WO1999001487A1 - 1,1-diphenyl ethylene-based thermoplastic elastomers - Google Patents

1,1-diphenyl ethylene-based thermoplastic elastomers Download PDF

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WO1999001487A1
WO1999001487A1 PCT/EP1998/003701 EP9803701W WO9901487A1 WO 1999001487 A1 WO1999001487 A1 WO 1999001487A1 EP 9803701 W EP9803701 W EP 9803701W WO 9901487 A1 WO9901487 A1 WO 9901487A1
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block
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monomers
copolymers
block copolymers
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PCT/EP1998/003701
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German (de)
French (fr)
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Konrad Knoll
Evelin Endres
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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
    • 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
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/32Monomers containing only one unsaturated aliphatic radical containing two or more rings

Abstract

The invention relates to copolymers or block copolymers, comprising at least one block A of vinyl aromatic monomers a1) and 1,1-diphenyl ethylene or the derivatives thereof whose aromatic rings are substituted, optionally by alkyl groups with up to 22 C atoms a2) which can be obtained by anionic polymerization, in addition to block polymers with at least one block A and at least one optionally hydrogenated block B of diene b) which can be obtained by sequential anionic polymerization.

Description

Thermoplastic elastomers based on 1, 1-diphenylethylene

description

The 'invention relates to copolymers or block copolymers with at least one block A composed of vinylaromatic monomers al) and 1, 1-diphenylethylene or its on the aromatic rings optionally having alkyl groups having up to 22 carbon atoms substituted derivatives a2) obtained by anionic polymerization, and block copolymers having at least one block a and at least one, optionally hydrogenated, block B made from dienes b), obtainable by sequential anionic polymerization.

Furthermore, the invention relates to a process for the preparation of the copolymers, their use for the preparation of molding compositions and the molding compositions obtainable from the copolymers.

Thermoplastic elastomers (TPE) are polymers predominantly block or graft polymers, both thermoplastic and elastic properties. Because of the incompatibility caused by the blocks of polymer phase separation into a soft phase as a continuous matrix and a hard phase in the form of isolated, usually spherical inclusions, the TPE's behavior below the glass transition temperature of the hard phase as physically cross-linked elastomers. But since they are not chemically crosslinked, they can be processed above the glass transition temperature of the hard phase as thermoplastics. Their preparation, properties and uses are described in detail in "Thermoplastic Elastomers", G. Holden, N. Legge, R. Quirk and E. Schroeder (Ed.), 2nd edition, Hanser Publishers, Munich 1996.

As thermoplastic elastomers based on styrene-butadiene block copolymers with the structure ABA block from US 3,265,765 for example, are known. You have better hydrolysis resistance, better miscibility with nonpolar Blend ingredients such as oils compared to the class of thermoplastic urethanes (TPU) and are usually cheaper in price. Thermoplastic olefins (TPO) show a poorer return - assets. Due to the lower glass transition temperature of about 90-95 ° C of the styrene blocks, the thermoplastic elastomers have a lower heat resistance based on styrene-butadiene.

It has therefore been tried, the glass transition temperature of the styrene block copoly by erisation to increase with α-methyl styrene or substitution of styrene by α-methylstyrene, or by p-tert-butylstyrene. Due to the low ceiling temperature of α-methyl styrene, the polymerization with this monomer is difficult and leads to thermally labile polymers with a high residual monomer content. Hard blocks based on p-tert. however, butylstyrene are relatively well tolerated with the polybutadiene and newspaper so gen no or poor phase separation. However, the phase separation is critical to the morphology of training and thus for the mechanical property profile of the thermoplastic elastomer.

Thermoplastic elastomers with copolymer blocks (S / DPE) to

Base 1, 1-diphenylethylene and styrene and polybutadiene blocks (B) are disclosed in JP 3079-613 A and W. Trepka in J. Polym. Be, Part B (1970), page 499 -. Described 503rd After the specified process conditions, however, the installation of 1, 1-diphenylethylene is incomplete, resulting in deteriorated mechanical properties.

Copolymers of styrene and 1, 1-diphenylethylene with low residual monomer contents are known from WO 95/34586. Block copolymers of copolymer blocks (S / DPE) on the one hand and polybutadiene on the other hand are described in the German patent application P 19623415th

It is an object of the present invention, copolymers or Copo- lymerblöcke from vinyl aromatic monomers al) and 1, 1-diphenyl - ethylene or optionally provide the on the aromatic rings with alkyl groups having up to 22 carbon atoms substituted derivatives a2), in particular, even at low molecular weights have a narrow molecular weight distribution.

