WO1997047672A1 - Copolymeres sequences et matieres thermoplastiques de moulage les contenant - Google Patents

Copolymeres sequences et matieres thermoplastiques de moulage les contenant Download PDF

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Publication number
WO1997047672A1
WO1997047672A1 PCT/EP1997/002818 EP9702818W WO9747672A1 WO 1997047672 A1 WO1997047672 A1 WO 1997047672A1 EP 9702818 W EP9702818 W EP 9702818W WO 9747672 A1 WO9747672 A1 WO 9747672A1
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Prior art keywords
block
monomers
atoms
alkyl radical
block copolymers
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PCT/EP1997/002818
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German (de)
English (en)
Inventor
Konrad Knoll
Wolfgang Loth
Hermann Gausepohl
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Basf Aktiengesellschaft
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Priority to EP97927084A priority Critical patent/EP0904308A1/fr
Publication of WO1997047672A1 publication Critical patent/WO1997047672A1/fr

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    • 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
    • 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

Definitions

  • Block copolymers and thermoplastic molding compositions containing them Block copolymers and thermoplastic molding compositions containing them
  • the present invention relates to block copolymers with blocks A and B of the following general structure
  • Ri H or alkyl radical with 1-22 C atoms
  • R 2 H or alkyl radical with 1-22 C atoms
  • n for an integer in the range from 1 to 5 and m for an integer in the range from 2 to 20
  • the invention further relates to mixtures of the block copolymers according to the invention with copolymers of monomers of the formulas I and II and their use.
  • Rubber-modified styrene polymers have been known for a long time and are produced industrially on a large scale. They have good toughness and flowability, but have the disadvantage that softening points above 98 ° C. are difficult to achieve. Therefore, attempts have already been made to lower the glass transition temperature by using ⁇ or nucleus-substituted compounds of the
  • ⁇ -substituted polystyrenes such as e.g. Depolymerize poly- ⁇ -methylstyrene very easily and core-substituted polystyrenes cause only a slight increase in the softening point and are also very expensive.
  • the object of the present invention was therefore to develop a product with increased softening point and low residual monomer content while maintaining the toughness and thermal resistance of impact polystyrene.
  • block copolymers with blocks A and B of the general structures (AB) n , ABA, BAB, X [(AB) n ] m , X [(BA) n ] m , X (ABA) m and X (BAB ) m available, where A for a block based on dienes and B for a block of a copolymer of monomers of the general formula I and II, B for a block of polymers of the general formula II, X for the rest of a m-functional coupling tels, n is an integer in the range from 1 to 5 and m is an integer in the range from 2 to 20.
  • dienes are suitable as diene components for block A, but those with conjugated double bonds such as butadiene, isoprene, dimethylbutadiene and phenylbutadiene are preferred.
  • the molecular weights (weight average values M w ) of block A of the block copolymers according to the invention are generally in the range from 10,000 to 500,000, preferably from 50,000 to 350,000 and in particular from 70,000 to 250,000.
  • the copolymer block B is built up from monomers of the formula I and II.
  • the monomers of the general formula I are 1, 1-diphenylethylene and its derivatives which are optionally substituted on the aromatic rings by alkyl groups having up to 22 C atoms.
  • Preferred alkyl groups as substituents are alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, i- and n-propyl and n-, i- or tert. Butyl, to name a few.
  • the unsubstituted 1,1-diphenylethylene is particularly preferably used itself.
  • the monomers of the general formula II are styrene and its derivatives substituted in the ⁇ -position or on the aromatic ring with alkyl groups having 1 to 4 carbon atoms.
  • Preferred alkyl groups are those mentioned above for monomers of formal I as preferred; unsubstituted styrene itself is particularly preferred.
  • the molar ratio of the units derived from monomers I to units derived from monomers II is generally in the range from 1: 1 to 1:25, preferably from 1: 1.05 to 1:15 and particularly preferably in the range of
  • the copolymer block B is preferably constructed statistically from in each case one or more monomers of the structural formula I and in each case one or more monomers of the structural formula II.
  • a copolymer of styrene and 1,1-diphenylethylene is particularly preferred.
  • the statistical structure of the block B with that of the hard matrix is similar, particularly be preferred.
  • the molecular weight M w of block B is generally 20,000 to 500,000, but preferably 50,000 to 300,000.
  • the symbol "X" means the rest of an m-functional coupling means.
  • the coupling center X is formed by the reaction of the living anionic chain ends with an at least bifunctional coupling agent. Examples of such compounds are found in U.S. Patents 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
  • the ratio of blocks A and B is generally in the range from 90:10 to 20:80.
  • A: B ratios of 90:15 to 65:35 are preferred for producing the so-called cell structure of the disperse phase and from 60:40 to 45:55 for producing a capsule particle morphology.
  • the relationships between the morphology of the block rubber and the morphology of the disperse phase in the impact-resistant polystyrene are described in detail (see, for example, A. Echte, Advances in Chem. Ser. 222 (1989, 15)).
