WO1997047672A1 - Block copolymers and thermoplastic mounlding compounds containing them - Google Patents

Block copolymers and thermoplastic mounlding compounds containing them 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
block copolymers
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PCT/EP1997/002818
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German (de)
French (fr)
Inventor
Konrad Knoll
Wolfgang Loth
Hermann Gausepohl
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Basf Aktiengesellschaft
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02Macromolecular 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
    • C08F297/04Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions 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
    • C08L53/02Compositions 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

Abstract

Block copolymers with blocks A and B of the general structure (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 or X [(B - A - B)n]m in which A is a diene-based block and B is a block of copolymers from monomers of the general formulae (I) and (II), where R1 = H or an alkyl radical with 1-22 C atoms, R2 = H or an alkyl radical with 1-22 C atoms, R3 = H or an alkyl radical with 1-4 C atoms, a = 0, 1, 2, 3, 4 or 5, b = 0, 1, 2, 3, 4 or 5, X is the radical of an m-functional coupling agent, n is a whole number in the range from 1 to 5 and m is a whole number in the range from 2 to 20.

Description

Block copolymers and those containing thermoplastic molding compositions

description

The present invention relates to block copolymers with blocks A and B of the following general structure

(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 or

X [(B - A - B) n] m

in which

A for a block on the basis of dienes,

B is a block of copolymers of monomers of the general formulas I and II,

Figure imgf000003_0001

With

Ri = H or alkyl with 1-22 C atoms R 2 = H or alkyl with 1-22 C atoms R 3 = H or alkyl with 1-4 C atoms, a = 0, 1, 2, 3, 4, or 5 b = 0, 1, 2, 3, 4 or 5

X is the radical of an m-functional coupling agent n is an integer in the range of 1 to 5 and m is an integer in the range 2-20

stand. Furthermore, the invention relates to mixtures of the inventive block copolymers having Copolymeπεaten from monomers of For¬ mel I and II and their use.

Rubber-modified styrene polymers have long been known and are produced industrially on a large scale. They have good toughness and flowability, but have that softening is las¬ above 98 ° C is difficult to achieve sen the downside. It has therefore already been attempted, the glass temperature through the use of α or ring-substituted compounds of the

Styrene raise. The disadvantage of this approach is ever nevertheless the fact that α-substituted polystyrenes such as poly-α-methylstyrene depolymerize very light and kernsubsti-substituted polystyrenes cause only a slight increase in the Erwei monitoring point and are also very expensive.

Another method is to styrene with 1, 1-diphenyl - to copolymeπsieren ethylene as H. Yuki and J. Hotta et al. describe (Bulletin Chem. Soc. Jap., Vol. 40, p 2659 (1967)). After the process described therein is obtained chemically non-uniform products that lead to poor mechanics. to remove sungsmethoden with the usual Entga¬ for polystyrene is obtained also products with a high residual monomer content which are not commercially ver¬ cycled: Auf¬ due to the incomplete conversion and the impossibility of the 1, 1-Dιphenylethylen (277 ° C boiling point). The products are also not schlagzah modified and therefore already useless for most applications.

It is an object of the present invention to develop a product with a higher softening point and niedri gen residual monomer to obtain the toughness and the thermal resistance of the impact-resistant polystyrene.

This object was solved by erfmdungsgemaß block copolymers according to Claim. 1

Preferred block copolymers are erfmdungsgemaße requirements Suggested the lower and shown in the following description.

According to the present invention are block copolymers with Block 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 represents ge for disposal, wherein a represents a block on the basis of dienes and B for a block of a copolymer of monomers of the general formula I and II, B is a block of polymers of the general formula II, X is the residue of a m- functional means of Kopplungsmit-, n is an integer in the range of 1 to 5 and m stand for an integer in the range 2 to 20

As the diene component for the block A is in principle all dienes are suitable, but preferred are those compounds with conjugated Doppelbin¬ as butadiene, isoprene, dimethylbutadiene and phenylbutazones diene.