Furthermore, block copolymers should with good hydrolysis resistance, thermal stability, high tear strength, good resilience - are able and good heat resistance are provided. In particular, the heat resistance to thermoplastic elastomers to be improved based on styrene-butadiene with otherwise comparable properties.

Furthermore, a well-feasible process for the preparation of the copolymers should be provided.

Accordingly were copolymers or block copolymers nylethylen with at least one block A composed of vinylaromatic monomers al) and 1,1-diphenyl or its optionally substituted on the aromatic rings with alkyl groups having up to 22 carbon atoms derivatives a2), ER hältlich by anionic found polymerization, whereby to form the copolymer or the block a, an initiator solution consisting risationsinitiator from the reaction product of an anionic polymethacrylates and at least the equimolar amount of monomers a2) are used.

Furthermore, block copolymers obtainable by sequential anionic polymerization found with at least one block A and at least one, optionally hydrogenated, block B made from dienes b)], in which are carried out successively the following steps:

I) forming of a block A by

1.1) Preparation of an initiator solution consisting of the reaction product of an anionic polymerization initiator and at least the equimolar amount of monomers a2),

1.2) addition of any remaining residual amount of monomers a2) and 60 to 100% of the total amount of monomers al),

1.3) addition of any remaining residual amount of monomers al) after a conversion of at least 80% of added in the previous steps of monomers,

wherein the concentration of the polymerization after the last monomer addition, wt .-% is at least 35,

II) subsequent formation of a block B by

II.1) addition of the polymerization parameters influencing additive,

II.2) adding the dienes b) and

where appropriate, the following subsequent steps

III) adding a chain-stopping or coupling agent,

IV) hydrogenation of the block copolymer,

V) Isolation and work-up of the block copolymers according to known per se,

VI) addition of stabilizers.

Furthermore, a process for the preparation of the copolymers was found by anionic polymerization according to the above method steps. The copolymers or the blocks A consist of vinyl aromatic monomers al) and 1, 1-diphenylethylene or its to the aromati ¬'s rings optionally having alkyl groups with up to 22 C atoms, before ¬ Trains t having 1 to 4 carbon atoms such as methyl , ethyl, i- and n-propyl and n-, i- or tert-butyl substituted derivatives a2). As vinyl- arbmatische monomers al) are preferably styrene and its sub ¬-substituted in α-position or on the aromatic ring containing 1 to 4 carbon atoms derivatives, for example α-methylstyrene, p-methylstyrene, ethylstyrene, tert. Butylstyrene, vinyltoluene. Sonders loading is preferred as monomer a2) the unsubstituted

1, 1-diphenylethylene itself is used. The molar ratio of the units a2 from 1, 1-diphenylethylene or its derivatives) can be derived to units derived from the vinylaromatic monomer al), is generally in the range of 1: 1 to 1: 25, preferably from 1: 1.05 to 1: 10 and more preferably in the range of 1: 1.1 to 1: 3.

The copolymers or the blocks A are preferably constructed randomly and have a molecular weight Mw of generally 1000 to 500,000, preferably 3000 to 100,000, particularly preferably 4000 to 30 000. Especially preferred are copolymers or block A consisting of styrene and 1, 1-diphenylethylene. For applications in which special emphasis is placed on a high heat resistance, to choose the molar ratio of monomers a2) to monomers al) as possible close to 1: 1 and receives a glass transition temperature of the copolymers or the blocks A in the range of 120 to 180 ° C ,

As the diene b) for the block B are in principle all dienes are suitable, but preferred are those having conjugated double bonds such as 1, 3-butadiene, isoprene, 2, 3-dimethylbutadiene, 1, 3-pentadiene, 1, 3-hexadiene, phenylbutadiene, piperylene or mixtures thereof. 1,3-butadiene and isoprene are particularly preferred. The diene block may be partially or fully hydrogenated or unhydrogenated. By the hydrogenation of polyisoprene one therefore passes to ethylene-propylene blocks or of Polybutadienblök- ken to polyethylene or polyethylene-butylene blocks corresponding to the 1, 2-vinyl content of the unhydrogenated butadiene block. By hydrogenation, the block copolymers are thermally stable and especially to aging and weather-resistant. The molecular weights Mw of the blocks B are generally in the range from 10,000 to 500,000, preferably 20,000 to 350,000 and more preferably 20,000 to 200 000. The glass transition temperatures of the blocks B are generally below -30 ° C, preferably below -50 ° C. The weight of the sum of all the blocks A to the total block copolymer is generally 5 to 95 wt .-%. For use as thermoplastic elastomers, this proportion is preferably 5 to 50 wt .-%, particularly preferably 25 to 35 wt .-%, for use as impact-resistant, transparent materials 50 bfs 95 wt .-%, preferably 65 by weight to 85th -%.

