CZ91299A3 - Thermoplastic materials for producing plastics and their use - Google Patents

Abstract

The thermoplastic materials after the plastics production consist of A) 30 to 98 wt. % of graft polymer composed of 30 to 90 wt. % graft core of crosslinked acrylic rubber and 10 to 70 wt. % grafted envelope, consisting of a mixture of 50-100 % by weight of styrene compound or (C 1-6 -alkyl) acid ester acrylic or methacrylic acid, or styrenic mixtures compounds and (C 1-6 alkyl) esters of acrylic acid or acid methacrylic and 0 to 50% by weight of at least one other monomer, Β) 1 to 50% by weight of thermoplastic polymer aC) 1 to 70% by weight of a rubber-elastic block copolymer.

Description

Thermoplastic materials for the production of plastics and their use

QbJ and with t ....... techniques

The invention relates to thermoplastic materials for the manufacture of plastics and to their use.

BACKGROUND OF THE INVENTION [0002] Many plastics applications have a wide range of applications, in particular flexible leather-like films with interior finishes, leather. It is usually produced

The foils of the specified foil are used extensively in, for example, cars, or as replacements by calendering or extrusion.

The main component of these films is currently polyvinylchloride (PVC), which contains a plasticizer and often other vinyl polymers. However, the films are only conditionally stable to aging and, in addition, plasticizers may escape over time.

EP-A 526 813 discloses thermoplastic materials for the production of plastics from highly cross-linked acrylic rubber with a graft envelope of methyl methacrylate or styrene / acrylonitrile, partially crosslinked acrylic rubber, an ethylene-vinyl acetate copolymer and also optionally other styrene-based and / or acrylic compound-based polymers. However, under forming conditions, such as foils, these materials tend to undergo undesired degradation reactions.

In DE-A 42 11 412 mixtures of styrene and acrylonitrile polymers and thermoplastics having a graft casing of an astomer polymer are recommended as film materials. The production of such graft polymers is demanding in terms of process performance, making it difficult to maintain production quality.

In particular, the films as well as the known plastics materials do not have the properties in their entirety and have a high hardness, which does not achieve the desired rough skin (sof t-touch).

satisfactory deep-drawing Shore, so it never resembles the surface

The essence of the invention

The invention consists of materials for the production of plastics of consistent quality and furthermore, for example, as a degradation reaction, the materials obtainable by molding must be prepared, in particular by deep-drawing properties and high resistance to further shore.

The task of solving thermoplastic, which are easy to manufacture, workable without loss of quality, molding, please consider the film. Furthermore, for the production of plastics, of which the films are characterized by good (high ductility to cracking) and also low hardness

In view of this, thermoplastic materials have been found for the production of plastics

A) 30 to 98 wt. % of the graft polymer of (a) 30 to 90 wt. Ϊ a rubber-elastic graft core comprising a copolymerization and / or) 80 to 99.99 wt. % of one or more (C 1 -C 10 alkyl) acrylic esters, k (2) 0.01 to 20 wt. % of cross-linked monomers and (a) 0 to 40 wt. % of one or more additional monomers, and) 10 to 70 wt. % grafted envelopes from • · • ·

(A) 50-100 wt. % styrene compound of formula

R ²

wherein R ¹ and R ² are hydrogen or C 1 -C 8 -alkyl, or (C 1 -C 6 -alkyl) acrylic or methacrylic acid ester, or a mixture of a styrene compound and (C 1 -C 6 -alkyl) acrylic acid ester or 2) 0 to 50 wt. % of one or more additional monomers,

B) 1 to 50 wt. % of thermoplastic polymer of bi) 50 to 100 wt. b2) 0 to 50 wt.% of styrene or .beta.-methyl styrene or mixtures thereof; and b3) 0 to 50 wt. % of one or more additional monomers; and

