DE2643757C2 - Mixtures of hydrogenated styrene-butadiene block polymers with polycarbonates, processes for their preparation and their use - Google Patents

Description

(D

wherein X = Ci-C ₅ - alkylene or - alkylidene, exist or of mixtures of polycarbonates with

recurring syrup units of the formula (1) and polycarbonates based on not ο, ο, ο ', ο'-tetra- |

methyl-substituted bisphenols, the total content of the mixture of ο, ο, ο ',, ο'-tetramethylsubstltu- ®

lerten structural units is not less than 50%, and possibly additionally
c) known aggregates.

2. Process for the preparation of the mixtures according to claim 1, characterized in that either

(A)

(A. 1) Solutions of components a and b combined and
• ^{1 (l} (A.2) then water vapor and combined solution in water at temperatures from 60 to 120 ° C

simultaneously introduced and

(A.3) the resulting polymer crumbs dried after separating off the water or that the solvent after combining the solutions of components a and b, it is evaporated in evaporation screws, or that

• tf (B) the components a and b without solvent in substance in suitable units at temperatures from 150 ° C up to 280 ° C.

3. Use of the mixtures according to claim 1 with a higher proportion of soft segment B for production of technical rubber articles.

· "'4. Use of the mixtures according to claim 1 with a predominant proportion of hard segment A and

Polycarbonate b) for the production of moldings.

Block copolymers composed of alternately linear or branched segments A and B, in which A is polymer blocks from vinyl aromatics and B polymer blocks of conjugated dienes or blocks from statistical Mean copolymers of dienes with vinyl aromatics are known (segment polymers). You have thermo-5Ii elastomeric properties, d. H. they can be thermoplastically deformed in the heat and have at room temperature the character of elastomers. A disadvantage is their reduced useful life with increased Temperature, their poor ozone resistance, in many cases insufficient abrasion resistance and too low Tear strength.

Improved products can be obtained if one part or all of the double bonds or benzene nuclei hydrogenated.

On the other hand, polycarbonates made from ο, ο, ο ', ο'-tetramethyl-substituted bisphenols are known, the one have excellent heat resistance and oiling stability. However, their toughness is common to many Purposes not sufficient.

It has been found that by mixing said polycarbonates with hydrogenated segment polymers

¹¹ i thermoplastic rubbers are obtained with improved properties'. For example, the fitness for use at elevated temperature, e.g. B. characterized by measuring the tensile strength, elongation and hardness as well as abrasion, tear resistance and resistance to ozone and oxygen flow

improved.

It has also been found that, conversely, the polycarbonates are improved in their toughness and processability by admixing segment polymers. The transparency of the polycarbonate can be retained without any special measures. The stability of these mixtures against discoloration and degradation during processing despite the presence of alkali is noteworthy. In addition, the resistance to noise can be improved.

This invention relates to mixtures of

1) 99 to 1% of a subsequently hydrogenated block copolymer composed of an alternating linear or branched arrangement Segments A and B, in which A polymer blocks of vinyl aromatic compounds with Tg> 20 ° C (hard segment) and B polymer blocks made of conjugated dienes with Tg <0 ° C (soft segment) and

2) 1 to 99% aromatic polycarbonates, the linear chains of which are made up of at least 50% structural units of the formula

(D

where X = Ci-C ₅ -alkylene or -alkylidene lsi, or of mixtures of polycarbonates with recurring structural units of the formula (1) and polycarbonates on baths not ο, ο, ο ', ο'-tetramethyl-substituted bisphenols, where the total content the mixture of ο, ο, ο ', ο'-tetramethyl-substituted structural units is not less than 50% , and optionally additionally 3) known additives.

Aromatic polycarbonates whose linear chains are made up of at least 50% structural units of the formula

(D

in which X = Ci-Cs-alkylene or -alkylidene exist, are known. They are described in the German Offenlegungsschriften 20 63 050, 15 70 703, 22 11 957 and 22 48 817. In principle, they are produced from ο, ο, ο ', ο'-tetramethyl-substituted bisphenols and phosgene in a manner known per se. , Ο'-tetramethyl substituted 'the structural unit ο, ο, ο, ο'-tetramethylsubstltuierten bisphenols will get "mixed" polycarbonates, in which only a portion - - According to the invention at least 50%' by concomitant ^ss non ο, ο, ο.