For suitability as thermoplastic elastomers, the morphology is important, which is established by the incompatibility of the A and B blocks. The blocks B aggregate in the soft phase forming the continuous matrix and is responsible for the rubber-elastic behavior at the use temperature. The A blocks are predominantly in the form of isolated, usually spherical inclusions which act as physical crosslinking points. Particularly suitable as thermoplastic elastomers are block copolymers or star block copolymers symmetrical with external blocks A.

The anionic polymerization is initiated by means of organometallic compounds. As initiators the usual alkali can limetallalkyle or aryls are used. Conveniently, organolithium compounds such as ethyl-, propyl, isopropyl, n-butyl, sec-butyl, tert. -butyl, phenyl, Hexyldiphenyl-, hexamethylene, butadienyl, isoprenyl or polystyryllithium. , 1-Diphenylhexylli- is particularly preferably 1 thium used that easily ethylene from the reaction of 1, 1-diphenyl- with n- or sec.-Butyllithium is available. The amount of initiator required is determined by the desired molecular weight and is usually in the range of 0.002 to 5 mole percent based on the monomer to be polymerized.

Suitable solvents are inert solvents are compared with the organometallic initiator. Suitably used are aliphatic, cycloaliphatic or aromatic hydrocarbons, such having 4 to 12 carbon atoms such as pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, decalin, iso-octane, benzene, alkylbenzenes such as toluene, xylene or ethylbenzene, or suitable mixtures.

After completion of construction, the molecular weight can be "living"

Polymer ends are optionally reacted with conventional chain-stopping or coupling agents in amounts usually depend on the employed amount of initiator. Suitable chain terminators are protic substances or Lewis acids, such as water, alcohols, aliphatic and aromatic carboxylic acids and specific inorganic acids such as carbonic acid, phosphoric acid or boric acid are suitable.

The block copolymers, for example, halides of aliphatic or araliphatic hydrocarbons such as 1, 2 -Dibromethan, bischloromethylbenzene, silicon tetrachloride, dialkyl or diaryl can bi- or mehrfunktio- nelle compounds siliziumdichlorid, alkyl or Arylsiliziumtrichlorid, tin tetrachloride, polyfunctional aldehydes, such as Therephtalsäuredialdehyd, ketones, esters, anhydrides or epoxides are used. Carbonsäureester are preferred such as ethyl acetate used as a coupling agent when the block copolymer is not hydrogenated. In the hydrogenated block copolymer is preferably used

1, 2 -Dibromethan or diepoxides, in particular diglycidyl ethers, such as 1, 4-butanediol diglycidyl ether.

As a polymerization parameters influencing the additive (Ran- domizer), for example, Lewis bases such as polar, aprotic solvents, or hydrocarbon-soluble metal salts may be used. As Lewis bases, for example, dimethyl ether, diethyl ether, ethylene glycol, dimethyl ether Diethylenglykoldime-, tetrahydrofuran, tetrahydro furfuryl as tetrahy- can drofurfurylmethylether or tertiary amines such as pyridine, tri - methylamine are used triethylamine and tributylamine or peralkylated bi- or oligoamines as tetramethylethylenediamine. These are usually used in concentrations of 0.1 to 5 percent by volume to the solvent. Among the hydrocarbon-soluble metal salts used are preferably alkali metal or alkaline earth metal salts of primary, secondary and especially tertiary alcohols, particularly preferably the potassium salts as Kaliumtriethylcarbinolat or Kaliumtetrahydrolinaloolat. The molar ratio of metal salt to initiator is usually from 1: 5 to 1: 200, preferably 1: 30 to 1: 100.

Selection and amount of randomizer to be selected depending on the desired final product. For polymers which are not intended for hydrogenation, and when a high 1, 4-vinyl content is desired, for example, in the case of use of butadiene, it preferably employs a hydrocarbon-soluble potassium salt. For polymers which are subsequently hydrogenated, tetrahydrofuran is preferably used. The amount is chosen for this purpose so that for example in the case of using a butadiene 1, 2-vinyl content of about 20 to 50% results. In the inventive method, the total amount of the monomers a2) is preferably initially charged in a solvent and admixed with the polymerization initiator. but it is also possible to add portions of monomers a2) or the solvent only at a 5 later. The amount of polymerization initiators tör results from any existing, removable by titrating protic impurities in monomers and solvent plus the amount from the desired molecular weight and the total monomer to be polymerized

10 calculated amount. Preferably is n- or sec-butyllithium used, which is within a few hours, generally ranging from 0.5 to 40 hours at 20 to 70 ° C) with the monomers a2 completely to 1, 1-diphenylhexyllithium or the corresponding reacting substituted derivatives. To preferably at 40 to

15 70 ° C tempered template 60 to 100%, preferably metered from 70 to 90% of the total, required to form the block A quantity of monomers al). The feed time depends on the reactivity of the monomers used and the concentration and is generally between 0.5 and 10 hours at a

20 temperature of 40 to 70 ° C. The addition of the remaining amount of the monomers al) generally takes place after a conversion of about 80%, preferably more than 95% of the monomers charged or previously added. The block A is poly merized at high monomer concentration, and achieves a reduction of the residual monomers a2)

may be the 25th In general, the concentration of the polymerization after the last monomer addition is at least 35 wt.%, Particularly preferably more than 50 wt .-%.