The molecular weights (weight average values M w) of the block A of the inventive block copolymers are generally within the range from 10,000 to 500,000, preferably 50,000 to 350,000 and in particular 70,000 to 250,000.

The copolymer block B is built up from monomers of formula I and II.

The monomers of the general formula I is 1, 1-diphenylethylene, and the optionally substituted on the aromatic rings with alkyl groups having up to 22 carbon atoms derivatives. Preferred alkyl groups as substituents are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, i- and n-propyl and n-, i- or tert. Butyl, to name a few. but is particularly preferably the unsubstituted 1, is 1-diphenylethylene itself einge¬.

The monomers of general formula II are styrene and its in α-position or on the aromatic ring substituted with alkyl groups having 1 to 4 carbon atoms derivatives. Preferred alkyl groups are those described above for monomers of formula I mentioned as being preferred; unsubstituted styrene itself is particularly preferred.

The molar ratio of the units derived from monomers I ab¬ lead to units, which is derived from monomers II is generally in the range of 1: 1 to 1: 25, preferably from 1: 1.05 to 1: 15 and especially preferably in the range of

1: 1.1 to 1: 10. Since the monomers of the formula I usually do not polymerize by itself, products with molar ratios greater than 1: 1 is not a simple way zugäng¬ Lich.

The copolymer block B is preferably constructed statistically composed of one or more monomers of structural formula I and in each case one or more monomers having the structural formula II. Particularly preferred is a copolymer of styrene and 1, 1-diphenylethylene. Thus, compatibility of the copolymer block B is ensured with the hard matrix, the statisti¬ specific structure of the block B with the similarly the hard matrix, besond- ers is to be preferred. The molecular weight M w of the block B is generally from 20,000 to 500,000, but preferably 50,000 to 300,000.

The symbol "X" is the radical of an m-functional coupling agent. The coupling center X is formed by the reaction of le¬ reproduced anionic chain ends with an at least bifunctional coupling agent. Examples of such compounds are disclosed in U.S. Patents 3,985,830, 3,280,084, 3,637,554 and 4,091,053 to find.

The ratio of the blocks A and B is generally in the range of 90:10 to 20:80. preferably, A: B ratios of 90:15 to 65:35 for the production of so-called cell structure and the dispersed phase is from 60:40 to 45:55 for generating a Kapselteilchen- morphology.. The connection between the morphology of the rubber block and the morphology of the dispersed 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 of invention to the invention can be prepared by conventional methods of rule anioni¬ chemistry, such as, for example, describes M. Morton. (M. Morton> Anionic Polymerization: Pnnciples and Practice <Academic Press, New York 1983).

However, in order to obtain a chemically uniform copolymer block B, it is advantageous to produce the block rubber continuous or feed process; this will be described later in detail in the preparation of the component B of the inventive thermoplastic molding compositions.

In the inventive block copolymers, the units enthal¬ th derived from an m-functional coupling agent X, X reacted after the polymerization with the living an¬ ionic chain ends, whereby the structures according to claim 1 formed.

Examples of suitable coupling agents are described in US 3,985,830, 3,280,084, 3,637,554 and 4,091,053 to find. For example only be mentioned here, epoxidized glycerides, such as epoxidized Leinsamenόl or soybean oil; divinylbenzene is also suitable. the living anionic end on the side of the B block is located, then the epoxy and / or ester groups is preferably coupled with compounds containing; However, forms the A block the active end, divinylbenzene is preferably used for coupling. The block transitions can both sharply divided as well "ver¬ smears" to be.

By "smeared" transition is understood to mean a piece of chain of the molecule, in which the monomers of the block A are distributed with the monomer of block B statistically. The desired Molekularge¬ weight of the blocks is adjusted by the ratio of initiator to monoethylenically mer.

To improve the Witterungε- and Thermooxidationsbeständig- the inventive block copolymers ness the diene blocks may be partially or fully hydrogenated. Processes for this purpose are known and, for example, EP 471,415, US 4,656,230 and US 4,629,767 described in the literature.