  • the block copolymers according to the invention can be prepared by customary methods of anionic chemistry, as described, for example, by M. Morton. (M. Morton> Anionic Polymerization: Pnnciples and Practice ⁇ Academic Press, New York 1983).
  • Suitable coupling agents are found in US 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
  • Epoxidized glycerides such as epoxidized linseed oil or soybean oil may be mentioned here only by way of example; divinylbenzene is also suitable.
  • the living anionic end is on the side of the B block, then it is preferably coupled with compounds which contain epoxy and / or ester groups; however, if the A block forms the active end, divinylbenzene is preferably used for the coupling.
  • the block transitions can be both sharply separated and "smeared".
  • a “smeared” transition means a chain piece of the molecule in which the monomers of block A are randomly distributed with the monomers of block B.
  • the desired molecular weight of the blocks is set via the ratio of initiator to monomer.
  • the diene blocks can be partially or completely hydrogenated. Methods for this are known and in the literature, e.g. EP 471 415, US 4,656,230 and US 4,629,767.
  • thermoplastic molding compositions are made available which contain 1 to 99, preferably 3 to 70 and in particular 4 to 40% by weight of a block copolymer according to the invention and 1 to 99, preferably 30 to 97 and in particular 65 to Containing 96% by weight, based on the polymer content, of copolymers of the monomers of the formulas I and Ha (as described hereinabove), the polymerization of the latter component taking place in the presence of the block copolymers.
  • the monomers of the formulas I and II reference is made to the description of block B of the block copolymers according to the invention in order to avoid repetitions.
  • copolymers as component A are described in DE-A 44 20 917, to which reference is made here.
  • the molar ratio of the units derived from monomers I to units derived from monomers II is generally in the range from 1: 1 to 1:25, preferably from 1: 1.05 to 1:15 and particularly preferably in the range of
  • the block copolymers according to the invention are preferably dissolved in a monomer mixture of the structural formulas I and II and, if appropriate, an inert solvent, and this solution is preferably polymerized using organometallic initiators.
  • inert solvent is understood to mean a solvent which does not react with the organometallic initiator.
  • Suitable solvents are, for example, cyclohexane, methylcyclohexane, benzene, toluene, ethylbenzene or xylene.
  • polar, aprotic solvents can be added. Diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether or, in particular, tetrahydrofuran are suitable, for example.
  • the polar cosolvent is added to the non-polar solvent in a small amount of approx.
  • THF is particularly preferred in an amount of 0.1-0.3% by volume.
  • the anionic polymerization is initiated using organometallic compounds.
  • organometallic compounds Compounds of alkali metals, especially lithium, are preferred.
  • initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyllithium.
  • the organometallic compound is added as a solution in a chemically different (inert) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is generally in the range from 0.002 to 5 mol%, if it is based on the monomers.
  • the polymerization temperature can be between 0 ° and 130 ° C. Temperatures of 50 ° -90 ° C. are preferred. Generally, under isothermal conditions, i.e. polymerized while keeping the polymerization temperature constant.
  • Block copolymers can be carried out continuously in one as well as in several process stages. To achieve better rubber utilization, ie to increase the soft phase portion, it is advisable to carry out the polymerization in at least two process stages, the monomer mixture being divided according to the conversion desired in the individual process stages and metered into each stage. A detailed description of a possible method of this type is described in DE 42 35 977. A further possibility of producing the desired impact-resistant products is first to produce the block rubber in a one-pot process and then to complete the polymerization with renewed initiation and further feeding in of the monomer mixture of the structural formulas I and II. The process is described in DE 42 35 978.
  • the living chain ends are generally covered with a proton-active substance, e.g. Alcohols or acids such as carbonic acid or formic acid or deactivated with water.
  • a proton-active substance e.g. Alcohols or acids such as carbonic acid or formic acid or deactivated with water.
  • the solution can then be degassed by customary methods, if appropriate using stripping agents such as water or nitrogen, and - if desired - provided with auxiliary agents such as lubricants, antistatic agents, antioxidants, etc.
  • the crosslinking of the rubber in the disperse particles has an influence on the mechanical properties of the polymer. It can be influenced either via the degassing temperature and / or by adding peroxides after the polymerization.
  • reaction times are generally in the range from 0.1 to 24, preferably from 0.5 to 12 and in particular from 1 to 10 hours.
  • component a) it is also possible to use block copolymers with blocks a x and a 2 of the general structures (a ⁇ -a2) n , al-a2- a l, a2- a l-a2,
  • A represents a block of a copolymer of Mo ⁇ nomers of the general formulas I and II
  • B for a block of polymers of the general formula II
  • X for the remainder of an m-functional coupling agent
  • n for an integer in the range from 1 to 5
  • m for an integer in the range of 2 to 20 are available.
  • the coupling agent X reacts with the living anionic chain ends, as a result of which the structures described above are formed.