In the preparation of the block copolymers having at least one block B 30, a block A is first as described above, then a block B is formed by sequential anionic polymerization.

After formation of the A-block, before the addition of the dienes b) the polymerization parameters influencing the 35 addition of the polymerization solution is added. Thereafter, block B by addition of the dienes b) is polymerized. Before or during the addition of the diene, it is advisable to dilute the reaction mixture with an inert solvent, to ensure adequate mixing 40 and heat dissipation. The polymerization temperature for the block B is preferably 50 to 90 ° C, when using polar, aprotic solvents as randomizer particularly preferably 50 to 70 ° C.

45 It would also be possible to repeat the method steps with the exception of the initiator solution and thus to block sequences (AB) n where n is an integer greater than 1 to move or attach only a direct WEI A block. However, this is not generally carried out, since the added in process step II.1 Randomizer usually interfere with the copolymerization of the monomers al) and a2) and would have to be removed from the reaction solution, or leads to polymers with inferior properties.

The resulting AB block copolymer may be terminated by chain termination or coupling agent, or in the case of bifunktionel- len coupling means to linear triblock copolymers or in the case of higher functional coupling agents linked to form star-shaped block copolymers.

The inventive method is not limited to the solution. For example, the process can be simply applied to the dispersion. For this purpose, it is advantageous to use an anionic polymerization initiator with respect to the inert dispersion medium in which the A-block is not soluble, such as propane, butane, isobutane, pentane or its branched isomers, hexane, heptane, octane or Isook- tan. In order to obtain a small particle size, are generally added from 0.1 to 2 -.% Of a dispersant added. Suitable dispersants are for example styrene / butadiene diblock copolymers having a high molecular weight as possible, for example, 100 000 g / mol.

The novel block copolymers can be hydrogenated anschießend by established methods. The hydrogenation of the block copolymers can be done on the other hand conventional rules which are well known in the olefinic polymers for reactions on the one hand and for the hydrogenation of double bonds. Suitable for this purpose catalysts from iron group metals, especially nickel and cobalt in combination with suitable reducing agents such as aluminum alkyls.

For example, a solution of hydrogenation catalyst is conveniently prepared as follows: To a l% solution of nickel acetylacetonate in toluene is added a 20% solution of triisobutylaluminum in hexane at room temperature, wherein the weight - ratio of nickel acetylacetonate to triisobutylaluminum in the range of 1 : 4. After the weakly exothermic reaction, the fresh catalyst solution is added to the polymer solution and pressurized with hydrogen. Per kg polymer are 1.5 g (0.15 wt.%) Nickel acetylacetonate sufficient; when the reaction mixture is particularly pure, already satisfy 0.15 g. The recoverable hydrogenation depends on catalyst concentration, hydrogen pressure and reaction temperature. Targeted degrees of hydrogenation of over 95% are 15 bar hydrogen partial pressure at and temperatures between 180 and 200 ° C reached after 30 to 120 minutes. At temperatures around 120 ° C, the hydrogenation takes 8 to 16 hours. Prerequisite for a good space-time yield is a good mixing of the hydrogen gas. For this purpose, an effective stirrer is required with good vertical mixing, which also creates surface so that the gas can go into solution. so-called gassing of these are very suitable sungsrührer. After completion of the hydrogenation, the colloidally dispersed nickel, which dyes the polymer solution black can be oxidized up by decolorization with a hydrogen peroxide-acetic acid mixture.

The hydrogenation can - especially on an industrial scale - of course be carried out with other homogeneous and heterogeneous hydrogenation catalysts. Particularly interesting is the hydrogenation on a fixed bed catalyst because contamination of the polymer is avoided by catalyst residues.

The work-up of the polymer solution is carried out by the conventional methods of polymer technology, for example by degassing extruders or in cases with polar solvents such as alcohols or by dispersing in water and remove the solvent by stripping.

Usually, the block copolymers are mixed with stabilizers. Stabilizers which are suitable for example, hindered phenols such as Irganox® 1076 or Irganox® 3052 from Ciba-Geigy, Basel or α-tocopherol (vitamin E).

