EP0804495A1 - Copolymerisat sequence, et procede permettant de le produire par polymerisation anionique - Google Patents

Copolymerisat sequence, et procede permettant de le produire par polymerisation anionique

Info

Publication number
EP0804495A1
EP0804495A1 EP96939037A EP96939037A EP0804495A1 EP 0804495 A1 EP0804495 A1 EP 0804495A1 EP 96939037 A EP96939037 A EP 96939037A EP 96939037 A EP96939037 A EP 96939037A EP 0804495 A1 EP0804495 A1 EP 0804495A1
Authority
EP
European Patent Office
Prior art keywords
block
units
monomer
block copolymers
styrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96939037A
Other languages
German (de)
English (en)
Inventor
Axel Gottschalk
Reimund Stadler
Karsten Jung
Susanne Brinkmann
Vittoria Balsamo-Hernandez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0804495A1 publication Critical patent/EP0804495A1/fr
Withdrawn legal-status Critical Current

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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
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes

Definitions

  • Block copolymer and process for its preparation by anionic polymerization Block copolymer and process for its preparation by anionic polymerization
  • the invention relates to a novel block copolymer consisting of at least one block A, made up of units of styrene or its technical equivalents (a) and at least one block C, made up of units of a cyclic lactone (c), which can be obtained by amonomic polymerization and a Process for its manufacture.
  • the invention relates in particular to block polymers in which ⁇ -caulrolactone is used as the cyclic lactone (c).
  • the invention further relates to the use of the block copolymers according to the invention for the production of moldings, films or fibers, and to the moldings, films or fibers made from the block copolymers according to the invention.
  • the invention further relates to the use of the block copolymers as phase mediators.
  • Block copolymers in the construction of which styrene and diene monomers are involved, are usually prepared by anionic polymerization. It is also known to convert the living chain ends of polybutadiene remaining in the anionic polymerization prior to further reaction with polymers such as polystyrene with certain coupling reagents Capping This has the advantage that the desired block copolymers can be obtained more quickly and that branched block copolymers can be built up using more functional coupling reagents (see, for example, Morton ", Anionic Polymerization-Pnnciples and Practice", Academic Press, New York, London , 1983, pages 226-230).
  • the diphenylethylene has the effect that the reactivity of the living chain end is reduced and side reactions are thus reduced.
  • t ⁇ union block copolymers have indeed high molecular weights and a narrow molecular weight distribution
  • the implementation of Ketten ⁇ end with diphenylethylene is problematic because it often runs too slow and does not take place quantitatively.
  • an essentially quantitative conversion is required if side reactions are to be suppressed and high yields are to be achieved. This is particularly necessary for processes that are to be carried out on an industrial scale.
  • the object of the invention was to find a polymerization process of the type mentioned at the outset with which block copolymers of this type can be produced quickly, in high yields and purities and with a narrow molecular weight distribution.
  • Ar 1 CH 2 C ⁇ ⁇ ⁇ >
  • Ar 1 and Ar 2 independently is aryl substituted by C ⁇ ⁇ C to 8 ⁇ alkyl or Ci to Cs-alkoxy or halogen may be mono- or polysubstituted, is reacted.
  • a further block B composed of units (b) of a diene, is first added to the living end of block A before the reaction with the diarylethylene I or block C in a manner known per se so that Copolymers of the type of the known rubber-elastic styrene-butadiene block copolymers are obtained, which are then modified by means of block C.
  • the diarylethylene I it has, however, proven to be desirable to add at least one further monomer unit (a) to the block B beforehand. Ingenuity it is sufficient if 1 to 5 equivalents of the monomer unit (a) are added.
  • 1, 1-diphenylethylene is expediently used as diarylethylene I, butadiene-1,3 or isoprene as monomer (b).
  • the block copolymers obtainable by the process according to the invention contain at least one block A which is composed exclusively or essentially of units of styrene or its technical equivalents.
  • conjugated dienes are used as monomers (b) if a block B is provided.
  • monomers (b) e.g. 1,3-butadiene or isoprene
  • other linear and cyclic dienes e.g. those with 4 to 8 carbon atoms into consideration. Examples include 1, 3-butadiene, 1, 3-pentadiene, 2-methylbuta- l, 3-diene, 2, 3-dimethyl-buta-1, 3-diene and conjugated hexadienes, preferably 1,3-hexadiene. Any mixtures of different monomers (b) can also be used to build up block B.
  • the average molecular weight of block A, as well as block B and block C, is not critical in a wide range. In general, the average molecular weights are selected in accordance with the desired properties of the block copolymer. Typically, the average molecular weight is (number average value ⁇ M n) of each block A, optionally B and C of each block in the range from 5000 to 500,000, preferably from 10,000 to 100,000 [g / mol].
  • the block copolymers ⁇ obtainable by the process of this invention may also contain at least one further block D of similar molecular weight, made up of anionically polymerizable monomer (d) containing a functional group.
  • Ais monomers (d) are particularly preferably the C 1 -C 8 -alkyl esters of methacrylic acid or acrylic acid or mixtures thereof.