  • suitable coupling agents can be found in US Pat. Nos. 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
  • Epoxidized glycerides such as epoxidized linseed oil or soybean oil may be mentioned here only by way of example; divinylbenzene is also suitable.
  • the living anionic end is on the side of the B block, then it is preferably coupled with compounds which contain epoxy and / or ester groups; forms but the A block is the active end, divinylbenzene is preferably used for coupling.
  • the block transitions can be sharply separated or "smeared”.
  • a “smeared” transition is understood as a chain piece of the molecule in which the monomers of block A are randomly distributed with the monomers of block B.
  • the desired molecular weight of the blocks is set via the ratio of initiator to monomer.
  • reaction times are generally in the range from 0.1 to 24, preferably from 0.5 to 12 and particularly preferably from 1 to 15-10 hours.
  • the thermoplastic molding compositions according to the invention can contain 0 to 3000, preferably 0 to 2000 and particularly preferably 100 to 1000 ppm of monomers of the formula I. These are preferably monomers of the same formula as the monomers incorporated into component A) during the polymerization.
  • thermoplastic molding compositions according to the invention can contain 0 to 500, preferably 0 to 200 and in particular 20 to 100 ppm of monomers of the formula II. These are preferably monomers of the same chemical formula as used in the production of component A) were used.
  • components C) and D) relate to the weight of component A in the thermoplastic molding compositions.
  • thermoplastic molding compositions according to the invention can be 0 to 90, preferably up to 60 and in particular up to
  • Preferred polymers are styrene polymers such as impact-resistant or crystal-clear polystyrene or else polyphenylene ether polymers, optionally in a mixture with styrene polymers.
  • thermoplastic molding compositions according to the invention can contain up to 50% by weight, based on the total weight of the thermoplastic molding composition, of further additives and processing aids as component F).
  • additives are known to the person skilled in the art and are described in the literature, so that detailed information is unnecessary here. Examples include fibrous and particulate fillers, stabilizers against heat and UV light, mold release agents and lubricants. Pigmentation of the molding compositions according to the invention is of course also possible.
  • Flame-proof products with a high softening point can be produced particularly advantageously with the molding compositions according to the invention.
  • the molding compositions are treated with halogen or / and phosphorus or phosphorus-nitrogen-containing flame retardants by customary processes, e.g. by extrusion or calendering, be intimately mixed.
  • Crude DPE (Aldrich or production by reacting phenylmagnesium bromide with acetophenone, acetylation with acetic anhydride and thermal elimination of acetic acid) is passed through a column with at least 50 theoretical plates (rotating belt column; for larger quantities, column with Sulzer packings) distilled to 99.8% purity.
  • the mostly pale yellow distillate is filtered through a 20 cm Alox column (Woelm alumma for chromatography, anhydrous), titrated with 1.5 N sec-butyllithium until a strong red color and distilled in vacuo (1 mbar).
  • the product thus obtained is completely colorless and can be used directly in the anionic polymerization.
  • the cyclohexane (H) used as solvent was dried over anhydrous aluminum oxide and titrated with the adduct of sec-butyllithium and 1,1-diphenylethylene until it turned yellow.
  • the butadiene (Bu) was derived from triisobutyl aluminum, the
  • DPE 1, 1-D ⁇ phenylethylen
  • s-BuLi sec-butyllithium
  • S Styrene
  • Bu stands for 1,3-butadiene, S for styrene and DPE for 1,1-diphenylethylene. Furthermore, the ratio information relates to the weight.
  • Example 1a 2.52 kg of styrene, 1.68 kg of DPE and 7.8 kg of butadiene were polymerized analogously to Example 1a, starting with 150 ml of 1 m BuLi solution. Instead of isopropanol, 5.55 g of ethyl formate in 100 ml of cyclohexane were metered in over the course of 5 minutes and the procedure was then continued as in Example 1a.
  • the individual reactors had a volume of 1 and 2 1 (boiler) and 4 1 each (tower reactors).
  • the solution of the block copolymer from Example 1 in ethylbenzene was fed continuously to the first stirred kettle at a rate of 0.5 kg / h.
  • a 1% n-butyllithium solution was also fed continuously to the reactor at a rate of 40 ml / h.
  • the total feed of a mixture of styrene and diphenylethylene in a ratio of 2: 1 was 1.0 kg / h and was divided between the reactors in a ratio of 1: 2: 3: 3.
  • the polymerization temperature in the individual reactors was 70 ° C. (Ri), 70 ° C. (R 2 ), 80 ° C. (Tx) and 90 ° C. (T 2 ).
  • the conversion after the last tower reactor was 99.8%.
  • the polymer stream flowing out of the last reactor was mixed with a 1.5-fold excess of water and CO 2 , based on the initiator.
  • the polymer solution was then fed to a degassing device and degassed at 260 ° C. and 10 mbar.
  • the block rubber produced according to Example 2 was, as in
  • Example 3 described, processed to a molding composition according to the invention.
  • the product was acidified with formic acid and stabilized with 1.35 g of Irganox 1076 and Irganox 3052 and 0.5% T ⁇ snonylphenyl phosphite.
  • the cyclohexane (CH) was removed in vacuo overnight at 60 ° C.
  • the white mass was subsequently dried at 180 ° C. for 2 hours and pressed into test specimens at 250 ° C.
  • the electron micrograph showed capsule particles with an average particle diameter of 0.3 ⁇ m.