The block copolymers can also be adjusted by the addition of plasticizers in mechanical properties such as elasticity and jerk subfund. Plasticizers compatible with the B blocks formed of the soft phase, such as aliphatic mineral oil are preferred. They are usually used in amounts of from 10 to 90 wt .-%, based on the molding composition.

Furthermore, the block copolymers can be processed into molding compositions and fen with compatible polymers and other Zusatzstof-, such as processing aids, lubricants and Entgasungsstoffen, fillers and reinforcing agents, and flame retardants are mixed homogeneously in conventional amounts.

The copolymerizable prepared by the novel method ren or copolymer A have also with lower overall molecular weights Mw below 40,000 g / mol, in particular 15 000 g / mol has a narrow molecular weight distribution. This is of particular block copolymers of importance, which are used as thermoplastic elastomers. A broad molecular weight distribution of the blocks A leads to a high proportion of very low block length and therefore to a greater compatibility with the blocks B formed of the elastomeric phase. This proportion is therefore not effective for the physical crosslinking in thermoplastic elastomers.

Examples:

Purification of 1, 1 -Diphenylethylen (DPE)

Commercially available DPE was on a column of minde ¬ least 50 theoretical plates; distilled at 99.8% purity (spinning band column for larger quantities column with Sulzer packings). The most pale yellow distillate through a 20 cm Alox column (Woelm alumina for chromatography, anhydrous), filtered, titrated with 1.5 N See-butyllithium until a red color and strong in vacuo (1 mbar) distilled over. 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 solvent was dried over anhydrous alumina and titrated with the adduct of sec-butyl lithium and 1, 1-diphenylethylene until a yellow coloration. The 1, 1-diphenylethylene (DPE) was distilled from sec-butyllithium (s-BuLi). Styrene (S) and butadiene were dried over alumina immediately prior to use at -10 ° C.

The coupling means ethyl acetate, and 1, 2 -Dibromethan were dried over alumina. 1, 4 -Butandioldiglycidylether (Grilonit RV ® 1806, Fa. Ems chemistry, Linz, Österreicht) was brought to a purity of 99.5% by fractional distillation under high vacuum at 0.1 mbar.

The molecular weights were determined by gel permeation chromatography measured vs. polystyrene standards from. Polymer Laboratories in THF. Detection by refractometry.

As a measure of the efficiency of the coupling step, the coupling yield of the GPC was distribution (gel permeation chromatography) as the ratio of coupled products (in the neighboring following examples, three-block copolymers) to the sum of coupled products and non-coupled polymers determined. The determination of the double bond content was determined by Titra ¬ tion Wijs (iodometry).

The mechanical properties were dependent on the temperature at norm small rods determined in a tensile test according to DIN 53 455.

Preparation of unhydrogenated S / DPE-Bu-S / DPE-block copolymer

Example 1:

In a 50 1 reactor 2.9 kg cyclohexane, 0.79 kg 1, 1-diphenylethylene and 150 ml of a 1 molar s-Butyllithiumlö- solution were introduced into n-hexane and stirred at 50 ° C for 14 h. The solution was then heated to 60 ° C and 1.88 kg of styrene was added over 6 minutes. After 10 minutes, a further 0.21 kg were

Styrene with 1.5 kg / h added. , 25 minutes after completion of the styrene - were to admit was diluted with 18.1 kg of cyclohexane. The obtained S / DPE copolymer had a molecular weight M n of 9804 g / mol, M w of 11854, Mp (peak maximum) of 11990, M w / M n of 1.21 and a glass transition temperature of 128 ° C. To the cooled to 50 ° C polymer solution 2 ml of a 10 wt .-% strength Kaliumtetrahydrolinalo- were olate solution was added. were subsequently first 2.04 kg butadiene with 8 kg / h, then added with 4.08 kg 4 kg / h. After a postreaction of 110 minutes at 50 ° C a 3-state-stellar solution of ethyl acetate was treated with 40 ml of cyclohexane. The block copolymer had a molecular weight M w of 117280 and the coupling yield was 90%. The viscosity number (0.5% in toluene) was 93, the melt flow index MVI (200 ° C / 21.6 kg) 10.9 ml / 10 min. The double bond content was determined according to Wijs to 66.5%.

The block copolymer obtained was for stabilization with 63 g of trisnonylphenyl phosphate (TNPP), 27 g of vitamin E, 45 g of octadecyl 3 (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox® 1076 from Ciba-Geigy) and 27 g of 2, 6-di-tert-butyl-p-cresol (Kerobit® TBK) and 112.5 ml of a 4 molar solution of formic acid in ethanol.