According to a further embodiment of the present invention, thermoplastic molding compositions are provided, comprising 1 to 99, preferably 3 to 70 and especially 4 to 40 -.% Of a block copolymer according to the invention and 1 to 99, preferential 30 to 97 and particularly 65 to 96 wt -.%, based on the polymer content, of copolymers of the monomers of formulas I and For¬ Ha (as described hereinabove) include, wo¬ is carried out at the polymerization of the last-mentioned component in the presence of the block copolymer. Regarding the description of the monomers of formulas I and II of the block copolymers according to the invention reference should be made to avoid repetition, the description of the block B.

Particularly preferred copolymers as component A are described in DE-A 44 20 917 is referred to herein.

The molar ratio of the units derived from monomers I ab¬ lead to units, which is derived from monomers II is generally in the range of 1: 1 to 1: 25, preferably from 1: 1.05 to 1: 15 and especially preferably in the range of

1: 1.1 to 1: 10. Since the monomers of the formula I usually do not polymerize by itself, products with molar ratios greater than 1: 1 is not a simple way zugäng¬ Lich.

Block copolymers of the invention are compositions for the production of the thermoplastic form-in the present invention preferably a monomer of the structural formulas I and II and, if appropriate dissolved in a inert solvent and this solution is preferably polymerized using organometallic initiators. By "inert solvent" Such a solvent is then em were ver¬ which does not react with the organometallic initiator.

It can be used both aliphatic and aromatic hydrocarbons. Suitable solvents are for example cyclohexane, methylcyclohexane, benzene, toluene, ethylbenzene or xylene.

To achieve higher polymerization rates can ge rings amounts of polar aprotic solvents are added. Suitable examples are diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether or especially tetrahydrofuran. The polar cosolvent is added to the nonpolar solvent in a small amount of ca.

0.5 -. 5% by volume added. THF is particularly preferably .-% in an amount of 0.1-0.3 vol.

The anionic polymerization is initiated by means of organometallic compounds. Compounds of Alkalime¬ metals, particularly lithium, are preferred. Examples of initiators are methyl lithium, ethyl lithium, propyl, n-butyl lithium, sec. Butyllithium and tert. Butyl lithium. The organometallic compound is added as a solution in a chemically mdiferrenten (iner- th) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is usually in the m range of 0.002 to 5 mol%, when referred to the monomers.

The polymerization temperature can be between 0 ° and 130 ° C. 90 ° C - temperatures of 50 ° are preferred. In general, that is polymerized lymerisationstemperatur while keeping constant the Po under isothermal conditions.

The polymerization of said monomers in the presence of

Block copolymers can be carried out both in a reren in meh¬ process stages. To achieve better utilization of rubber, that is, to increase the Weichphasenan¬ part is expedient to carry out the polymerization in at least two process stages, wherein the Monomergemiseh is correspondingly divided to the desired process stages in the individual sales and metered in each stage. A detail¬ profiled description of a possible such a process is described in DE 42 35 977th Another way to prepare the desired impact-resistant products, is to produce the rubber block in the one-pot process, first, and then to lead with renewed initiation and further feeding of the monomer mixture of the structural formulas I and II the polymerization. The process is described in DE 42 35 978th

To ensure a complete conversion of the monomers having the Strukturfor¬ mel I, it is convenient to them completely copolymerize in the last process stage, with a small additional amount of styrene or its derivatives.

After the polymerization, in general, the living chain ends with a proton-active substance, for example, alcohols or acids, such as carbonic acid or formic acid or with water tivated destak-. The solution can then by customary methods, if appropriate using stripping agents such as water or nitrogen degassed and - if desired - with auxiliary agents such as lubricants, antistatic agents, antioxidants, etc. are provided.

The crosslinking of the rubber in the dispersed particles has Ein¬ flow on the mechanical properties of the polymer. It can be influenced either via the degassing temperature and / or by addition of peroxides after the polymerization.

