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WO2001068769A1 - Composition polymere - Google Patents

Composition polymere Download PDF

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Publication number
WO2001068769A1
WO2001068769A1 PCT/EP2001/003125 EP0103125W WO0168769A1 WO 2001068769 A1 WO2001068769 A1 WO 2001068769A1 EP 0103125 W EP0103125 W EP 0103125W WO 0168769 A1 WO0168769 A1 WO 0168769A1
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Prior art keywords
polymeric composition
block
polymer
polymerisable compound
curable polymeric
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PCT/EP2001/003125
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English (en)
Inventor
Olivier Roumache
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Shell Internationale Research Maatschappij BV
Kraton Polymers Research BV
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Shell Internationale Research Maatschappij BV
Kraton Polymers Research BV
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Priority to AU2001250391A priority Critical patent/AU2001250391A1/en
Publication of WO2001068769A1 publication Critical patent/WO2001068769A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L53/005—Modified block copolymers
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • 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
    • C08L53/025—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 modified

Definitions

  • the present invention relates to a curable polymeric composition.
  • a curable polymeric composition comprising a thermoplastic block copolymer, a radically polymerisable compound and a radical initiator.
  • the invention further relates to a process for curing the curable polymeric composition; to a cured polymeric composition; to a block copolymer; to a thermoplastic blend; and to articles containing the curable polymeric composition, the cured polymeric composition, the block copolymer or the thermoplastic blend.
  • thermoplastic elastomers are well known in the art and many thermoplastic elastomers are available commercially.
  • An important class of thermoplastic elastomers is the class of styrenic block copolymers. These block copolymers are typically characterised by at least two polymer blocks of primarily polymerised monovinyl aromatic hydrocarbon monomers, separated by at least one olefinic polymer block, such as an optionally hydrogenated polymer block of primarily polymerised conjugated diene monomers.
  • a generally accepted theory to explain the behaviour of styrenic block copolymers is the so-called domain theory. It is thought that the monovinyl hydrocarbon polymer block (s) of a block copolymer molecule form domains with other monovinyl aromatic hydrocarbon blocks of other block copolymer molecules . The domains form physical cross-links between the block copolymer molecules . At a temperature above the glass transition temperature of the olefinic polymer block, but below the glass-transition temperature of the monovinyl aromatic hydrocarbon polymer blocks, the block copolymer is physically cross-linked and elastomeric.
  • the domains Upon heating the block copolymer above the glass-transition temperature of the monovinyl aromatic hydrocarbon blocks, the domains are softened and the block copolymers become melt-processable . Upon cooling, the domains are formed again.
  • the glass-transition temperature of e.g. a styrene polymer block is about 95 °C.
  • a styrenic block copolymer, containing styrene polymer blocks as the monovinyl aromatic hydrocarbon blocks above this glass-transition temperature, the viscosity and the elasticity of the block copolymer remains high due to the non-Newtonian behaviour of the melt, even at high shear rates, compared to homopolymer of the same molecular weight. This behaviour is attributed to the persistence of a two-phase "domain" structure that persists in the melt below the so-called order-disorder transition temperature.
  • a glass-transition temperature of about 95 °C for polystyrene blocks is not sufficient.
  • a so-called "endblock” resin with a much higher glass-transition temperature is often added.
  • endblock resins include polyphenylene oxide and poly ( ⁇ -methylstyrene) .
  • the endblock resin is typically compatible with the monovinyl aromatic hydrocarbon block, but not with the olefinic polymer block.
  • the glass—transition temperature of the aromatic domains can be increased by this method, and, hence, the operating window, the proper blending of the end-block resin into the block copolymer has to take place at a very high temperature, well above the glass transition temperature of the end-block resin. Moreover, the blend viscosity is increased relative to the block copolymer at moderate processing temperature. Accordingly, it would be desirable if a polymeric composition could be found, capable of decreasing the viscosity of styrenic block copolymers during processing and, preferably, capable of imparting good high temperature properties, whilst preferably retaining other useful properties of the polymeric composition.
  • the present invention relates to a curable polymeric composition
  • a curable polymeric composition comprising
  • thermoplastic block copolymer containing at least two polymer blocks A separated by at least one polymer block B, wherein polymer block A is primarily a poly (monovinyl aromatic hydrocarbon) block or primarily a poly(C3 ⁇ C7 alkenoic acid ester) block, and polymer block B is primarily an aliphatic elastomeric polymer block;
  • a radically polymerisable compound that is at least partially compatible with polymer blocks A, and not compatible with polymer block B, wherein the weight percentage of radically polymerisable compound is in the range from 0.1 to 3 times the weight percentage of polymer blocks A, where both weight percentages are basis the total of block copolymer and radically polymerisable compound; and (in) a radical initiator that is at least partially compatible with the polymer blocks A and/or the radically polymerisable compound, and not compatible with polymer block B.
  • the radically polymerisable compound is at least partially compatible, preferably compatible, with polymer blocks A and acts as a solvent, weakening the domains formed by the A blocks.
  • the radically polymerisable compound forms a resin that is typically compatible with the same polymer blocks A, but not with polymer blocks B and preferably imparts good high temperature properties on the cured polymeric composition.
  • the cured polymeric composition is typically still thermoplastic.
  • the present invention further relates to a process for the preparation of a cured polymeric composition, which comprises radically polymerising the radically polymerisable compound in the curable polymeric composition as described herein at a temperature below the order-disorder transition temperature of the polymeric composition.