The stabilized block copolymers could be processed without the addition of oil on a twin-screw extruder ZSK 25/2 at 180 ° C. The mechanical properties were determined on injection-molded standard rods and are summarized in Table 1 below. Example 2:

In a 50 1 reactor 8.4 kg cyclohexane, 0.98 kg 1, 1-diphenylethylene and 120 ml of a 1 molar s-Butyllithiumlö- solution were introduced into n-hexane and stirred at 50 ° C for 14 h. Subsequently, 2.62 kg styrene with 12 kg / h was added, the temperature was maintained at 50 ° C. 30 minutes after completion of the addition of styrene was diluted with 12.6 kg of cyclohexane. The S / DPE copolymer obtained had a molecular weight M n of 15146 g / mol, M w of 17391 g / mol, Mp of 18332 and M w / M n = 1.15 and a glass transition temperature of 130 ° C. To the polymer solution 10 ml of a 10 wt .-% strength Kaliumtetrahydrolinaloolat solution were added. were subsequently first 1.80 kg butadiene with 8 kg / h, then added with 3.60 4 kg / h. The viscous orange polymer solution, after a reaction time of 1.5 h gray. C was then treated with 70 ml of a 3 molar solution of ethyl acetate in cyclohexane at 50 °. The block copolymer had a molecular weight M w of 121720 g / mol, the coupling yield was 89%. The viscosity number (0.5% in toluene) was 91, the melt flow index (200 ° C / 21.6 kg) 1.9 ml / 10 min. The double bond content was determined according to Wijs to 50%.

The block copolymer obtained was for stabilization with 63 g of TNPP, 27 g of vitamin E, 45 g of 2 '-Acryloyloxi-3, 3' -di-tert-butyl-2 '- hydroxy-5, 5' -dimethyldiphenylmethan (Irganox® 3052 Ciba-Geigy) and 27 g of 2, 6-di-tert-butyl-p-cresol (Kerobit® TBK) and 90 ml of a 4 molar solution of formic acid in ethanol.

The stabilized block copolymers were extruded in a twin-screw extruder ZSK 25/2 at 180 ° C with addition of 30% white oil DAB 10 (Minog® 70 of the Fa. Wintershall AG).

Example 3:

In a 50 1 reactor 1.5 kg cyclohexane, 1.67 kg 1, 1-diphenylethylene and 300 ml of a 1 molar s-Butyllithiumlö- solution were introduced into n-hexane and stirred at 50 ° C for 14 h. Subsequently, 1.21 kg of styrene with 1 kg / h was added, the temperature was maintained at 50 ° C. 30 minutes after completion of the addition of styrene was diluted with 19.5 kg of cyclohexane, and cooled to 40 ° C. The obtained S / DPE copolymer had a molecular weight Mn of 3754 g / mol, M w of 4445 g / mol, Mp of 4676 g / mol, M w / M n = 1.18 and a glass transition temperature of 152 ° C. To the polymer solution 70 ml of freshly titrated tetrahydrofuran was added. were subsequently first 2.04 kg butadiene with 8 kg / h, then added with 4.08 3 kg / h. After a postreaction of 20 minutes at 40 ° C 4-butanediol diglycidyl ether were mixed with 35 ml of 1, was added. The block copolymer had a molecular weight M w of 58180 g / mol, the coupling yield was 88%. The viscosity number (0.5% in toluene) was 55. The double bond content was determined according to Wijs 5 52.4%. The 1, 2-vinyl content was 43.2%.

Example 4:

In a 50 1 reactor 1.5 kg cyclohexane, 1.12 kg 0 1, 1-diphenylethylene, and 57.1 ml of a 1 molar s-Butyllithiumlö- solution were introduced into n-hexane and stirred at 50 ° C for 14 h. , 8 kg of styrene with 1 kg / h was then added 0, where the temperature was maintained at 50 ° C. 30 minutes after completion of the addition of styrene was diluted with 22.5 kg of cyclohexane, and cooled to 40 ° C. The S 5 obtained / DPE copolymer had a molecular weight M n of 9450 g / mol, M w of 10420 g / mol, Mp of 10220 g / mol, M w / M n = 1.10. To the polymer solution 70 ml of freshly titrated tetrahydrofuran was added. were subsequently first 1.36 kg butadiene with 8 kg / h, then added with 2.72 3 kg / h. After a post-0 reaction of 20 minutes at 50 ° C 4-butanediol was treated with 8.3 ml of 1 - glycidyl ether was added. The block copolymer had a molecular weight M w of 213500 g / mol, the coupling yield was 85%. The viscosity number (0.5% in toluene) was 55. The double bond content was determined according to Wijs to 59.7%. The 5 1,2-vinyl content was 42.6%.