Preference is given to polycarbonates whose linear chains consist of at least 75% structural units of the formula (1) exist. Polycarbonates which only consist of structural units of the formula (1) are particularly preferred.

The polycarbonate units of the formula (1) can, for. B. the following ο, ο, ο ', ο'-tetramethyl-substituted bisphenols * underlie:

Bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -ethane

1,1 -Bis (3,5-dlmethyl-4-hydroxyphenyl) propane

2,2-bis- (3,5-dlmethyl-4-hydroxyphenyl) -propane 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -butane 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -butane 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane

3,3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane.

Of these bisphenols, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane is particularly preferred.

Examples of not ο, ο, ο ', ο'-tetramethyl-substituted bisphenols, which are used to produce the "mixed" polycarbonates or for the production of polycarbonates from non-ο, ο, ο ', ο'-tetramethyl-substituted units are:

Hydroquinone

Resorcinol

Dihydroxydlphenyls

Bls- (hydroxyphenyl) alkanes M)

Bls- (hydroxyphenyl) cycloalkane bis (hydroxyphenyl) sulfides

Bis (hydroxyphenyl) ether

Bis (hydroxyphenyl) ketones

Bis (hydroxyphenyl) sulfoxides M.

Bis- (hydroxyphenyl) -sulfones a, cr'-bis (hydroxyphenyl) -dilsopropylbenzenes as well as their core alkylated and core halogenated compounds.

These and other suitable aromatic dihydroxy compounds are described in US Pat. 29 99 835, 31 48 172, 32 71 368, 29 91 273, 32 71 367, 37 80 078, 30 14 891 and 29 99 846 and in German Offenlegungsschrift 15 70 703 described.

Particularly preferred are:

2,2-bis (4-hydroxyphenyl) propane
1,1-bis (4-hydroxyphenyl) cyclohexane
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane
i «a, cf'-bis (4-hydroxyphenyl) -p-diisopropylbenzoi.

The polycarbonates can by incorporating small amounts of polyhydroxy compounds, e.g. B. 0.05 to 2.0 mol% (based on the bisphenols used), be branched. Polycarbonates of this type are z. Tie German Offenlegungsschriften 15 70 533, 21 16 974, 21 13 347, British patents 8 85 442,

'S 10 79 821 and in US Pat. No. 3,544,514. Some of the polyhydroxy compounds that can be used are for example phloroglucinol, 4,6-dimethyl-2,4,6-tii- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxypfienyl) -phenylmethane, 2,2-bis [4,4- (4,4'-di-hydroxydi-I

phenyD-cyclohexyl-propane, 2,4-bis- (4-hydroxyphenyl-4-isopropyl) -phenol, 2,6-bis- (2'-hydroxy-5'-methylbenzyl) -4-methyl-phenol, 2,4-dihydroxybenzoic acid, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, 1,4-

- "Bis- (4 ', 4" -dihydroxy-trlphenyl-methyU benzene.

The polycarbonates usually have molecular weights M _n , from 10,000 to 200,000, preferably from 20,000 to 60,000.

The hydrogenated segment copolymers required to produce the polymer mixtures can be according to various known methods can be produced. According to DE-OS 19 40 278, for example living block polymers of type A-ßO-Li © by coupling with carboxylic acid esters in segment polymers from Convert type A-B'-A. Here A means a polystyrene block, B a polydiene block and Li means lithium, B ' has twice the molecular weight of B. DE-OS 16 45 298 describes a process in three stages, after which first styrene is polymerized with lithium alkyls to form a living polystyrene block, then butadiene is added and after its polymerization again styrene, so that a segment polymer of the