The reaction times are generally in the range of 0.1 to 24, preferably from 0.5 to 12 h and especially 1 to 10

As component a) block copolymers may also with blocks a x and a 2 of the general structures (aι-a2) n, al-a2 a l, a l-a2 a2,

X [(aι-a 2) n] m. X [(a 2 -aι) n] m, X (aι-a2 -aι) m X and (a 2 -a! -a 2) m Availability checked for ¬ supply provided, wherein A represents a block of a copolymer of Mo ¬ nomeren of the general formula I and II, B is a block of polymers of the general formula II, X is the radical of an m-functional coupling agent, n is an integer in the range of 1 to 5 and m is an integer in the range of 2 are to 20th

The coupling agent reacts X after the polymerization with the living anionic chain ends, whereby the above be¬ signed structures. Examples of suitable Kopp¬ are treatment compositions in US 3985830, 3280084, 091053 to find 3,637,554 and fourth For example only, are here epoxidized glycerides, such as epoxidized linseed oil or soybean oil called; divinylbenzene is also suitable. the living anionic end on the side of the B block is located, then the epoxy and / or ester groups is preferably coupled with compounds containing; JE forms but the A block the active end, divinylbenzene is preferably used for coupling.

The block transitions can be both sharply divided as well as "comparable 5 lubricates" his.

By "smeared" transition is understood em stucco chain of the molecule, in which the monomers of the block A are distributed with the monomer of block B statistically. The desired molecular weight of the blocks 10 is set by the ratio of initiator to monoethylenically mer.

The reaction times are generally in the range of 0.1 to 24, preferably from 0.5 to 12 h and particularly preferably 1 to 15 10th

As component C) the inventive thermoplastic molding compositions can contain from 0 to 3000, preferably from 0 to 2000 and especially vorzugt 100 to 1000 ppm of monomers of the formula I contain. 20 Preferably, these are the same monomers as the mel For¬ eingebau¬ in the polymerization in the component A) th monomers.

As component D), the inventive thermoplastic 25 molding compositions from 0 to 500, preferably 0 to 200, and especially 20 to 100 ppm of monomers of the formula II. These monomers of the same chemical formula are preferred as development in Herstel¬ of component A) were used.

30 The quantities of the component C) and D) are based on the weight of component A in the thermoplastic molding compositions.

As component E) according to the invention the thermoplastic molding compositions may contain from 0 to 90, preferably up to 60 and more preferably up

35 percent to 30 -.%, Based on the total weight of the molding composition, of other components. Basically hinsicht¬ Lich the structure of these other polymeric components not be¬ sondere limitation; However, polymers which zu¬ least some degree of tolerability with the component are preferred

40 A) since otherwise the mechanical properties are usually not satisfactory. Preferred polymers are styrene polymers such as impact resistant or glass-clear polystyrene or polyphenylene ether polymers, optionally in admixture with styrene polymers.

45 Furthermore, the inventive thermoplastic molding compositions as component F), up to 50 wt.%, Based on the total weight of the thermoplastic molding composition further Zusatz¬ materials and contain processing aids. Such possible additives are known to the expert and described in the literature, it is therefore unnecessary here detailed information. Exemplary fibrous and particulate fillers, stabilizers may be mentioned against heat and UV light, mold release agents and lubricants. A pigmentation of the inventive molding compositions is of course possible.

Particularly advantageous flame-retardant products can wer¬ manufactured with high softening point with the inventive molding compounds to. For this purpose, the molding compositions are to be intimately mixed with halogen- and / or phosphorus or phosphorus-nitrogen containing flame retardants according to conventional processes, for example by extrusion or calendering.