  • use is made, for example, of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, Octyl, 2-ethylhexyl, nonyl, decyl, lauryl or stearyl acrylate, preferably methyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate, and mixtures of these monomers. If such a block to one
  • the type A block is to be polymerized, it is expedient to prepare the living chain end in question in a manner known per se Way to implement with a diphenylethylene of formula I.
  • Methyl methacrylate and mixtures of these monomers (d) are preferably used as esters of methacrylic acid.
  • block copolymers with blocks from other monomers D which have functional groups, such as -OH, -SH, -NHAlkyl and others.
  • functional groups such as -OH, -SH, -NHAlkyl and others.
  • Such polymerization processes in the presence of protective groups are e.g. in S. Nakahama et al, Prog. Polym. Be. Vol. 15, 299-335, 1990.
  • Such monomers include, for example, p-aminostyrene, p-hydroxystyrene, p-vinylbenzoic acid, acrylic or methacrylic acid, acrylic or methacrylamide, maleic acid and their imides or C 1 -C 8 -alkyl esters, fumaric acid and their imides or ci- Ci L -alkyl esters, itaconic acid and their imides or -C-C ⁇ n-alkyl esters, acrylic or methacrylnit ⁇ l or hydroxyalkyl (meth) acrylates.
  • the molecular weight (number average M n ) of block D can vary within wide limits, but is generally in the range from 5,000 to 500,000, preferably in the range from 10,000 to 100,000 [g / mol].
  • styrene monomers (a) are styrene, p-chlorostyrene, ⁇ -methylstyrene, p-methylstyrene, methyltoluene and p-t-butylstyiol.
  • Block A can also be constructed from a mixture of different monomers. However, styrene is preferably used alone.
  • the block copolymers obtainable by the process according to the invention are mostly block copolymers of the type AC or three-block copolymers of the type ABC. However, they can also be, for example, three-block copolymers of the BABC type. It is also possible that they are multi-block copolymers, for example up to 10-block copolymers. In most cases, however, they do not contain more than five or six blocks, since such block copolymers can be readily produced, but are generally too expensive for technical applications.
  • the block copolymers obtainable by the process according to the invention each contain the block (s) as outer blocks, since these are always polymerized last.
  • Particularly preferred block copolymers are polybutadiene-b-poly (- ⁇ -caprolactone), polystyrene-b-poly-butadiene-b-poly (-e-caprolactone).
  • the particularly preferred block copolymers include those in which polybutadiene is is built and has a high proportion of 1, 4 -linking units.
  • the average molecular weights (number average M n ) of the block copolymers obtainable by the process according to the invention are generally not significantly higher than 1,000,000 [g / mol] and are generally not significantly lower than 10,000 [g / mol]. In general, they are in the range from 50,000 to 500,000 [g / mol].
  • Preferred block copolymers have molecular weights (number average M n ) in the range from 75,000 to 250,000 [g / mol].
  • the block copolymers are produced by anionic polymerization.
  • Alkali metal organic compounds preferably lithium alkyl compounds such as methyl lithium, ethyl lithium, n- or s-butyllithium or s-propyllithium, are among the suitable initiators.
  • N- or s-Butyllithiam is particularly preferably used. If, in a known manner, instead of monofunctional initiators, multifunctional - e.g. If bifunctional compounds are used, one obtains, which is easy to see, block copolymers with a mirror-image structure, of which half have the structure according to the invention.
  • Solvents for anionic polymerization can be used which are chemically indifferent to the polymer anions formed. These include straight-chain or branched aliphatic hydrocarbons, such as n-hexane or n-octane, and simple or substituted cyclo aliphatic hydrocarbons, e.g. Cyclohexane or methyl - cyclohexane.
  • Aromatic hydrocarbons for example benzene, toluene or ethylbenzene, can also be used as solvents. It is also possible to use mixtures of different solvents. Cyclohexane and ethylbenzene are among the preferred solvents.
  • ethers such as tetrahydrofuran or diethyl ether and tertiary ames, for example tetramethylethylene diamine or py ⁇ dm, can be present as cosolvents.
  • their proportion in the total amount of solvent is not more than 0.01 to 20, preferably from 0.01 to 2,% by weight.
  • Tetrahydrofuran is usually preferred as a cosolvent.
  • the polymerization to the nonpolar block A or, if appropriate, Bm can be carried out in a nonpolar solvent or solvent mixture, while the polymerization to the polar block C can be carried out in a polar solvent.
  • This can be done by adding a polar solvent to the reaction mixture after the end of the polymerization of a non-polar block.
  • all or part of the non-polar solvent can be learned beforehand from the reaction mixture, for example by distilling off or using reduced pressure.
  • the aforementioned can be used as non-polar solvents; aliphatic or cycloaliphatic ethers, in particular tetrahydrofuran, are preferred as polar solvents
  • the polymerization is carried out, as usual, with inert gas at temperatures from -100 to + 120 ° C., preferably from -80 to + 80 ° C. In general, work is carried out at pressures in which the monomers and solvents do not evaporate at the temperature of the polymer
  • the anionic polymerization is carried out in several stages, in each of which the monomers of the individual blocks are completely polymerized out.
  • the order in which the blocks are produced is not essential to the invention.
  • each living end consisting of a residue of a block B, 1 to 20, preferably 1 to 10 equivalents of the styrene monomer (s) (a) should generally be used.