- ¹ "structure ABA results. If the addition of monomers is repeated, multi-segment products can be obtained. According to DE-AS 15 20 543, living di-block polymers of structure AB-Li are coupled with polyfunctional couplers such as polyepoxides or polyaziridinyl compounds to form segment polymers of structure (AB) _n K, where K is the coupler molecule and η is its functionality. According to DE-AS 19 05 422, the coupling of living di-block polymers with diesters can take place

- ^ produce from polyfunctional lithium compounds. This is obtained, for example, from lithium metal and Naphthalene and subsequent reaction with styrene. Poly-Li compounds made from are known Lithium alkylene and Divlnylbenzol, which can carry up to 50 functional groups. The suitably controlled Implementation of such polyfunctional lithium compounds leads to star-shaped segment polymers. After DE-OS 25 04 118 are segment polymers by the gradual addition of a) styrene, b) styrene mixture and

c) styrene again prepared in the presence of Llthiumalkyl and a polar compound, the middle Block is formed as an elastomeric random copolymer of diene and styrene.

It is also possible to use segment polymers which are obtained by coupling block polymers with peroxides are obtained, as described, for example, in DE-OS 2,457,389 and US Pat. No. 3,819,766 are. Segment polymers which are formed by coupling block polymers with sulfur halides are also suitable obtained; these are mentioned in DE-OS 24 57 388. More examples of star-shaped Segment polymers are described in DE-OS 25 29 065.

The monomers used to produce the hard segments A can be: styrene, vinylnaphtahlin, cr-methylstyrene and alkylstyrenes. Styrene is preferably used. Monomers for the production of the elastic Segments are conjugated dienes such as 1,3-butadiene, isoprene, plperylene, whereby the elasto-

^? "meren segments, which are present as random copolymers, in addition to butadiene and isoprene, in particular styrene, can be used as comonomer.

The molecular weight of the hard segments A can be 5,000 to 250,000, preferably 10,000 to 50,000; the molecular weight of the elastomeric soft segments can be 10,000 to 500,000, preferably 20,000 to 80,000.
The hydrogenation of the segment polymers is known and can be carried out according to various methods.

For example, Raney nickel can be used as a catalyst. It is also possible to combine cobalt or nickel salts with aluminum alkyls. In addition, noble metal salts such as rhodlum halides can also be used. The double bonds can be hydrogenated completely or partially, depending on the requirements for ozone resistance.
The percentage of the hard component in the segment polymer depends on the desired properties

'' "shafts of the polymer mixture from the polycarbonate with the segment polymer.

Improved thermoplastic rubbers are preferably composed of 2 to 50 wt .-%, particularly preferably from 10 to 35 wt .-% of the polycarbonates and, preferably, of 98 to 50 wt .-%, particularly preferably from 90 to 65 parts by weight ¹ Y, the Segment polymer. The Segmentpolymerisat itself contains 10 to 60, preferably 20 to 50 C! Ow.- ¹ Hi Iliirlsegmcnlc and 90 to 40, preferably 80 to 50 wt .-% Wclchscgmcntc.

Improved ^ΙΛ polycarbonates are preferably composed of 10 to 90, particularly preferably from 15 to 80 wt .-%> Segmentpolymerisat and preferably from 90 to 10, particularly preferably from 85 to 20 parts by weight 96 polycarbonate. The fragment polymer itself contains 10 to 90, preferably 30 to 80% by weight of hard segments and 90 to 10, preferably 70 to 20% by weight, wax segments.

The polycarbonate / segment polymer blends can be produced by combining solutions of the individual components or by combining the pure components. From the obtained solutions, the polymer mixture can be isolated by a stripping process by introducing simultaneously water vapor and solution at temperatures from 6O ⁰ C to 120 ⁰ C. Here, the polymer mixture falls in the form of crumbs, which after separating the water by known methods, such as. B. drying in vacuum, in a drying screw or on belt dryers. The polymer can also be freed from the solvent directly from the solution in evaporation screws. The preparation of mixtures without solvent can be carried out at temperatures of 150 ° C to 280 ⁰ C, in suitable equipment such as roll mills or kneaders.