  • the present invention further relates to a cured polymeric composition, obtainable by curing the curable polymeric composition as described herein; and to a block copolymer containing at least two polymer blocks A, and at least one polymer block B, wherein polymer block B is primarily an aliphatic elastome ⁇ c polymer block and polymer block A is primarily a monovinyl aromatic hydrocarbon polymer block further containing polymerised (radically polymerisable compound), obtainable by curing the curable polymeric composition as described herein.
  • the present invention relates to articles containing the curable polymeric composition, the cured polymeric composition or the block copolymer.
  • the order-disorder transition temperature is the temperature at which the A and B blocks of the block copolymer are sufficiently compatible to form a single phase.
  • the order-disorder transition temperature is well known m the art and described extensively in e.g. Thermoplastic Elastomers - A Comprehensive Review, edited by N.R. Legge, G. Holden and H.E. Schroeder (1987), Carl Hanser Verlag Kunststoff, Chapter 12/3 by T. Hashimoto, incorporated herein by reference.
  • the order-disorder transition temperature is dependent on any other components in the polymeric composition that may strengthen or weaken the domain structure of the block copolymer m the polymeric composition.
  • the order-disorder transition temperature is determined by small-angle X-ray scattering (SAXS) profiles, as described in the above referenced publication.
  • SAXS small-angle X-ray scattering
  • the order-disorder transition temperature can be approximated by alternative methods such as proton NMR or DMTA as described by CD. Han and J. Kim m ⁇ Macromolecules (1989), 22, p.383-394' and m ⁇ Journal of polymer science Part B: Polymer Physics 25, p.1741 (1987) and 26, p.677 (1988)').
  • DMTA Dynamic Mechanical Thermal Analysis
  • Such mixture is said to be compatible if transparent and without any bleeding out or macroscopic separation of one ingredient from the mixture.
  • two ingredients are said to be incompatible if the said mixture exhibits a non-transparent (i.e. milky) appearance and/or if at least one ingredient has a macroscopically evident tendency to bleed out of the mixture.
  • This compatibility concept has been described in US patent specification No. 3,917,607, incorporated herein by reference.
  • Block copolymers are well known in the art and available commercially. A variety of polymerisation processes can be employed, but anionic polymerisation in the presence of an organic alkali-metal-containing initiator is preferred.
  • Polymer block A is primarily a poly (monovinyl aromatic hydrocarbon) block or primarily a poly(C3 ⁇ C7 alkenoic acid ester) block, such as a poly (acrylate) block. Both polymer blocks are anionically polymerisable.
  • polymer block A For the purposes of this invention "primarily" means in relation to polymer block A, that the polymer block A is composed of at least 75% by weight, preferably at least 90% by weight of monovinyl aromatic hydrocarbon or C3-C7 alkenoic acid ester as the case may be.
  • the remainder of the block is typically a polymerised olefinic monomer or, respectively, a C3-C7 alkenoic acid ester or a monovinyl aromatic hydrocarbon.
  • mixtures of several C3-C7 alkenoic acid esters or several monovinyl aromatic hydrocarbons may be employed.
  • polymer block A is substantially composed of the same polymerised monomer, that is, more preferably, polymer block A is composed of at least 95% by weight of a monovinyl aromatic hydrocarbon or a C3-C7 alkenoic acid ester.
  • polymer block A is a poly (monovinyl aromatic hydrocarbon) block.
  • Polymer block B is primarily an aliphatic elastomeric polymer block.
  • polymer block B For the purposes of this invention "primarily" means in relation to polymer block B, that the polymer block B is composed of at least 75% by weight, preferably at least 90% by weight of an aliphatic elastomer. The remainder of the block is typically polymerised C3-C7 alkenoic acid ester and/or monovinyl aromatic hydrocarbon. More preferably, polymer block B is substantially composed of the same polymerised monomer, that is, more preferably, polymer block B is composed of at least 95% by weight of an aliphatic elastomer. Preferably, polymer block B is a hydrogenated poly (conjugated diene) block.
  • the block copolymer typically has the structure A-B-A' , A-B-A'-B', (A-B)nX or (A-B) pX (B' ( -A' ) r ) q, wherein X is the residue of a coupling agent, A' and B' are polymer blocks of the same or different molecular weight as polymer blocks A and B respectively and polymer blocks A' and B' are selected from the same group of chemical compounds as polymer blocks A and B respectively; n > 2; p > 1; r is 0 or 1; q > 1; and (r*q + p) > 2.
  • the block copolymer may be a blend of block copolymers and/or may contain up to 80% by weight of a diblock copolymer containing one polymer block A and one polymer block B, basis the total block copolymer content.
  • the preferred amount of diblock copolymer very much depends on the targeted end-use. Thus, if for instance it is desired to provide a tacky adhesive composition, the desired amount of diblock copolymer may be rather high.
  • the diblock copolymer content is not more than 40% by weight, more preferably not more than 30% by weight.
  • the block copolymer does not contain diblock copolymer.
  • the block copolymer may be prepared by any method known in the art and is typically be prepared by anionic polymerisation.
  • the block copolymer may be prepared by anionic polymerisation using the well-known full sequential polymerisation method, optionally in combination with re-initiation, or the coupling method.
  • Anionic polymerisation of block copolymers is well known in the art and has e.g. been described in US patent specification Nos.
  • a conjugated diene is polymerised and the olefinic unsaturation selectively hydrogenated using hydrogenation catalysts.
  • Selective hydrogenation of conjugated dienes is also well known in the art and has e.g. been described in US patent specification Nos. 3,595,942, 3,700,633, 5,925,717; 5,814,709; 5,886,107; and 5,952,430, incorporated herein by reference.