C) 1-70 wt. % rubber-elastic block copolymer produced by anionic polymerization of monomers with the participation of a potassium compound that is soluble in non-polar solvents (step 1) and subsequent complete or near complete hydrogenation of olefinic double bonds of the polymers comprised in step 1) (step 2) and which is substantially formed of at least one hard phase forming block A having a mono-polymer unit of vinyl aromatic monomer, or a block B forming the first rubber-elastic (soft) phase and having a diene monomer or block A and block B and at least one soft phase forming elastomeric block B / A having statistically one polymer units of vinylaromatic monomers as well as diene, wherein the transition temperature Tg to glass block A is above 25 ° C and block B / A before hydrogenation is below 25 ° C and the volume ratio of block A to block B / A is chosen such that below The hard phase clay over the entire block copolymer is 1 to 40 volumes. % and the diene by weight is less than 50 wt. %.

The invention further relates to such plastics-making materials in which components C) are produced in a special way and to plastics-making materials in which the components have a special composition or chemical structure, the use of such plastics-making materials for the production of films and moldings as well as films and moldings of these materials for the manufacture of plastics, and the use of such films and moldings.

Component A) is present in the plastics material according to the invention, based on the sum of components A), B) and C), with a proportion of 30 to 98 wt. preferably 40 to 90 wt. % X and particularly preferably 50 to 82 wt. %. This component is a graft copolymer of particles which is composed of a rubber-elastic core ak) (soft component) and the envelope grafted as) (hard component) grafted thereon.

The component ak) is present in a proportion of 30 to 90 wt. %, preferably 40 to 80 wt. % and in particular 50 to 75 wt. relative to component A).

The grafted core ax) is obtained by polymerizing the monomer mixture, based on ax), consisting of a) (i) 80 to 99.99 wt. %, preferably 85 to 99.5 wt. % and particularly preferably 90 to 99 wt. % of one or more (C1-C10-alkyl) acrylic acid esters, k / 2, 0.01 to 20 wt. % X, preferably 0.5 to 10 wt. % and particularly preferably 1 to 5 wt. % crosslinked monomers; and

and (3) 0 to 20 wt. %, preferably 0 to 5 wt. % of one or more additional monomers.

Particularly suitable alkyl esters of acrylic acid (and alkyl acrylate) and / or i are those derived from ethanol, 2-ethylhexanol and especially n-butanol. The acrylic acid alkyl ester can be used alone, or else a mixture of multiple and alkyl acrylates with different alkyl radicals.

Crosslinked monomers ak / 2 are bi- or polyfunctional monomers, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid;

6 dialkyl ether and divinyl ether of bifunctional alcohols such as ethylene glycol and buta-1,4-diol, diester of acrylic acid and methacrylic acid with said bifunctional alcohols, 1,4-divinylbenzo 1 and tri and 1-cyanurate. Particularly preferred are the acrylic ester and tricyclododenes 1 and 1 of the following formula

= C'se states:

styrene, styrene derivatives

R ²

I (I);

known as dihydrodicyclopentadienylacrylan as well as the allyl ester of acrylic acid and methacrylic acid.

In addition, the component (a) of the plastics material may, at the expense of the monomers (a) and (a), contain other monomers (aK / 3) which vary to some extent the mechanical and thermal properties of the core. As an example of these monoethylene unsaturated comonomers and (K) 3 vinylaromatic monomers such as formula I

J 2 wherein R ¹ and R ² denote hydrogen or C 1 -C 6 -alkyl, methyl and tri-, and acrylic acid. methacrylic acid, dicarboxylic acids such as maleic acid and formic acid as well as their anhydrides such as maleic anhydride, nitrogen functional monomers such as dimethylaminoethyl acrylate, dimethylaminoethylacrylate, vinyl midazoline, vinyl pyrrole and don, vinycaproactam, vinyl amide carbazo1

C 1 -C 4 -alkyl methacrylic acid ester such as methyl methacrylan, ethyl methacrylan, n-propyl methacrylan, isobutyl methacrylate, secundary butyl methacrylate, tertiary butyl methacrylate as well as hydroxyethyl acrylate, aromatic acrylic phenylacrylic acid, phenylacrylic acrylate and phthalic acid acrylate , benzylmethacrylate, 2-phenylethyl acrylate, 2-phenylethylmethacrylan, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate, an unsaturated ether such as vinylmethyl ether and mixtures of these monomers.