Example 5:

In a 50 1 reactor 1.5 kg cyclohexane, 1.67 kg 0 1, 1-diphenylethylene and 300 ml of a 1 molar s-Butyllithiumlö- solution were introduced into n-hexane and stirred at 50 ° C for 14 h. Subsequently, 1.21 kg of styrene with 1 kg / h was added, the temperature was maintained at 50 ° C. 30 minutes after completion of the addition of styrene was diluted with 19.5 kg of cyclohexane, and cooled to 40 ° C. Of the

35 obtained S / DPE copolymer had a molecular weight M n of 4480 g / mol, M w = 5096 g / mol, Mp of 5277 g / mol, M w / M n of 1.14. To the polymer solution 70 ml of freshly titrated tetrahydrofuran was added. were subsequently first 2.04 kg butadiene with 8 kg / h, then added with 4.08 3 kg / h. After a further

40 of 20 minutes at 40 ° C was treated with 19.4 ml of 1, 2-dibromoethane. The block copolymer had a molecular weight M w of 56662 g / mol, the coupling yield was 83%. The viscosity number (0.5% in toluene) was 47. The double bond content was determined according to Wijs to 60.8%. The 1, 2-vinyl content was

45 43%. Preparing hydrogenated S / DPE-Bu-S / DPE-block copolymer

example 6

Preparation of the hydrogenation catalyst:

In a round bottom flask in 1125 ml of a saturated nickel acetylacetonate at room temperature (about 10 g / 1) were added with stirring added to a solution of 192.5 ml of a 20 wt.% Solution of triisobutylaluminum in n-hexane was added under nitrogen in toluene. When the slightly exothermic reaction escaped isobutanol and the temperature rose to 50 ° C.

The polymer solution from Example 3 was heated in a 50 1 stirred reactor at 60 ° C and treated with a freshly prepared catalyst suspension. The mixture was then hydrogenated at 120 ° C and a pressure of 18 bar with hydrogen. After 25 h, a residual double bond content was determined by 22.6%. After another 17.5 hours the solution was cooled to 60 ° C. The double bond content was 18.5%.

Subsequently, the reaction solution was treated oxidatively with 300 ml of a mixture of 3.6 1 water, 360 ml of a 30% hydrogen peroxide solution and 200 ml of 98% acetic acid at 60 ° C, the residue washed with water and dried.

In order to stabilize the hydrogenated S / DPE-Bu-S / DPE Blockcopo- were mers, each with 0.1 wt .-% Irganox 3052 and Kerobit® TBK added.

The viscosity number (0.5% in toluene) was 51 ml / g.

The mechanical properties were on standard small bars (punched out from the press plates) is determined at 23 ° C. Tensile strength: 25 MPa; Elongation at break: 1,014%; Shore hardness A: 69th

example 7

The polymer solution from Example 4 was hydrogenated analogously to Example 6. Fig. The double bond content was 2.6%. The Shore A hardness was 54.7. example 8

Preparation of the hydrogenation catalyst:

To a suspension of 15 g of nickel acetylacetonate in 250 ml

Of toluene was added under nitrogen and vigorous stirring, a solution of 350 ml of a 20 wt.% Solution of triisobutylaluminum in n-hexane and allowed to react for 15 minutes.

The polymer solution from Example 5 was heated in a 55 1 stirred reactor at 90 ° C and treated with a freshly prepared catalyst - mixed suspension. bar was then hydrogenated with hydrogen at 140 ° C and a pressure of 18th After 3 and after 6 hours of subsequent dosing of the catalyst suspension was carried out (in each case based on 10 g of nickel acetylacetonate), a residual double bond content of 2% after 24 h determined.

Subsequently, the reaction solution was oxidatively oxide solution with 300 ml of a mixture of 3.6 1 water, 360 ml of a 30% hydro- gen and 200 ml of 98% acetic acid, treated at 60 ° C, the residue washed with water and dried.

In order to stabilize the hydrogenated S / DPE-Bu-S / DPE-block copolymers were each with 0.1 wt .-% Irganox 3052, 0.1 wt .-% Irganox 1076 and Kerobit® TBK added.

The viscosity number (0.5% in toluene) was 50 ml / g. The melt flow index MVI (200 ° C / 21.6 kg) was 15.7 mL / 10 min ..

Double bond content of 3.1%. The mechanical properties are summarized in Table 1 below.

Table 1 shows the mechanical properties of the unhydrogenated S / DPE-Bu-S / DPE-block copolymers of Example 1 and the hydrogenated S / DPE-ethylene-S / DPE-block copolymer of Example 8 are shown at different temperatures. The results demonstrate the very high heat resistance of the novel block copolymers.