  • the living end (s) of block B is particularly preferably capped with 1 to 5 equivalents of styrene monomer (a).
  • 1 to 10 preferably 1 to 5, in particular 1 to 3 equivalents are generally used per equivalent of a living chain end.
  • the anionic polymerization is generally ended by adding water or alcohols such as methanol or isopropanol to the reaction mixture in order to deactivate the end groups or excess initiator which are still living.
  • the block copolymers obtained if they contain polybutadiene blocks, can be converted by hydrogenation treatment into polymers in which the aliphatic unsaturated bonds are wholly or partly saturated, i.e. which have a degree of hydrogenation of 50 to 100% by weight, preferably 70 to 100 and in particular 90 to 100% by weight.
  • the hydrogenation is preferably carried out using molecular hydrogen and catalysts based on metals or metal salts of the eighth group of the periodic table.
  • a heterogeneous phase it can e.g. with Raney nickel or preferably in a homogeneous phase with catalysts based on salts, in particular carboxylates, alkoxides or enoates of cobalt, nickel or iron, which are combined with metal alkyls, in particular with aluminum alkyls, or homogeneously by diimines produced in situ from e.g. Tosyl hydrazide take place.
  • Processes for the selective hydrogenation of block copolymers are i.a. in U.S. Patents 3,113,986 and 4,226,952.
  • the polymerization mixture can, as usual, either be heated directly to dryness or treated with steam, the solvent being distilled off. It can also be precipitated in an excess of a non-solvent such as ethanol and mechanically separated and dried or worked up by extruder degassing.
  • a non-solvent such as ethanol
  • the block copolymers obtainable by the process according to the invention can be processed to give moldings, films or fibers. This can be done, for example, by conventional methods such as extrusion or injection molding.
  • the block copolymers are also suitable as phase mediators in polymer blends, for example for mixtures of styrene polymers with polycarbonates, styrene / acrylonitrile copolymers, polyphenylene ethers and polycarbonates, polyphenylene ethers and / or polyarylene ethers such as polyarylene ether sulfones or ketones with polycarbonates.
  • Benzene was used as the solvent for the anionic polymerization, to which a small amount of styrene and enough butyllithium had been added before the start of the polymerization until the light yellow color of the anion formed.
  • the calculated amount of s-butyllithium was introduced as the initiator and the required amount of styrene (s) was added at 40 ° C.
  • s styrene
  • After 4 hours of polymerization a sample of the solution was taken, precipitated in methanol and the molecular weight of the polystyrene block determined. The required amount of butadiene (b) was condensed into the reaction mixture at -10 ° C. and polymerized at 40 ° C.
  • the molecular weights and compositions of the three-block copolymers were then determined by means of GPC and X H-NMR spectroscopy.
  • the molecular characteristics of various three-block copolymers are given in Table 1.
  • the phase behavior of the block copolymers was determined by differential scanning calorimetry (DSC) examined.
  • the corresponding data are compiled in Table 2, from which it can be seen that the three-block copolymers were present in micro-phase separation, which is advantageous with regard to their mechanical properties and their use as phase mediators.
  • the mechanical properties of the block copolymers were determined in tensile-strain experiments. For this purpose, films from toluene solution (Fig. 1) as well as at 180 ° C on melt-pressed samples (Fig. 2) were examined. The 4 cm long samples were clamped in a tension-stretching apparatus and stretched at a speed of 20 mm / min.
  • the three-block copolymers with a higher content of ⁇ -caprolactone behaved like typical semicrystalline polymers.
  • SBC three-block copolymers with a high styrene content also showed very high toughness after melt pressing, as can be seen in the maximum ductility of 600%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un procédé de production, par polymérisation anionique, de copolymérisats séquencés contenant au moins une séquence A, comprenant des unités de styrène ou ses équivalents techniques (a) et au moins une séquence C, comprenant des unités d'un lactone cyclique (c). Ce procédé se caractérise en ce qu'avant réaction avec le monomère (c), l'extrémité de la chaîne vivante subsistant après constitution de la séquence A est mise à réagir avec un diaryléthylène, notamment du 1,1-diphényléthylène, dans des conditions de polymérisation anionique. Avant la réaction avec le diaryléthylène, une autre séquence B, comprenant des unités d'un diène et en outre au moins une autre unité monomère (a) sont ajoutées de préférence à l'extrémité vivante de la séquence A, de manière connue en soi. L'invention concerne également l'utilisation du copolymérisat séquencé pour produire des corps moulés, des films ou des fibres ou comme médiateur de phase dans des mélanges polymères. L'invention concerne en outre les corps moulés, les films ou les matériaux fibreux produits à l'aide desdits copolymérisats séquencés.
EP96939037A 1995-11-15 1996-11-14 Copolymerisat sequence, et procede permettant de le produire par polymerisation anionique Withdrawn EP0804495A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19542643A DE19542643A1 (de) 1995-11-15 1995-11-15 Verfahren zur Herstellung von Blockcopolymerisaten durch anionische Polymerisation
DE19542643 1995-11-15
PCT/EP1996/004990 WO1997018250A1 (fr) 1995-11-15 1996-11-14 Copolymerisat sequence, et procede permettant de le produire par polymerisation anionique