Suitable additives are, for example, polystyrenes, polymethyl methacrylate or styrene-acrylic copolymers, Silicas of various origins, silicates and other minerals, wood flour, soot or glass fibers, Effect substances, dyes, pigments, thermal, oxidation, UV and other stabilizers, plasticizers, lubricants, Mold release agents, flame retardant additives such as halogenated organic compounds, Metal oxides, metal salts and organic phosphates.

The mixtures can be made softer by adding oils. One can be aliphalic, naphthenic or use aromatic oils. Also the use of polyolefin oils and polydolefin oils is possible. It is also possible to use higher-boiling allphosphatic, araliphatic and aromatic esters.

The mixtures can be stabilized with customary rubber stabilizers, for example from Type of alkylated mono- or polynuclear phenols or thioethers of alkylated phenols. Also is that Addition of synergistic compounds, for example of the thiobisalkanoic acid ester type and the Alkylphenylphosphines possible.

The polymer mixtures with a higher proportion of soft segment B can be used for production technical rubber items! like shoe soles, hoses, seals. Those with a predominant share of Hard component A and polycarbonate are suitable for the production of saponification-stable, impact-resistant, highly heat-resistant Shaped bodies, such as pipes, for example. Housing parts and containers.

example 1

100 parts of a commercially available hydrogenated triblock styrene / butadiene copolymer were abbreviated to A) with 20 parts and B) with 30 parts of a polycarbonate made from tetramethylbisphenol A (= 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl! -Propane) MPOy ,,, = 1.30 mixed as toluene solutions. After the addition of 0.5 phr di-tert-butyl-methyl-phenol, the rubber was isolated by precipitation with ethanol. Drying in vacuo at 70 ° C. yielded an elastic material , the test values of which were compiled in Table 1. For comparison, the analogous test values of the uncut hydrogenated block copolymer were entered. In addition to an improvement in the moduli, there was, in particular, a considerable improvement in the heat resistance, evident from the values of the Shore hardness at 100 ^° C. and 120 ° C, and the strengths at 8O ⁰ C. also improved is the Weiterreißfestigkeil (Str.).

Table 1

sample

D M 300/500% H 23/70/100/120/150 ° C E 23/70 ° C Str. F (80 ° C) D (80 ° C)

A 14.0 315 13.1

B 17.4 185

hydrogenated block copolymer 16.7 555 3.5

83 78 68 55 29 54/58 130 6.2 345
87 83 75 65 34 57/54 165 7.2 320
78 67 39 27 23 57/60 97 2.5 425

Abbreviations: F = strength, D = elongation, M = modulus (tension value), H = Shore Α hardness, E = rebound elasticity, Str. = Tear strength wedge according to Pohle (structure), F (80 °) or D (80 °) = strength or elongation measured at 80 ° C. The Values would srn standardization! DIN 53 504 ι

opmpccpn

Example 2

Analogously to Example 1, mixtures of 20 (A) and 30 phr MPC (B) each were produced from another commercially available hydrogenated block copolymer and MPC, and the values were compared with the uncut hydrogenated block copolymers. Here, too, the superiority of the mixtures in terms of heat resistance is clearly evident (Table 2).

Table 2

sample

M 300/500% H 23/70/100/120/150 ° C E 23/70 ° C Str. F (80 ° C) D (80 ° C)

A 15.0 280

B 20.4 280

hydrogenated block 20.0 530 copolymer

4.8 17.4

83 78 62 45 19 58/63 110 4.1 225

84 82 66 53 29 57/61 150 5.6 205
78 67 31 22 10 63/61 88 1.6 250

Claims (1)

Claims: 1. Mixtures of a) 99 to \% of a subsequently hydrogenated block polymer consisting of alternating linear or branched segments A and B, in which A polymer blocks made of vinyl aromatics with Tg> 20 ° C (hard segment) and B polymer blocks made of conjugated dienes with Tg <0 ° C (soft segment) mean and
b) 1 to 99% of aromatic polycarbonates, the linear chains of which are made up of at least 50% of structural units i "formula