Table 1: Mechanical properties

Figure imgf000017_0001

Figure imgf000018_0001

Failure of the sample; nb, not determined

Claims

Patentansprüche1. Or block copolymers with at least one block A composed of vinylaromatic monomers al) and 1, 1-diphenylethylene or its optionally substituted on the aromatic rings with alkyl groups having up to 22 carbon atoms derivatives a2), erhältlich by anionic polymerization, characterized in that , one daß to form the copolymer or the block a is a Starterlösung consisting of the reaction product of an anionic polymerization initiator and at least the equimolar amount of monomers a2), verwendet.2. Block copolymers having at least one block A gemäß claim 1 and at least one, optionally hydrogenated, block B serve out b), erhältlich by sequential anionic polymerization, characterized in that daß successively durchführt the following process steps: I ) form a block a durch1.1) preparation of Starterlösung consisting of the reaction product of an anionic polymerization initiator and at least the equimolar amount of monomers a2), 1.2) addition of any remaining residual amount of monomers a2) and 60 to 100% of the total amount of monomers al),
1.3) addition of any remaining amount of
Monomers al) after a conversion of at least 80% of added in the previous steps of monomers,
wherein the concentration of Polymerisationslösung wt .-% beträgt after the last monomer addition at least 35,
II) anschließenden formation of a block B by
II.1) addition of the polymerization parameters influencing additive,
II.
2) Addition of the dienes b) and
optionally III the anschließenden steps) adding a chain-stopping or coupling agent,
IV) hydrogenation of the block copolymer,
V) Isolation and work-up of the block copolymers according to known per se,
VI) addition of stabilizers.
3. Block copolymers according to claim 2, characterized gekennzeichent, daß the block copolymers by bi- or multi-functional coupling agent prepared symmetrical three-block copolymers or star block copolymers with außenliegenden Blöcken A mean the sum of the Blöcke A in the range of 5 to 50 wt .-%, based on the entire block copolymer, beträgt.
4. Block copolymers according to Ansprüchen 2 to 3, characterized in that daß in method step III) as a coupling agent Carbonsäureester doubly halogenated aliphatic or araliphatic hydrocarbons or diglycidyl ethers of aliphatic alcohols are used.
5. Non-hydrogenated block copolymers according to the Ansprüchen 2 to 4, characterized in that in process step daß II.1) kohlenwasserstofflösliches a metal salt as a polymerization parameters influencing the additive is used.
6. The hydrogenated block copolymer according to Ansprüchen 2 to 4, characterized in that in process step daß II.1) a polar, aprotic Lösungsmittel as a polymerization parameters influencing the additive is used.
7. A process for the preparation of copolymers gemäß the method steps according to Ansprüchen 1 or second
8. The use of copolymers gemäß the Ansprüchen 1 to 6 for producing molding compositions.
9. molding compositions erhältlich gemäß from the copolymers claim. 8
PCT/EP1998/003701 1997-06-30 1998-06-18 1,1-diphenyl ethylene-based thermoplastic elastomers WO1999001487A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018060015A1 (en) 2016-09-27 2018-04-05 Basf Se Star-shaped styrene polymers with enhanced glass transition temperature

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374961A2 (en) * 1988-12-23 1990-06-27 Asahi Kasei Kogyo Kabushiki Kaisha Shape memory polymer resin, resin composition and the shape memorizing molded product thereof
WO1995034586A2 (en) * 1994-06-16 1995-12-21 Basf Aktiengesellschaft Thermoplastic moulding material
WO1997047672A1 (en) * 1996-06-12 1997-12-18 Basf Aktiengesellschaft Block copolymers and thermoplastic mounlding compounds containing them

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374961A2 (en) * 1988-12-23 1990-06-27 Asahi Kasei Kogyo Kabushiki Kaisha Shape memory polymer resin, resin composition and the shape memorizing molded product thereof
WO1995034586A2 (en) * 1994-06-16 1995-12-21 Basf Aktiengesellschaft Thermoplastic moulding material
WO1997047672A1 (en) * 1996-06-12 1997-12-18 Basf Aktiengesellschaft Block copolymers and thermoplastic mounlding compounds containing them

Non-Patent Citations (1)

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Title
W. TREPKA: "SYNTHESIS AND PROPERTIES OF BLOCK POLYMERS OF 1,1 DIPHENYLETHYLENE AND BUTADIENE", JOURNAL OF POLYMER SCIENCE, PART B: POLYMER LETTERS, 1970, pages 499-503, XP002026769 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018060015A1 (en) 2016-09-27 2018-04-05 Basf Se Star-shaped styrene polymers with enhanced glass transition temperature

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