  • the selectively hydrogenated block copolymer to be used in the polymeric composition of the present invention typically at least 80%, preferably at least 90%, more preferably at least 95%, in particular at least 99% of the double bonds in the conjugated diene block (s) is hydrogenated.
  • the hydrogenation degree can be analysed using the nuclear magnetic resonance (NMR) method.
  • NMR nuclear magnetic resonance
  • the monovinyl aromatic hydrocarbon is chosen from the group of styrene, C ⁇ -C ⁇ alkylstyrene and C ] _-C_] dialkylstyrene, in particular styrene, ⁇ -methylstyrene, o-methylstyrene or p-methylstyrene, 1, 3-dimethylstyrene, p-tert . -butylstyrene or mixtures thereof, more preferably styrene or ⁇ -methylstyrene, most preferably styrene.
  • the C3-C7 alkenoic acid ester is a compound containing C3-C7 alkenoic acid ester groups of formula B,
  • R]_ is hydrogen or a C1-C4 alkyl group
  • R 2 is a C ] _-C3 alkane group
  • R3 is a C ⁇ -C ⁇ arene, alkane or cycloalkane group
  • R4 is hydrogen or a methyl group
  • a is 0 or 1, more preferably 0.
  • the C3-C7 alkenoic acid ester is even more preferably chosen from the group of acrylates, methacrylates, methylacrylates and methylmethacrylates (that is, in formula B, a is 0 and Ri and R4 are hydrogen or methyl), most preferably butylacrylate (i.e. in Formula B, a is 0; R j _ and R4 are hydrogen and R3 is a butyl group) .
  • the conjugated diene is chosen from conjugated dienes containing from 4 to 24 carbon atoms, more preferably from 4 to 8 carbon atoms, in particular butadiene or isoprene. If the conjugated diene is butadiene it is preferred to polymerise a substantial part of the butadiene via 1,2-addition rather than 1, 4-addition. Preferably, the amount of butadiene that is polymerised via 1,2-addition is at least 25% of the total amount of polymerised butadiene. In other words, the so-called 1,2-vinyl content prior to hydrogenation is preferably at least 25%, more preferably in the range from 30 to 90%.
  • polar compounds such as ethers, amines and other Lewis bases and more in particular those selected from the group consisting of dialkylethers of glycols.
  • Most preferred modifiers are selected from dialkyl ether of ethylene glycol containing the same or different terminal alkoxy groups and optionally bearing an alkyl substituent on the ethylene radical, such as monoglyme, diglyme, diethoxyethane, 1, 2-diethoxy-propane, l-ethoxy-2, 2-tert- butoxyethane, of which 1, 2-diethoxypropane is most preferred.
  • the polymer blocks A comprise from 5 to 90% by weight of the block copolymer, more preferably from 10 to 60% by weight, even more preferably from 10 to 45% by weight, in particular from 13 to 35% by weight .
  • the polymer blocks A typically have a weight average molecular weight in the range from 3,000 to 100,000; preferably from 4,000 to 60,000; more preferably from 5,500 to 15,000 g/mol .
  • the polymer blocks B typically have a weight average molecular weight m the range from 10,000 to 300,000; preferably from 30,000 to 180,000; more preferably from 35,000 to 100,000 g/mol .
  • the total block copolymer typically has a weight average molecular weight in the range from 16,000 to 1,000,000; preferably from 25,000 to 900,000. If the block copolymer is linear, more preferably the weight average molecular weight is m the range from 30,000 to 200,000, m particular m the range from
  • the block copolymer is radial, more preferably the weight average molecular weight of each arm is in the range 10,000 to 100,000 and the total weight average molecular weight is m the range 35,000 to 500,000.
  • Weight average molecular weight as referred to herein is real weight average molecular weight in gr/mole. It is re-calculated, taking into account the actual chemical composition of the polymer, its structure and the precise measurement of the real A blocks molecular weight determined by gel permeation chromatography in accordance with ASTM D 3536 using pure A homopolymer standards.
  • the radically polymerisable compound must be at least partially compatible with polymer blocks A and is not compatible with polymer blocks B. Moreover, preferably, the radically polymerisable compound after polymerisation is still compatible with polymer blocks A.
  • the radically polymerisable compound is preferably present in an amount such that the weight percentage of radically polymerisable compound is less than 2.5 times the weight percentage of polymer blocks A, wherein both weight percentages are basis the total of block copolymer and radically polymerisable compound. More preferably, the weight percentage of radically polymerisable compound is in the range from 0.5 to 2 times the weight percentage of polymer blocks A, on the same basis.
  • the radically polymerisable compound can suitably be any compound that satisfies the above criteria. It is thought that the solubility parameter of the radically polymerisable compound is typically close to the solubility parameter of polymer block A and not close to the solubility parameter of polymer block B.
  • the solubility parameter is well known to those skilled in the art and has been described in 'Polymer Handbook' third edition (1989) edited by J. BRANDRUP and E.H. IMMERGUT, John Wiley & Sons (ISBN 0-471-81244-7), incorporated herein by reference. The book describes a group contribution method, which can be used to estimate the solubility parameter of a chemical compounds based on the knowledge of their chemical structure and their density.
  • Solubility parameters calculated using the group contribution method and using the measured densities listed in the same book are ( (cal/cm ⁇ ) 1/2 ⁇ : amorphous polystyrene: 9.02; amorphous polyethylene: 8.26; amorphous polypropylene: 7.77; amorphous polybutene-1 : 7.89.
