable technique to distinguish between block copolymers and the polymer blends of their constituents since the translational diffusion coefficient reflect the change in shape and/or size of polymers. DOSY seeks to separate the NMR signals of different species according to their diffusion coefficient.
  • the 2D-DOSY spectroscopy also confirms the presence of some homopolymer of both C4-C6 and C8-C12, which is not the part of the block copolymer. This can be explained by the fact that the system is a controlled polymerization system rather than living polymerization. Hence, some of the chains of first C8-C12 olefin block have terminated and some unwanted chain transfer and termination reactions favor the formation of C4-C6 homopolymer.
  • olefin block copolymers using controlled cationic polymerization of C4-C6 and C8-C12 olefins.
  • the olefin block copolymer thus produced has multiple thermal transitions as seen by DSC and DMTA.
  • the GPC, SAXS and 2D-DOSY NMR spectroscopy techniques were used to successfully characterize the olefin block copolymers.
  • These olefin block copolymers find use in styrenic- based block hot melt adhesive or with immiscible multilayer films, thus improving inter-layer adhesion, as well as tackifying each block to produce a useful adhesive.
  • the olefin block copolymer when mixed with base polymer as described above, will preferably phase separate in the melt state and will partition at the interface, with the C4- C6 olefin block staying in the aliphatic portion of the base polymer and the C8-C12 olefin block in the aromatic portion of the base polymer.
  • the thermal and flow properties of the base polymer will be influenced also by the weight percent (wt%) of olefin block copolymer in each of the blocks of base polymer. If a prior art random copolymer-type tackifier is used, it typically resides in one of the phases of base polymer, thereby changing the thermal properties of only that block without affecting the other block.
  • Example 3 (olefin block copolymer versus blends and commercial tackifiers): Blends of 30 wt% of SIS block copolymer VectorTM 4111 (from Dexco), by weight of the blend, were prepared with 70 wt% of the following EscorezTM tackifiers (all from ExxonMobil) described in Table 1 and inventive olefin block copolymer, numbered here as in Table 2: (2) E5400; (3) E5600; (4) mixture of E7105 and El 102; (5) C8-C12 homopolymer; (6) poly(C9- b-C5) (the inventive olefin block copolymer); (7) C8-C12 and C4-C6 homopolymer mixture.
  • Homogenous blends were made by heating the block copolymer and tackifier at 190°C in a high speed mixer. The polymer blend was cooled and samples were prepared for DMTA measurements described above. Table 2 describes the T g of each segment as observed in DMTA, and compared with the T g calculated ("theoretical") using Fox-Flory equation.
  • Sample 1 is the SIS block copolymer VectorTM 4111 with no tackifier, showing two T g , the first T g at -50°C which corresponds to the isoprene phase present in the block copolymer, and the second T g at 100°C which corresponds to the hard styrene phase.
  • Commercially available tackifiers are selected in such a way, such as E5400 and El 102, remain in the aliphatic phase of block copolymer (midblock tackifier) whereas others, such as E5600 and E7105 remain in the more polar styrenic phase (end-block).
  • Sample 2 contains 30 wt% of Vector 4111 and 70 weight % of E5400.
  • the calculated value of the midblock Tg is 1°C, however, the DMTA showed -6°C.
  • the discrepancy observed can be explained by the fact that not all of the E5400 tackifier migrates to the isoprene phase.
  • the Sample 3 DMTA shows that the aromatic E5600 associates with the styrene phase of the SIS block copolymer and changes its T g , which can be seen by comparing the "component" T g and "measured” T g values in Table 2. However, the isoprene phase is unaffected.
  • the 50/50 mixture of El 102 and E7105 was blended with Vector 4111. Theoretically, the tackifier El 102 would migrate to the rubbery isoprene phase and E7105 into aromatic phase and change the corresponding transitions. However, only one broad transition is seen between 40 to 60°C.
  • Sample 5 is a blend of the SIS block copolymer with the C8-C12 homopolymer, and as expected, the homopolymer is compatible with the aromatic phase of the polymer and changes its T g without affecting the T g of the aliphatic phase.
  • Sample 6 is a blend of Vector 4111 with the Example 2 olefin block copolymer. In the melt state, it phase separate into different domains. The C4-C6 portion of the olefin block copolymer is compatible with the isoprene block of SIS block copolymer and changes its T g .
  • the C8-C12 part of the olefin block copolymer changes the T g of styrene domain.
  • the claimed polymer or polymer blend includes only the named components and no additional components that will alter its measured properties by any more than 10 or 20%, and most preferably means that additional components are present to a level of less than 5, or 4, or 3, or 2 wt% by weight of the composition.
  • additional components can include, for example, fillers, colorants, antioxidants, anti-UV additives, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers, often referred to as hydrocarbon polyethylenes, and other additives well known in the art.
  • the phrase "consisting essentially of means that there are no other process features that will alter the claimed properties of the polymer, polymer blend or article produced therefrom by any more than 10 or 20%.