The graft envelope _a ) is obtained by polymerizing a monomer mixture consisting of k)

and (i) 50 to 100 wt. preferably 60 to 95 wt. particularly preferably 65 to 85 hmo t n. % styrene compounds of the general formula (I)

R2 (AND)

wherein R ¹ and R ² are hydrogen or C 1 -C 6 -alkyl, or (C 1 -C 8 -alkyl) acrylic ester or methacrylic acid, or a mixture of styrene compound and (C 1 -C 3) (a) alkyl) acrylic ester or methacrylic acid; %, preferably 15 to 35 wt. % of one or more additional monomers.

As ρ-methylstyrene preferred.

The styrene compound of formula (I) (component a _s / i) is preferably used as well as styrene with styrene, α-methylstyrene with a C 1 -C 8 -alkylated core as or tertiary butylstyrene. Styrene is especially

Instead of styrene compounds or mixtures thereof, a C 1 -C 8 -alkyl ester of acrylic acid and / or methacrylic acid, especially those derived from methanol, ethanol, n- and iso -propanol, secondary and butanol and iso- butanol, pentanol, hexanol, tertiary heptanol, octanol and 2-ethylhexanol, and especially n-butanol. Particularly preferred is methylmethacrylic.

Further, the envelope _a ) can be formed at the expense of the monomers a / i) from other comonomers a / 2). The same recommendations apply to the as / 2) component as to the k and / 3) components.

Furthermore, for the maleimide, N-methyl-, also the monomers which other monomers refer to as N-cyclohexyl amino and as (2) as N-phenyl and are modified with acidic or basic functional groups, e.g. their anhydrides, optionally for (a) (3) said nitrogen functional monomers. Preferably, 1-methacrylonitrile maleimide is used for the component (a) and (c) ary (III), with acrylic tril being particularly preferred.

«· · · · ·

Preferably, the grafted envelope is _a ) styrene or methyl methacrylate or a mixture of wt. % methyl methacryian and an acrylonitrile residue of 65 to 85 wt. % of styrene and acrylonitrile residue formed from 40 to 90

1u or iu mixture.

the way they are

The graft polymers A can be obtained by known preferably emulsion polymerization at 30 to 80 ° C. Suitable as emulsifiers are, for example, the alkali metal salts of alkyl or alkylaryl sulfonic acids, alkyl sulfates, fatty acid sulfonates, salts of higher C 10 -C 30 fatty acids, sulfosuccinates, ether sulfonates or resin soaps. Preference is given to using alkali metal salts of alkyl sulfonates or fatty acids of 10 to 18 carbon atoms.

Water is preferably used to produce the dispersion if the dispersion produced has a solids content of 20 to 50 wt. %.

Suitable polymerization initiators are preferably free-radical formers, for example peroxides such as preferably peroxosulfate and azo compounds such as azodiisobutyronitrile. However, redox systems, in particular based on hydroperoxides, such as cumene hydroperoxide, may also be used. A molecular weight modifier, such as ethylhexyl thioglycol, dimerizing α-methylstyrene, may also be used.

and t-dodecyl mercaptan, terpinols

Buffer substances such as Na 2 HPO 4 / NaH 2 PO 4 or sodium bicarbonate may be used to obtain constant pH values, which preferably lie between 6 and 9.

Emulsifiers, initiators, regulators and buffer substances are used in conventional amounts, so no details are given.

The grafted cores may be particularly preferably produced

also by polymerizing monomers at (a) in the presence of a fine particle rubber latex.

In principle, it is also possible to produce the graft base layer according to a process other than emulsion polymerization, for example by powder or solution polymerization, and to subsequently emulsify the obtained polymers. Microsuspension polymerization using oil-soluble initiators such as lauroyl peroxide and t-butyl piperidine is also suitable. Methods for this are known.