  • the solubility parameter of the radically polymerisable compound should be in the range from
  • solubility parameter of the polymer block A preferably, in the range from -0.15 to +0.5.
  • the radically polymerisable compound preferably has a solubility parameter in the range from 8.52 to 10.02, preferably, in the range from 8.87 to 9.52.
  • the radically polymerisable compound is preferably chosen from the group of styrene, C;[-C4-alkylstyrene, C ⁇ _C4-dialkylstyrene, compounds containing C3-C7 alkenoic acid ester groups, divinyl benzene, and divinyl C1-C4 alkyl benzene.
  • the radically polymerisable compound is a compound containing C3-C7 alkenoic acid ester groups of formula A,
  • R ⁇ _ is hydrogen or a C1-C alkyl group
  • R is a C -C3 alkane group
  • R3 is a C_-Cg arene, alkane or cycloalkane group
  • R4 is hydrogen or a methyl group
  • a is 0 or 1
  • b is an integer in the range from 1 to 6.
  • the compound containing C3-C7 alkenoic acid ester groups is selected from those compounds represented by formula A in which a is 0 and b is an integer in the range from 1 to 4.
  • the curable polymeric composition is still thermoplastic after curing.
  • a thermoplastic polymeric composition can be prepared that is still processable at high temperatures and returns to the original form e.g. at room temperature. Accordingly, a thermoplastic composition can now been provided that is easily processable prior to curing, and after curing is still processable and has certain improved properties such as a higher temperature resistance.
  • the processability of the polymeric composition after curing is considered important e.g. from an environmental point of view as it allows recycling of the polymeric composition .
  • the radically polymerisable compound is chosen from monovinyl containing compounds, more preferably chosen from the group of styrene, C;[-C4-alkylstyrene, C]_-C4 ⁇ dialkyl- styrene, and saturated compounds containing one C3-C7 alkenoic acid ester group.
  • the radically polymerisable compound is chosen from divinyl or polyvinyl containing compounds .
  • the weight percentage of polymer block A, radically polymerisable compound, radical initiator, and any polymer block A compatible oil or resin is not more than 30%, and preferably not more than 25% by weight basis the total block copolymer and auxiliaries that are compatible with either the A or the B polymer blocks; and moreover it is preferred that the total weight average molecular weight of the block copolymer is not more than 125,000.
  • the present invention relates to a curable polymeric composition that is thermoset after curing, wherein the radically polymerisable compound is chosen from divinyl or polyvinyl containing compounds; wherein the total weight average molecular weight of the block copolymer is more than 160,000 if the weight percentage of polymer block A, radically polymerisable compound, radical initiator, and any polymer block A compatible oil or resin is less than 30% by weight basis the total block copolymer and auxiliaries that are compatible with either the A or the B polymer blocks.
  • Cured thermoset polymeric compositions are known in the art. Known cured thermoset polymeric compositions, however, are often cross-linked through the polymer block B. This has an adverse effect on elastomeric properties of the cured polymeric composition. It would be desirable if a system could be found that cross-links the polymer blocks A rather than B.
  • US patent specification No. 4,556,464 describes an endblock cross-linked block copolymer composition.
  • the block copolymer has the structure A-B-A, wherein B stands for a not-hydrogenated conjugated diene polymer block and A stands for a not-hydrogenated copolymer block of a conjugated diene and an aromatic hydrocarbon.
  • An acrylate that was compatible with the A blocks was used to cross-link the system. Despite the higher concentration of cross-links in the A blocks, a significant amount of cross-links were still made in the B block.
  • S-EB-S block copolymer where S stands for a polystyrene block and EB stands for an ethylene/butylene block (which is the structure that forms when hydrogenatmg a butadiene block) .
  • the polymeric composition is cured by electron beam radiation, which results m cross-linking through primarily the B blocks .
  • US patent specification No. 5,066,728 describes block copolymers of structure A-B-A, where the A blocks are more reactive than the B blocks when cured with electron beam radiation.
  • the A blocks consist of poly (2-phenyl- butadiene) and the B blocks consist of polybutadiene or polyisoprene.
  • the patent specification describes that the amount of cross-linking in the A blocks is significantly higher than for alternative polymeric systems known at the time. However, if good heat-agemg resistance, weatherability and resistance to oxidation are desired, then selectively hydrogenated block copolymers are preferred .
  • the curable polymeric composition of the present invention comprises a block copolymer containing little, if any, olefinic unsaturation; and upon curing the block copolymer is primarily cross-linked through the polymer blocks A and not through the polymer blocks B.
  • the curable polymeric composition of the present invention must comprise a radical initiator.
  • the radical initiator should be at least partially compatible with the polymer blocks A and/or the radically polymerisable compound, and, preferably, is not compatible with the B blocks.
  • suitable radical initiators include photo-mitiators and thermal radical initiators, that is, radical initiators which decompose at a certain temperature to form radicals.
  • thermal radical initiators examples include peroxide compounds and azo compounds. Many of such compounds are well known in the art and available commercially. Specific compounds differ m the temperature at which they decompose to form radicals. It s important to know the half-life of the thermal radical initiator for determining ts useful temperature range.
  • the temperature at which the half-life t ] _/ of benzoyl peroxide is one hour is 91 °C and the temperature at which the half-life is ten hours is 71 °C.
  • the temperature at which the half-life is ten hours is 71 °C.
  • the temperature at which the half-life is ten hours is 71 °C.
  • the temperature at which the half-life is ten hours is 71 °C.
  • the temperature at which the half-life is ten hours is 71 °C.
  • t-butyl perbenzoate the temperature is 125 °C or 105 °C for t ] _/ being 1 hour or 10 hours respectively.