Abstract

L'invention concerne des copolymères qui comportent au moins un bloc comportant des motifs dérivés d'oléfines en C8-C12, au moins un bloc comportant des motifs dérivés d'oléfines en C4-C6 et au moins un bloc comportant des motifs dérivés d'oléfines en C5/C10, chaque bloc ayant une masse moléculaire moyenne en nombre d'au moins 300 g/mole et deux températures de transition vitreuse (Tg). Les copolymères à blocs d'oléfines sont formés par combinaison d'une première oléfine avec un catalyseur dans au moins une première étape, pour former un premier bloc d'oléfine, et par combinaison d'une seconde oléfine avec le même catalyseur ou avec un catalyseur différent dans au moins une étape distincte, pour former un second bloc. Les copolymères sont utiles en tant qu'agents poisseux dans des compositions adhésives et dans des films.
PCT/US2017/067180 2016-12-22 2017-12-19 Copolymères à blocs d'oléfines aliphatiques/aromatiques WO2018118834A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020197018045A KR102250766B1 (ko) 2016-12-22 2017-12-19 지방족/방향족 올레핀 블록 코폴리머
EP17826663.1A EP3559063A1 (fr) 2016-12-22 2017-12-19 Copolymères à blocs d'oléfines aliphatiques/aromatiques
CN201780085457.9A CN110248974B (zh) 2016-12-22 2017-12-19 脂族/芳族烯烃嵌段共聚物
JP2019534349A JP7106544B2 (ja) 2016-12-22 2017-12-19 脂肪族／芳香族オレフィンブロックコポリマー

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201662437992P 2016-12-22 2016-12-22
US62/437,992 2016-12-22
EP17154543.7 2017-02-03
EP17154543 2017-02-03

Publications (1)

Publication Number Publication Date
WO2018118834A1 true WO2018118834A1 (fr) 2018-06-28

Family

ID=57965773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2017/067180 WO2018118834A1 (fr) 2016-12-22 2017-12-19 Copolymères à blocs d'oléfines aliphatiques/aromatiques

Country Status (1)

Country Link
WO (1) WO2018118834A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2317859A (en) 1939-02-17 1943-04-27 United Gas Improvement Co Styrene-polypiperylene copolymer
EP0183448A2 (fr) * 1984-11-21 1986-06-04 Exxon Research And Engineering Company Résines d'hydrocarbures
EP0879863A1 (fr) * 1993-05-25 1998-11-25 Minnesota Mining And Manufacturing Company Adhésif sensible à la pression et ruban adhésive comprenant un polymère bloc à plusieurs branches
WO1998057999A1 (fr) * 1997-06-17 1998-12-23 Exxon Chemical Patents Inc. Resines aromatiques modifiees a base de c5 brut

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2317859A (en) 1939-02-17 1943-04-27 United Gas Improvement Co Styrene-polypiperylene copolymer
EP0183448A2 (fr) * 1984-11-21 1986-06-04 Exxon Research And Engineering Company Résines d'hydrocarbures
EP0183448B1 (fr) 1984-11-21 1989-04-05 Exxon Research And Engineering Company Résines d'hydrocarbures
EP0879863A1 (fr) * 1993-05-25 1998-11-25 Minnesota Mining And Manufacturing Company Adhésif sensible à la pression et ruban adhésive comprenant un polymère bloc à plusieurs branches
WO1998057999A1 (fr) * 1997-06-17 1998-12-23 Exxon Chemical Patents Inc. Resines aromatiques modifiees a base de c5 brut