Abstract

L'invention concerne des copolymères séquencés compotant les séquences A et B de structure générale (A - B)n; A - B - A; B - A - B; X [(A - B)n]m, X [(B - A)n]m; X [(A - B - A)n]m ou X [(B - A - B)n]m où A désigne une séquence à base de diènes; B désigne une séquence de copolymères composés de monomères des formules générales (I et II), dans lesquelles R1 = H ou un reste alkyle ayant entre 1 et 22 atomes de C, R2 = H ou un reste alkyle ayant entre 1 et 22 atomes de C, R3 = H ou un reste alkyle ayant entre 1 et 4 atomes de C, a = 0, 1, 2, 3, 4 ou 5, b = 0, 1, 2, 3, 4, ou 5; X désigne le reste d'un agent de couplage m-fonctionnel, n vaut un nombre entier compris entre 1 et 5 et m vaut un nombre entier compris entre 2 et 20.
PCT/EP1997/002818 1996-06-12 1997-05-30 Copolymeres sequences et matieres thermoplastiques de moulage les contenant WO1997047672A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97927084A EP0904308A1 (fr) 1996-06-12 1997-05-30 Copolymeres sequences et matieres thermoplastiques de moulage les contenant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996123415 DE19623415A1 (de) 1996-06-12 1996-06-12 Blockcopolymerisate und diese enthaltende thermoplastische Formmassen
DE19623415.8 1996-06-12

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998045369A1 (fr) * 1997-04-04 1998-10-15 Basf Aktiengesellschaft Matiere de moulage thermoplastique modifiee de maniere a resister aux chocs
WO1999001487A1 (fr) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft Elastomeres thermoplastiques a base de 1,1-diphenylethylene
WO2001079319A1 (fr) * 2000-04-17 2001-10-25 Kraton Polymers Research B.V. Processus de couplage de copolymeres sequences styreniques

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004011345B4 (de) * 2004-03-05 2005-12-08 Basf Ag Verfahren zur Aufarbeitung von anionisch polymerisierten Styrolpolymeren

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374961A2 (fr) * 1988-12-23 1990-06-27 Asahi Kasei Kogyo Kabushiki Kaisha Resine de polymère à fonction de mémoire de forme, composition de résine et produit moulé à fonction de mémoire
WO1995034586A2 (fr) * 1994-06-16 1995-12-21 Basf Aktiengesellschaft Matiere moulable thermoplastique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374961A2 (fr) * 1988-12-23 1990-06-27 Asahi Kasei Kogyo Kabushiki Kaisha Resine de polymère à fonction de mémoire de forme, composition de résine et produit moulé à fonction de mémoire
WO1995034586A2 (fr) * 1994-06-16 1995-12-21 Basf Aktiengesellschaft Matiere moulable thermoplastique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATENBANK "CHEMICAL ABSTRACTS" (DATEN- ANBIETER: STN); Abs.115:161 018, Colombus,OH, USA; & JP 03 079 613 A (ASAHI CHEM.) 4.April 1991 *
W. TREPKA: "Synthesis and properties of block polymers of 1,1 diphenylethylene/styrene and butadiene", JOURNAL OF POLYMER SCIENCE, PART B: POLYMER LETTERS, vol. 8, 1970, pages 499 - 503, XP002026769 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998045369A1 (fr) * 1997-04-04 1998-10-15 Basf Aktiengesellschaft Matiere de moulage thermoplastique modifiee de maniere a resister aux chocs
WO1999001487A1 (fr) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft Elastomeres thermoplastiques a base de 1,1-diphenylethylene
WO2001079319A1 (fr) * 2000-04-17 2001-10-25 Kraton Polymers Research B.V. Processus de couplage de copolymeres sequences styreniques

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DE19623415A1 (de) 1997-12-18
EP0904308A1 (fr) 1999-03-31

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