  • the temperature is 105 °C or 88 °C for t]_/ being 1 hour or 10 hours respectively.
  • thermal radical initiator It belongs to the skilled of the skilled person to select an appropriate thermal radical initiator, with the appropriate half-life at the right temperature. As will be discussed in more detail herein after, care should be taken that the thermal radical initiator is used at a temperature that is below the order-disorder transition temperature of the block copolymer in the polymeric composition. Azo compounds and peroxy compounds have been discussed in detail in the Encyclopedia of Polymer Science and Engineering, John Wiley & Sons (1988), volume 2, pages 143-157 and volume 11, pages 1-21 respectively, incorporated herein by reference. It is expected that a particular useful group of thermal radical initiators are those initiators that are commonly used in the radical polymerisation of styrene to manufacture of polystyrene.
  • Examples of commercially available compounds are (see also volume 16, page 26 of the above encyclopaedia): 2, 2' -azobis (isobutyronitrile) ; 2,2'-azobis(2, 4 -dimethyl aleronitrile) ; l,l'-azobis- (cyclohexanecarbonitrile) ; benzoyl peroxide; t-butyl 2-methylperbenzoate; dicumyl peroxide; t-butyl cumyl peroxide; di-t-butylperoxide; 1 , 1-di ( t-butyl- peroxy) -3, 3, 5-trimethylcyclohexane; dilauroyl peroxide; di (2-ethylhexyl ) peroxydicarbonate; t-amyl peroctoate; t-butyl peracetate; t-butyl perbenzoate; 2 , 5-bis (benzoyl- peroxy) -2, 5-dimethylhe
  • the radical initiator is a photo-initiator.
  • Photo-initiators are known in the art and examples of suitable photo-initiators have been disclosed in European patent specification No. 0 696 761 and US patent Nos. 4,894,315; 4,460,675 and 4,234,676.
  • the photo-initiator is selected from optionally substituted polynuclear quinones, aromatic ketones, benzoin and benzoin ethers and 2 , 4 , 5-triarylimidazolyl dimers .
  • the photo-initiator is preferably selected from the group consisting of: (1) a benzophenone of the general formula (I) - I f
  • R 1 to R 6 independently represent hydrogen or an alkyl group having from 1 to 4 carbon atoms, preferably methyl, and wherein R ⁇ and/or R ⁇ have the same meaning as R ⁇ to R ⁇ or represent in addition alkoxy or 1 to 4 carbon atoms and wherein n has a value of 0, 1, or 2, optionally in combination with at least one tertiary a ine,
  • a sulphur-containing carbonyl compound wherein the carbonyl group is directly bound to at least one aromatic ring and is preferably of the general formula II wherein R", R!0, and RU each may represent hydrogen, alkyl of 1 to 4 carbon atoms, or an alkylthio having 1 to 4 carbon atoms, and
  • Examples of suitable compounds of category (1) are benzophenone, 2 , 4 , 6-trimethylbenzophenone, 4-methylbenzo- phenone, and eutectic mixtures of 2 , 4 , 6-trimethylbenzophenone and 4-methylbenzophenone (ESACURE TZT), or 2, 2-dimethoxy-l, 2-diphenylethan-l-one (IRGACURE 651) (ESACURE and IRGACURE are trademarks) .
  • These compounds may be employed in combination with tertiary amines, such as e.g. UVECRYL 7100 (UVECRYL is a trademark) .
  • Category (2) embraces compounds such as, e.g., 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- propanone-1, commercially available as IRGACURE 907.
  • An example of suitable mixtures (category (3)) is a mixture of 15 percent by weight of a mixture of 2-isopropyl- thioxanthone and 4-isopropylthioxanthone, and 85 percent by weight of a mixture of 2, 4 , 6-trimethylbenzophenone and 4-methylbenzophenone . This mixture is commercially available under the trade name ESACURE X15.
  • Photo-initiators of any one of the above categories (1), (2), and (3) may also be used in combination with other photo- initiators, such as e.g. UVECRYL P115 (a diamine) . Particularly useful is a combination of benzophenone or IRGACURE 651 and said UVECRYL P115.
  • the photo-initiator is selected from the group consisting of (i) benzophenone, or 2 , 2-dimethoxy-l , 2-di- phenylethan-1-one (IRGACURE 651) , (ii) a mixture of benzophenone or IRGACURE 651, and a tertiary amine, and (iii) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- propanone-1. Of these 2-methyl-l- [ 4- (methylthio) phenyl] - 2-morpholinopropanone-l or 2, 2-dimethoxy-l , 2-diphenyl- ethan-1-one are most preferred.
  • the photo-initiator is present in an amount from 0.005 to 15 parts by weight per 100 parts by weight of radically polymerisable compound, preferably from 0.1 to 5 parts by weight.
  • the curable polymeric composition as described herein may further comprise an aliphatic or cycloaliphatic diluent, or a mixture of diluents, compatible with polymer blocks B, but not with polymer blocks A preferably not with the radically polymerisable compound or the radical initiator.
  • Suitable aliphatic and cycloaliphatic diluents are: paraffinic process oils (e.g. CATENEX SM925); naphthenic oils; fully or highly hydrogenated process oils (e.g. ONDINA N68 or PRIMOL 352); waxes; liquid hydrogenated aromatic resins (e.g. REGALITE R1010) ; liquid polyalphaolefins (e.g. DURASYN 166) ; and liquid polymers such as hydrogenated polyisoprene, hydrogenated polybutadiene or polybutene-1 (CATENEX, ONDINA, PRIMOL, REGALITE and DURASYN are trademarks) .