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
GILLARD, T. M.; PHELAN, D.; LEIGHTON, C.; BATES, F.S., MACROMOLECULES, vol. 48, no. 13, 2015, pages 4733 - 4741
HILLMYER, M. A.; MAURER, W. W; LODGE, T. P.; BATES, F. S., J. PHYS. CHEM. B, vol. 103, 1999, pages 4814 - 4824
LUCASA, L. H.; OTTOA, W.H.; LARIVEB, C. K., J. OF MAGNETIC RESONANCE, vol. 156, no. 1, 2002, pages 138 - 145
MORRIS, K. F.; STILBS, P.; JOHNSON JR, C. S., ANAL. CHEM., vol. 66, no. 2, 1994, pages 211 - 215
REN, L.; LIU, K.; HE, Q.; OU, E.; LU, Y.; XU, W., ROYAL SOC. CHEM., vol. 6, 2016, pages 51533 - 51543
SAGDON, A.; KIM, E-H; LEE, C., BULL. KOREAN CHEM. SOC., vol. 26, no. 2, 2005, pages 331
T. SUN; P. BRANT; R. R. CHANCE; W. W. GRAESSLEY, MACROMOLECULES, vol. 34, no. 19, 2001, pages 6812 - 6820

Similar Documents

Publication Publication Date Title
Schulz et al. Precision polymers through ADMET polymerization
Xu et al. Synthesis and remarkable efficacy of model polyethylene-graft-poly (methyl methacrylate) copolymers as compatibilizers in polyethylene/poly (methyl methacrylate) blends
Pyun et al. ABA triblock copolymers containing polyhedral oligomeric silsesquioxane pendant groups: synthesis and unique properties
Schmidt et al. Morphological Behavior of Model Poly (ethylene‐alt‐propylene)‐b‐polylactide Diblock Copolymers
JP2010501719A (ja) メタセシスによる非晶質ポリマーセグメント交換によるブロックコポリマーの製造
WO2008027283A2 (fr) Production de copolymères métabloc par échange de segments polymères
CN104428348B (zh) 具有基本上不均匀组成分布和表现出热塑性弹性体性能的萜烯/异烯烃共聚物
Chanda et al. Controlling interlamellar spacing in periodically grafted amphiphilic copolymers
Buonerba et al. Crystalline syndiotactic polystyrene as reinforcing agent of cis-1, 4-polybutadiene rubber
JP2010501718A (ja) 高融点ポリマーセグメントのメタセシスによるランダムブロックコポリマーの製造
Morell et al. Synthesis of a new multiarm star polymer based on hyperbranched poly (styrene) core and poly (ε‐caprolactone) arms and its use as reactive modifier of epoxy thermosets
Puskas et al. Controlled/living carbocationic copolymerization of isobutylene with alloocimene
Métafiot et al. β-myrcene/isobornyl methacrylate SG1 nitroxide-mediated controlled radical polymerization: Synthesis and characterization of gradient, diblock and triblock copolymers
WO2011129771A1 (fr) Composition thermoplastique formée à partir d'acide polylactique et d'un copolymère greffé élastomère
JP6749502B2 (ja) トリブロックコポリマー
Buonerba et al. Improvement of tensile properties, self-healing and recycle of thermoset styrene/2-vinylfuran copolymers via thermal triggered rearrangement of covalent crosslink
US10800870B2 (en) Aliphatic/aromatic olefin block copolymers
EP3559063A1 (fr) Copolymères à blocs d'oléfines aliphatiques/aromatiques
WO2018118834A1 (fr) Copolymères à blocs d'oléfines aliphatiques/aromatiques
Switek et al. ABA triblock copolymers with a ring‐opening metathesis polymerization/macromolecular chain‐transfer agent approach
JP6806715B2 (ja) ジエンゴム／ポリプロピレン熱可塑性エラストマーコポリマー、それを含有する組成物、および調製方法
Malus et al. Structurally well-defined functionalized polyolefins and graft copolymers thereof as bitumen modifiers
Datta Rubber–Plastic Blends: Structure–Property Relationship
Coffin et al. Pseudo-tetrablock copolymers with ethylene and a functionalized comonomer
EP4046785A1 (fr) Procédé pour l'ajustement de la dureté d'un corps moulé et corps moulé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17826663

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197018045

Country of ref document: KR

Kind code of ref document: A

Ref document number: 2019534349

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017826663

Country of ref document: EP

Effective date: 20190722