The grafted envelope _a ) may be formed as a single layer, whereby the components as / i) and as / 2) are generally added simultaneously or added with a gradient. Multilayer can also be formed, to which component a® / i) is first polymerized and then component a1 / 2) or a mixture of components a1 / i) and as2). In this case, the ratio of the amounts of components as (1): as (2) can be constant or vary during the addition of the mixture, the gradient being continuous or stepped.

In addition, it is known to the person skilled in the art that the addition of graft monomers as (i) and as (2) can be carried out at once or by means of a feed process. The feed portion may be constant or variable. Combinations of these addition processes are also useful.

Preferably, the reaction conditions are matched to one another in a manner known per se, such that the polymer particles preferably have a uniform diameter d 50 in the range of 60 to 1500, in particular 150 to 1000 nm.

Instead of the unitary graft polymer A), various polymers can also be used to produce the thermoplastic material according to the invention, in particular with a distinctly different particle size. Such mixtures with a bimodal size distribution offer advantages in terms of further processing. Appropriate * · · »c ·

the particle diameters lie in the range 60 to 200 nm and in the range 300 to 1000 nm.

Dá 1 e they are also suitable grafted to 1ymery with more soft and hard packaging for example with structure ak) —as) —ak) —as) or as) —ak) —as) , primarily when greater c h of particles. If ex graft arise from monomers as) unrefined monomers, assigns to this quantity knows , which usually lies under 10 nm t n. % of component as), ma t e r i á 1

components A).

The component B) of the plastics material according to the invention is present in a proportion of 1 to 50, preferably 5 to 40 and particularly preferably 10 to 30 wt. based on the sum of components A), B) and C). Component B) is a thermoplastic polymer consisting of bi) 50 to 100 wt. preferably 55 to 95 wt. % and particularly preferably 60 to 85 wt. b2) 0 to 50 wt.% of styrene or α-methyl styrene or mixtures thereof; %, preferably 5 to 45 wt. % and particularly preferably 15 to 40 wt. % of acrylonitrile and also b3) 0 to 50 wt. %, in particular 0 to 40 wt. Jednoho, one or more additional monomers.

relative to component B). Possible monomers bz) are those mentioned for component ax (3) and (2).

Preferred monomers b3) are methacrylic acid alkyl and aryl esters as well as methacrylic acid amides. Preferred monomers b3) include methylmethacrylic acid,

- 12 maleic anhydride, maliminoamides, as well as appropriate amounts of glycidyl methacrylate, acrylic acid, methacrylic acid and dimethylaminoethyl acrylate;

For example, component B) of copolymers of 60 to 95 wt. % styrene and 5 to 40 wt. % a kr y 1 n i t r i 1 u. A copolymer of 60 to 85 wt. % styrene and 15 to 40 wt. % acrylic 1u.

The polymers Β), which are generally also referred to as SAN-polymers for their main components styrene and acrylonitrile, are known and in part commercially customary. They generally have a viscosity number VZ (determined according to DIN 53 726 at 25 ° C, 0.5 wt% in dimethyl form 1dehyde) of 40 to 160 ml / g, based on an average molar mass of 40000 to 2000000. slurry, precipitation and emulsion polymerization. Details of these procedures are described, for example, in the Kunststoffhandbuch, Hrg. R. Vieweg and 6. Daumiller, Volume V of Polystyrol, Car I-Hanser-Verlag Mtinchen 1969, pp. 118 et seq.

Polymer B) may also be a mixture of different copolymers of styrene, optionally α-methylstyrene and acrylonitrile, which differ, for example, in the acrylonitrile content or in the mean molar mass.