  • paraffinic process oils e.g. CATENEX SM925
  • naphthenic oils e.g. ONDINA N68 or PRIMOL 352
  • waxes e.g. ONDINA N68 or PRIMOL 352
  • liquid hydrogenated aromatic resins e.g. REGALITE R
  • the diluents may typically be present in an amount up to 2000 parts by weight per "100 parts by weight of polymer blocks B" , depending on the end-use application. In general, the amount of diluent will be in the range from 20 to 400 parts by weight.
  • the curable polymeric composition may further comprise a tackifying resin compatible with polymer blocks B, but not with polymer blocks A.
  • Tackifying resins are well known to those skilled in the art. A wide variety of different tackifying resins are available commercially.
  • the tackifying resin to be used in the present invention is preferably a partially or fully hydrogenated aliphatic hydrocarbon resin or rosin ester or a fully hydrogenated aromatic hydrocarbon resin.
  • suitable tackifying resins are: hydrogenated styrene-based resins such as REGALREZ resins designated as 1018, 1033, 1065, 1078, 1094 and 1126; REGALREZ 6108, a 60% hydrogenated aromatic resin; hydrogenated tackifying resins based on C5 and/or C9 hydrocarbon feedstocks such as ARKON P-70, P-90, P-100, P-125, P-115, M-90, M-100, M-110 and M-120 resins and REGALITE R-100, MGB-63, MGB-67, and MGB-70 resins; hydrogenated Polycyclopentadienes such as ESCOREZ 5320, 5300 and 5380 resins; hydrogenated polyterpene and other naturally occurring resins such as CLEARON P-105, P-115, P-125, M-105 and M-115 resins and EASOTACK H-100, H-115 and H-130 resins (REGALREZ, ARKON, ESCORE
  • EASOTACK are all trademarks
  • the tackifying resin typically has a softening point as determined by the Ring and Ball method (ASTM E 28) of at least 70 °C, preferably in the range of from 75 to
  • the tackifying resin is a fully hydrogenated hydrocarbon resin .
  • the tackifying resins, if present, may typically be present m an amount of up to 500 parts by weight per
  • polymer blocks B “100 parts by weight of polymer blocks B” , depending on the desired end-use application. In general, the amount of tackifying resin, if present, will be in the range from 10 to 200 parts by weight.
  • the curable polymeric composition may be blended with a polyolefm.
  • suitable polyolefms are polyethylene, polypropylene, polybutene-1, copolymers of these polyolefms, EPDM and other polyolefm elastomers, including those lower density polyolefms made with so-called metallocene catalysts .
  • the polyolefms may typically be present in an amount of up to 2500 parts by weight per "100 parts by weight of polymer blocks B" , depending on the desired end-use application.
  • thermoplastic blend may be produced upon curing of the curable polymeric composition, even if the said composition as such would be thermoset after curing.
  • thermoplastic vulcamsate can be formed by dynamic vulcanisation (curing) of the curable polymeric composition, whilst blending with a polyolefin in an extruder.
  • the extruder should operate at a temperature below the order-disorder temperature of the curable polymeric composition, but this is easily achievable, especially if relatively high molecular weight (Mw > 160,000 g/mol) block copolymers are used.
  • the present invention further relates to a thermoplastic blend comprising from 125 to 2500 parts by weight, preferably from 150 to 2000 parts by weight, of a polyolefin per 100 parts by weight of a curable polymeric composition or a cured polymeric composition as described herein.
  • a thermoplastic blend comprising from 125 to 2500 parts by weight, preferably from 150 to 2000 parts by weight, of a polyolefin per 100 parts by weight of a curable polymeric composition or a cured polymeric composition as described herein.
  • the polymeric composition as such is thermoset after curing.
  • Stabilisers such as antioxidants/UV stabilisers/ radical scavengers may in addition be present in the curable polymeric composition.
  • Preferred stabilisers include phenolic antioxidants, thio compounds and tris (alkyl-phenyl) phosphites.
  • antioxidants/ radical scavengers examples include pentaerythrityl-tetrakis (3, 5-di- tert-butyl-4-hydroxy-hydrocinnamate) (IRGANOX 1010); octadecyl ester of 3,5-bis ( 1, 1-di-methylethyl) -4-hydroxy benzene propanoic acid (IRGANOX 1076); 2,4-bis (n-octyl- thio) -6- (4-hydroxy-3, 5-di-tert-butylanilino) -1,3, 5-tria- zine (IRGANOX 565); 2-tert-butyl-6- (3-tert-butyl-2 ' -hy- droxy-5-methylbenzyl ) -4-methylphenyl acrylate (SUMILIZER GM) ; tris (nonylphenyl) phosphite; tris (mixed mono- and di-
  • Curing processes that induce radical polymerisation with a radical initiator are well known in the art. As set out herein before, it is important that the curing is carried out at a temperature below the order-disorder transition temperature of the polymeric composition. If the curing is carried out above this temperature, little cross-linking in the polymer blocks A will take place (for thermoset compositions) and e.g. the high temperature properties or other desired properties will not improve at all or not to the same extent.
  • the curable polymeric composition is cured by actinic radiation.
  • actinic radiation This can be daylight or an artificial actinic radiation source.
  • the photo-mitiator used is most sensitive in the ultraviolet range. Therefore, preferably, the artificial radiation source should furnish an effective amount of this radiation, more preferably having an output spectrum the range from 200 to 500 nm, even more preferably in the range from 230 to 450 nm.