Examples

Purification of 1, 1-Dιphenylethylen (DPE)

Crude DPE (Aldrich or preparation by reaction of phenylmagnesium bromide with acetophenone, anhydride acetylation with Essigsaure- and thermal elimination of acetic acid) is (column Drehband¬; for larger quantities column with Sulzer packings) on a column of at least 50 theoretical plates distilled at 99.8% purity. The most pale yellow distillate (chromatography Woelm Alumma for the chromatograms, anhydrous) column with a 20 cm Alox filtered, and titrated with 1.5 N sec-butyllithium until a red color hefty in vacuo (1 mbar) uber- distilled. The product thus obtained is completely colorless and can be used directly in the anionic polymerization.

Cleaning of the monomers and solvents

The cyclohexane used as a loose means (H) was dried over wasser¬ free Alummiumoxid and titrated with the adduct of sec-butyl lithium and 1, 1-Dιphenylethylen to yellowing. The butadiene (Bu) of triisobutylaluminum was that

1, 1-Dιphenylethylen (DPE) of sec-butyllithium (s-BuLi) Removing distilled. As the initiator was used a 0.5 molar solution of s-BuLi in cyclohexane. Styrene (S) was dried over alumina immediately prior to use. All polymerizations were carried out under purified nitrogen under rigorous exclusion of air and moisture.

In the following examples, Bu stands for 1, 3-butadiene, S is styrene and DPE for 1, 1-diphenylethylene. Furthermore, the Verhaltnisangaben are by weight.

example 1

Producing a Bu-S / DPE block copolymers (Bu: S / DPE = 60:40 S: DPE = 2: 1)

In a 55 1 stirred reactor equipped with a cross-beam stirrer, were added 5 1 cyclohexane, 1.6 kg of styrene and 0.8 kg of DPE and initially charged at 60 ° C with 1 molar s-Butyllithiumlosung to be¬ beginning forming red color titrated. After starting the reaction with 75 ml of 1 m BuLi solution, the temperature of the reaction mixture was adjusted to 70 ° C and added simultaneously to the reaction has subsided a further 1.5 kg of styrene and 0.8 kg of DPE on the jacket cooling. two 50 g portions of styrene After 30 min the black-red solution added within 10 minutes, until the typical lithium polystyrene orange-red color persisted. It was diluted with 23 1 of cyclohexane and so fed in under cooling 7, 2 kg of butadiene that 80 ° C was not exceeded. After the reaction was neutralized with 10 ml of isopropanol and acidified with C0 2 / water. The colorless solution was evaporated in vacuo in a vented extruder by the solvent and granulated.

GPC: Mn = 155 000 g / mol; M w = 165 000 g / mol (Mischeichung for PS and PBu 40:60).

example 2

Preparation of a S / DPE-Bu-S / DPE block copolymers (Bu: S / DPE = 65:35 S: DPE = 1.5: 1).

Analogously to Example la were 2.52 kg of styrene, 1.68 kg polymerized DPE and 7, 8 kg of butadiene, eluting with 150 ml of 1 m BuLi solution was gestar- tet. Instead of isopropanol, 5.55 g of ethyl formate were added in 100 ml of cyclohexane within 5 minutes and then worked further as in Example la.

GPC: 1. Peak (10% share): M (peak maximum) = 79 000 g / mol; 2. Peak (90% share): M (peak maximum) = 160 000 g / mol. example 3

15 parts of the block copolymer prepared according to Example 1 wur¬ the dissolved in 45 parts of ethylbenzene.

There was a cascade of 2 boilers (Ri, R 2) 2 and tower reactors (Ti, T 2) is used (see FIG. DE 17 70 392). The individual reactors had a volume of 1 1 and 2 (boiler) and in each case 4 1 (tower reactors).

The solution of the block copolymer from Ex. 1 in ethylbenzene was continuously fed to the first stirred tank at a rate of 0.5 kg / h. Also continuously has the actuator Re¬ a l% strength n-butyllithium solution at a rate of 40 ml / h, respectively. Of the total feed of a mixture of styrene and diphenyl ethylene in the ratio 2: 1 was 1.0 kg / h and was applied to the reactors in the ratio 1: 3: 3 split. 2 The Polyme¬ risationstemperatur 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 reactor tower was 99.8%. The sequent abflie¬ polymer stream from the last reactor was added with a time related to the initiator 1.5-fold excess of water and C0. 2 The polymer solution was fed to a degassing vessel and degassed at 260 ° C and 10 mbar.