Publications (1)

Publication Number Publication Date
EP0804495A1 true EP0804495A1 (fr) 1997-11-05

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EP96939037A Withdrawn EP0804495A1 (fr) 1995-11-15 1996-11-14 Copolymerisat sequence, et procede permettant de le produire par polymerisation anionique

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US (1) US5932663A (fr)
EP (1) EP0804495A1 (fr)
DE (1) DE19542643A1 (fr)
WO (1) WO1997018250A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19642489A1 (de) * 1996-10-15 1998-04-16 Basf Ag Verfahren zur Herstellung von Pfropfcopolymeren
US6642322B2 (en) 1998-01-21 2003-11-04 The University Of North Carolina At Chapel Hill Methods of making telechelic oligomers, methods of making block copolymers, and novel block copolymers
DE10029697A1 (de) * 2000-06-16 2001-12-20 Basf Ag Feststoffhaltige Bindemittelzusammensetzung mit radikalisch polymerisierten Blockcopolymeren
FR2909093B1 (fr) * 2006-11-28 2012-07-13 Arkema France Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable.
US20100010147A1 (en) * 2008-07-08 2010-01-14 Kraton Polymer U.S. Llc Adhesives prepared from diphenylethylene containing block copolymers
US20100010154A1 (en) * 2008-07-08 2010-01-14 Kraton Polymers U.S. Llc Gels prepared from dpe containing block copolymers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE785664A (fr) * 1971-07-02 1973-01-02 Stamicarbon Procede de preparation de copolymeres sequences
US4360643A (en) * 1979-04-04 1982-11-23 Phillips Petroleum Company Method of preparing lactone block copolymers
DE3540047A1 (de) * 1985-11-12 1987-05-14 Basf Ag Polymerisationsinitiator und dessen verwendung zur herstellung von lactonblockcopolymerisaten
DE3607627A1 (de) * 1986-03-07 1987-09-10 Bayer Ag Thermoplastische blockcopolymere auf der basis von cyclischen carbonaten oder estern
JPS62241956A (ja) * 1986-04-15 1987-10-22 Denki Kagaku Kogyo Kk 不飽和ポリエステル樹脂収縮防止剤
CA2030916C (fr) * 1989-11-29 2000-06-13 Makoto Katoh Melange a base de resines offrant des proprietes antistatiques permanentes
JPH03190911A (ja) * 1989-12-20 1991-08-20 Nippon Paint Co Ltd 星型共重合体およびその製造方法
FR2686088B1 (fr) * 1992-01-10 1995-06-23 Atochem Elf Sa Procede de fabrication de polycondensats multisequences, en etoile ou en reseaux par couplage a l'aide de di- ou multi-aldehydes, et polycondensats ainsi obtenus.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9718250A1 *

Also Published As

Publication number Publication date
US5932663A (en) 1999-08-03
WO1997018250A1 (fr) 1997-05-22
DE19542643A1 (de) 1997-05-22

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