  • Particularly suitable UV sources are FUSION bulb lamps having output maxima at 260-270 nm, 320 nm and 360 nm ("H" bulb), at 350-390 nm ("D” bulb) or at 400-430 nm (“V” bulb) (FUSION is a trademark) .
  • Combinations of these FUSION bulb lamps may also be used.
  • H and D bulb lamps are particularly useful, while a combination of D bulb and H bulb can also be suitably applied.
  • a further example of a suitable source of UV radiation is a mercury-vapour lamp such as a 300 W/inch (300 W/2.5 cm) UV mercury medium pressure lamp from American UV Company.
  • the gel permeation chromatogram of cured block copolymers contained higher molecular weight species than originally present prior to curing.
  • radically polymerisable monomer in particular acrylate monomers, oligomers and/or polymers are grafted onto polymer blocks A, m particular poly (styrene) blocks A.
  • the present invention further relates to a block copolymer containing at least two polymer blocks A, and at least one polymer block B, wherein polymer block B is primarily an aliphatic elastome ⁇ c polymer block and polymer block A is primarily a monovmyl aromatic hydrocarbon polymer block further containing polymerised radically polymerisable compound, which block copolymer is obtainable by curing a curable polymeric composition as described herein.
  • the cured polymeric composition can be used many end-use applications where e.g. a better temperature resistance is required and/or there is a need for easier processing of the polymeric composition.
  • Typical end-use applications include oil gels, adhesives, sealants, coatings, printing plates, polymer modification and elastome ⁇ c compounds for a variety of applications.
  • the low viscosity of the curable polymeric composition opens up a whole new array of possible products. For example, it should now be possible to provide a solvent-less transparent DIY sealant that comprises the curable polymeric composition and a photo-initiator. The sealant is applied with shear at room temperature and the polymeric composition cures under the influence of daylight.
  • the present invention further relates to articles containing the curable polymeric composition as described herein; or the cured polymeric composition (or the block copolymer) as described herein.
  • EP Ethylene-Propylene block, or hydrogenated polyisoprene block.
  • KRATON D-1101 is a polystyrene-polybutadiene-polystyrene block copolymer (SBS) (KRATON is a trade mark) .
  • KRATON D-1107 is a polystyrene-polyisoprene-polystyrene block copolymer (SIS).
  • KRATON G-1750 is a (Ethylene-Propylene ) n star polymer of a molecular weight above 160,000 gr/mole containing no A block.
  • the drop point temperature was measured by placing the sample in a cup containing a hole at the bottom which is 0.28 cm in diameter. The sample was heated at a rate of 5 °C/min. The temperature at which a drop of sample flows through the hole of the cup is called the drop point temperature.
  • ASTM D3104-87 test method for softening point of pitches (Metier softening point method) . In order to measure the drop point of cured systems, the uncured system were put in cups and the cups were then irradiated in the same way as the films.
  • This example demonstrates the improved temperature resistance of a cured polymeric composition according to the invention.
  • the curable polymeric composition IV/2 (see table IV) was prepared as follows .
  • the photo-mitiator was first mixed in the liquid HDDA at room temperature. Both this premix and the diluent (ONDINA N68 oil) were then ⁇ dry mixed' with the block copolymer powder. Finally, this premixed compound was fed into a single screw extruder and extruded twice at 140 °C.
  • the strands ( ⁇ 1 cm diameter) were then cured via twenty passes under a 300 W/2.5 cm (300 W/mch) UV bulb at 10 m/mm .
  • the cured strands where then cut m pieces and re-fed into the single screw extruder at 180 °C.
  • the polymeric composition IV/1 was prepared in an analogous fashion, but no HDDA was added and the polymeric composition was not cured.
  • the elastic modulus (G' ) at room temperature (corresponding to the tan ⁇ minimum) is more than double in IV/2 indicating the cohesion reinforcement induced by the cured radically polymerised compound.
  • the crossover point temperature referred to in the table as "maximum temperature at which tan ⁇ 1" clearly indicates a large increase of the elastic temperature resistance of IV/2 compared to IV/1.
  • the crossover point temperature is the transition temperature above which the viscous behaviour of the cured polymeric composition is predominant over the elastic behaviour.
  • ENDEX 155 is an endblock resin of polymerised alpha methyl styrene
  • PMMA is polymethyl methacrylate
  • PBT is polybutylene terephthalate
  • Formulations VI/1, VI/2 and Vl/3 were made by blending in a glass container at 140-150 °C the various ingredients.
  • VI/3 and VI/3b were first radiation cured at a temperature of about 140 °C (above its order-disorder transition temperature of 105 °C) , whereas VI/2 and VI/2b were first radiation cured at room temperature (below its order-disorder transition temperature) . Both VI/2b and VI/3b were cured a second time at room temperature. The results are set out in Table VI .
  • Table VI Table VI
  • the drop point temperature of VI/2 and VI/3 prior curing was 81 °C, which is lower than the comparative formulation VI/1 without HDDA. This demonstrates that prior to curing the HDDA acts as a solvent for the polystyrene domains. After curing the drop point temperature of VI/1 is unchanged, whereas the drop point temperature of VI/2 is increased by 25 °C to reach a value 17 °C above the reference VI/1 showing the effective reinforcing effect. VI/2 was thermoplastic even after curing. Repeated curing at room temperature (VI/2b) did not result m a further increase of the drop point temperature .
  • VI/3 was cured above the order-disorder transition temperature (ODT) and the increase in drop point was only 9 °C. The reached final drop point temperature is again similar to the drop point of the unmodified reference VI/1. Like VI/2, VI/3 was thermoplastic after curing. A second curing step at room temperature, below the ODT, did not result in any increase of the drop point temperature (see VI/3b) .