Volatiles: 0, 15%

example 4

The block rubber prepared according to Example 2 was prepared as in

Example 3 describes a novel molding material works ver¬.

Inlets to the reactor 1:

20% block copolymer solution of Example 2 in toluene

Flow rate 0.4 kg / h

1% n-butyllithium solution in cyclohexane

Flow rate: 40 ml / h

Inlets to the reactor 1, 2, 3, 4:

Mixture of styrene and 1, 1-diphenylethylene in the ratio 1.5: 1.0 and in a total amount of 1.2 kg / h, to the reactors in the ratio 1: was divided 3: 3: 2nd The reaction temperatures were:

70 ° C (Ri) 80 ° C (R 2) 80 ° C (Ti) 95 ° C (T 2)

Revenues for the second tower reactor was 99.5%. 5

It was worked up according to Example 3. FIG.

Examples 5 and 6

0 All experiments were performed in a double-walled 2 1 stirred reactor with a heating jacket, equipped with an anchor stirrer, conducted under rigorous exclusion of moisture and air under a nitrogen atmosphere. Before each experiment, the reactor was rendered inert with a boiling BuLi solution in cyclohexane. The sec- 5 butyllithium in cyclohexane was 0.5 molar.

example 5

Molecular structure: 0 Ii-butyl (S / DPE) 1- (S / DPE) 2

I 2 - (S / DPE) with I = 1 sec-butyl and Iι: I 2 = l: 22.4

Molecular mass [g / mol]:

Bu 200 000 25 (S / DPE) 1 60 000

(S / DPE) 2 60 000

Reaction:

30 Time [min] feed rate Temp. [° C] Remarks

0 CH 500 ml 25 0 s-BuLi 0.541 ml of 25

0-120 Bu 54,09g 67-73120 DPE 7.53 g 69 color change yellow-blue 35 120 S 69 8.7 g orange solution

Figure imgf000014_0001
180 CH 300 60 CH = cyclohexane 180-270 DPE 176.5 g 60-75 Simultaneous supply of S and

Phase separation (turbidity) at 215 min; 40180-270 204g DPE 60-75 min 90

270 ethanol 1 ml of 60 decolorization of the silky shimmering orange¬

45 colored solution to white working-up:

The product was acidified with formic acid and each 1.35 g of Irganox 1076 and Irganox 3052 and 0.5% Tπsnonylphenyl - phosphite stabilized. The cyclohexane (CH) was removed overnight at 60 ° C in vacuo. The white mass was 2 h at 180 ° C nach¬ dried and pressed at 250 ° C into test specimens.

Yield: 450 g (100% conversion); volatile portions: 0.25%;

T g (DSC): 158 ° C - 90 ° C

Monomer (FT-IR): S: 47.3%, DPE: 40.9%,

1, 4-trans-Bu: 7.4%, 1,4-cιs-Bu: 3.5%, 1,2-Bu: 1, 1%.

After each addition of monomer, a sample was taken and analyzed by GPC. The Molmassenzuwachs corresponded to the theory; the final sample showed a bimodal distribution with Dispersionsmdices

Mw / Mn of the two separated peaks of each <1.1.