  • the HDDA is dispersed, like the polystyrene polymer blocks, in the aliphatic phase where it cross-links without substantially reinforcing the polystyrene polymer blocks.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une composition polymère pouvant être traitée, qui renferme : 1) un copolymère séquencé thermoplastique contenant au moins deux blocs polymères A séparés par au moins un bloc polymère B ; le bloc polymère A est essentiellement un bloc poly(hydrocarbure aromatique monovinylique) ou essentiellement un bloc poly(ester d'acide alcénoïque en C3-C7), et le bloc polymère B est essentiellement un bloc polymère élastomère aliphatique ; 2) un composé capable de polymérisation radicalaire, qui est au moins partiellement compatible avec les blocs polymères A et non compatible avec le bloc polymère B. Le pourcentage en poids du composé capable de polymérisation radicalaire se situe entre 0,1 et 3 fois le pourcentage en poids des blocs polymères A ; les deux pourcentages en poids sont fondés sur le total du copolymère séquencé et du composé capable de polymérisation radicalaire ; et 3) un initiateur radicalaire au moins partiellement compatible avec les blocs polymères A et/ou le composé capable de polymérisation radicalaire, et non compatible avec le bloc polymère B. L'invention concerne de plus un procédé de préparation d'une composition polymère traitée ; une composition polymère traitée ; un copolymère séquencé obtenu par traitement de la composition polymère pouvant être traitée ; un mélange thermoplastique contenant la composition polymère pouvant être traitée ou la composition polymère traitée et une polyoléfine ; et des articles contenant l'une des compositions mentionnées.
PCT/EP2001/003125 2000-03-16 2001-03-16 Composition polymere Ceased WO2001068769A1 (fr)

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Cited By (8)

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WO2003035752A1 (fr) * 2001-10-18 2003-05-01 Kraton Polymers Research B.V. Composition polymere solide durcissable
EP1333058A1 (fr) * 2002-01-31 2003-08-06 KRATON Polymers Research B.V. Copolymère modifié à blocs styrènes et ses compositions avec les propriétés mécaniques et productivités améliorées
US7241540B2 (en) 2004-04-27 2007-07-10 Kraton Polymers U.S. Llc Photocurable compositions and flexographic printing plates comprising the same
CN100372875C (zh) * 2006-04-13 2008-03-05 上海交通大学 高分子型二苯甲酮光引发剂及其制备方法
CN100372877C (zh) * 2006-04-13 2008-03-05 上海交通大学 高分子型二苯甲酮光引发剂及其制备方法
US7785765B2 (en) 2005-05-11 2010-08-31 Asahi Kasei Chemicals Corporation Photosensitive resin composition
CN104119462A (zh) * 2014-07-16 2014-10-29 长沙新宇高分子科技有限公司 自供氢的二苯甲酮光引发剂及其制备方法
WO2018033296A1 (fr) * 2016-08-16 2018-02-22 Arkema France Compositions de séparation de phases induite par polymérisation pour réseaux à base d'acrylate

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EP0634453A2 (fr) * 1993-07-08 1995-01-18 Mitsui Petrochemical Industries, Ltd. Elastomère thermoplastique à base d'oléfine et son multicouche
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003035752A1 (fr) * 2001-10-18 2003-05-01 Kraton Polymers Research B.V. Composition polymere solide durcissable
EP1333058A1 (fr) * 2002-01-31 2003-08-06 KRATON Polymers Research B.V. Copolymère modifié à blocs styrènes et ses compositions avec les propriétés mécaniques et productivités améliorées
US7241540B2 (en) 2004-04-27 2007-07-10 Kraton Polymers U.S. Llc Photocurable compositions and flexographic printing plates comprising the same
US7785765B2 (en) 2005-05-11 2010-08-31 Asahi Kasei Chemicals Corporation Photosensitive resin composition
CN100372875C (zh) * 2006-04-13 2008-03-05 上海交通大学 高分子型二苯甲酮光引发剂及其制备方法
CN100372877C (zh) * 2006-04-13 2008-03-05 上海交通大学 高分子型二苯甲酮光引发剂及其制备方法
CN104119462A (zh) * 2014-07-16 2014-10-29 长沙新宇高分子科技有限公司 自供氢的二苯甲酮光引发剂及其制备方法
WO2018033296A1 (fr) * 2016-08-16 2018-02-22 Arkema France Compositions de séparation de phases induite par polymérisation pour réseaux à base d'acrylate
CN109641998A (zh) * 2016-08-16 2019-04-16 阿科玛法国公司 基于丙烯酸酯的网络的聚合诱导的相分离组合物
KR20190042613A (ko) * 2016-08-16 2019-04-24 아르끄마 프랑스 아크릴레이트-기반 네트워크를 위한 중합-유도된 상-분리 조성물
TWI659047B (zh) * 2016-08-16 2019-05-11 阿科瑪法國公司 用於以丙烯酸酯為主的網狀物之聚合引發相分離組成物
US11001664B2 (en) 2016-08-16 2021-05-11 Arkema France Polymerization-induced phase-separating compositions for acrylate-based networks
KR102287447B1 (ko) 2016-08-16 2021-08-09 아르끄마 프랑스 아크릴레이트-기반 네트워크를 위한 중합-유도된 상-분리 조성물
CN109641998B (zh) * 2016-08-16 2022-04-15 阿科玛法国公司 基于丙烯酸酯的网络的聚合诱导的相分离组合物

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