The electron micrograph showed capsule particles having an average particle diameter of 0.3 microns.

example 6

Molecular structure:

Il-butyl (S / DPE) I2 (S / DP / E) with I = sec-butyl and II: 12 = 1: 22.4

Molecular mass [g / mol]:

Bu 200000

(S / DPE) 60000

reaction:

Time [min] feed rate Temp. [° C] Remarks

0 CH 500 ml 25

0 s Bull 0, 541 ml of 25

0-120 Bu 54,09g 67-73

120 s-BuLi 12,14m 60

CH 120 300 60

120-210 DPE 176,5g 60-75 Simultaneous supply of S and

120-210 204g 60-75 DPE about 90 mm; Phasen¬ separation (turbidity) at 225 mm

210 ethanol 1 ml of 60 decolorization of the silky shimmering orange¬ colored solution to white

Work-up:

It was worked up analogously to Example first

Yield: 434 g (100% conversion); volatiles: 0.29%;

T g (DSC): 158 ° C and - 90 ° C the monomer composition (FT-IR): S: 47.0%, DPE: 40.8%, 1,4-trans-Bu: 7.6%, 1, 4-cis-Bu: 3.6%, 1,2-Bu: 1.2%.

After each addition of monomer, a sample was taken and analyzed by GPC. The Molmassenzuwachs corresponded to the theory; the final sample showed a bimodal distribution with Dispersionsmdices Mw / Mn of the two separated peaks of each <1.1.

Claims

claims
1. Block copolymers with blocks A and B of the following general structure
(AB) n AB - AB - A - BX [(AB) n] m, X [(B - A) n] m, X [(AB - A) n. m or X [(B - A - B) n] m
in which
A for a block on the basis of dienes,
B is a block of copolymers of monomers of the, corresponding to general formulas I and II
Figure imgf000017_0001
With
R l = H or alkyl with 1-22 C atoms R 2 = H or alkyl with 1-22 C atoms R 3 = H or alkyl with 1-4 C-atoms a = 0, 1, 2, 3, 4 or 5 b = 0, l, 2, 3, 4 or 5
X is the radical of an m-functional coupling agent n is an integer in the range of 1 to 5 and m is an integer in the range 2-20
stand.
A thermoplastic molding material containing, as essential components there are suitable a) 1 to 99 wt.%, Copolymers of the monomers corresponding to general formulas I and II
Figure imgf000018_0001
0
With
Ri = H or alkyl with 1-22 C atoms R 2 = H or alkyl with 1-22 C atoms R 3 = H or alkyl with 1-4 C atoms, a = 0, 1, 2, 3, 4, or 5 b = 0, l,
2, 3, 4 or 5
b) 1 to 99 wt -.% of a block copolymer according to claim 1. An¬
wherein component a) by polymerization of the monomers in the presence of component b) is prepared.
3. Block copolymers according to claim 1, containing styrene as monomer of formula 1 and 1.1-diphenyl ethylene as the monomer of formula II.
4. Use of block copolymers according to claim 1 for Herstel¬ development of polymer blends with styrene polymers.
5. A thermoplastic molding material containing, as essential components there are suitable, a block copolymer according to claim 1.0 to 3000 ppm of monomers of the general formula I and 0 - 500 ppm of monomers of the general formula II.
6. The use of block copolymers or the thermoplastic form-compositions according to one of claims 1 to 2 or 4 to Herstel¬ development of fibers, films and Formkόrpern.
PCT/EP1997/002818 1996-06-12 1997-05-30 Block copolymers and thermoplastic mounlding compounds containing them WO1997047672A1 (en)

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Cited By (3)

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WO1998045369A1 (en) * 1997-04-04 1998-10-15 Basf Aktiengesellschaft Impact-resistant modified thermoplastic moulding compound
WO1999001487A1 (en) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft 1,1-diphenyl ethylene-based thermoplastic elastomers
WO2001079319A1 (en) * 2000-04-17 2001-10-25 Kraton Polymers Research B.V. A process for coupling styrenic block copolymers

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998045369A1 (en) * 1997-04-04 1998-10-15 Basf Aktiengesellschaft Impact-resistant modified thermoplastic moulding compound
WO1999001487A1 (en) * 1997-06-30 1999-01-14 Basf Aktiengesellschaft 1,1-diphenyl ethylene-based thermoplastic elastomers
WO2001079319A1 (en) * 2000-04-17 2001-10-25 Kraton Polymers Research B.V. A process for coupling styrenic block copolymers

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EP0904308A1 (en) 1999-03-31 application

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