The proportion of component C) in the plastics material is 1 to 70% by weight, based on the sum of components A), B) and C). %, preferably 5 to 50 wt. % and particularly preferably 8 to 40 wt. %. Component C) is a rubber-elastic block copolymer that is produced by anionic polymerization of monomers with the participation of a potassium compound that is soluble in non-polar solvents (step 1) and

The subsequent complete or near complete hydrogenation of the olefinic double bonds of the polymers contained in step 1) (step 2) and which is essentially formed from at least one block A constituting it. a hard phase and having single polymer units of vinyl aromatic monomer; or

- a block B forming the first rubber-elastic (soft) phase and having a single polymer diene monomer, or

- block A and block Ba

- at least one soft phase B / A block having statistically unidirectional units of vinyl aromatic monomers as well as a diene, wherein the transition temperature Tg to block the A block is above 25 ° C and the B / A block before hydrogenation is below 25 ° C, and the volume ratio of block A to block B / A is selected such that the hard phase fraction of the cellular block copolymer is 1 to 40 volumes. % and the diene by weight is less than 50 wt. %.

More detailed information on the structure and manufacture of component C) is given below and in DE-OS 44 20 952, which is expressly referred to herein.

The soft phase (block B / A) is obtained by statistical copolymerization in inyl aromatic monomers and dienes.

For example, the hydrogenated block copolymer C can be represented by one of formulas 1 to 11:

(1) (AB / A) _n

-14 (2) (AB / A) n, preferably AB / AA (3) B / A- (AB / A) n, (4) X - ((AB / A) n) m + i, (5) X - ((B / AA) rt) m + i, preferably X - (- B / AA) 2, (6) X - ((AB / A) n - A) m + i, (7) X - ( (B / AA) nB / A) m + 1, (8) Y - ((AB / A) n) m + 1, (9) Y - ((B / AA) n) m + 1, preferably Y- (-B / A-A) 2, (10) Y - ((AB / A) n A) m + 1, (11) Y - ((B / AA) n-B / A) m + 1, where A means vjny1 aromatic block and B / A means soft »

X represents the residue of the n-functional initiator, Y the residue of the m-functional binder and m and n the natural numbers of 1 to 10, and wherein the diene units are convertible by hydrogenation to ethene-butene units.

Preferred is a block copolymer whose soft phase B / A is divided into blocks (12) (B / A) i- (B / A) 2, (13) (B / A) i- (B / A) 2- ( B / A) i, (14) (B / A) i- (B / A) 2- (B / A) ₃ , whose vinylaromate / diene ratio may vary between B / A blocks or within the range (B / A) i -> (B / A) 3 can be varied (in particular may increase), the Tg of the continuously glass transition of each sub-block before hydrogenation being below 25 ° C. Variant (14) is particularly preferred.

A particularly preferred hydrogenated formula has a block copolymer of C (2) (A-B / A) n-A.

• ·

- 15 Especially

C) of formula (19) A-B / A-A.

hydrogenated block polymers are preferred

Also, B / A blocks and / or a block polymer having multiple A with different molecular weights of the molecule is preferred.

Also, a block can be replaced in place of a block A formed exclusively of vinylaromatic units

B from polymerized diene monomers, since it is only a matter of producing a rubber-elastic block polymer. Such copolymers may have, for example, structures (15) to (18) (15) B- (B / A), (16) (B / A) -B- (B / A), (17) (B / A) iB - (B / A) 2, (18) B- (B / A) 2 - (B / A) 2,

Aromatic, preferred styrene as vinyl, as well as mixtures of these compounds isoprene. also piperylene, of these compounds.

the compound within the meaning of the invention is α-methyl styrene and vinyltoluene; and preferred dienes are butadiene and

1-phenylbutadiene as well as styrene mixtures.

apply

A particularly preferred monomer combination is butadiene and all subsequent weight and volume data are given for these combinations.

The B./A block is formed from 75 to 30 wt. % styrene and 25 to 70 wt. % butadiene. More preferably, the soft block has a butadiene content of between 35 and 70% and a styrene content of between 65 and 30%.

4 · 4 · 4 · 4 · 4 · · · · · · · · ·

The weight fraction of diene in the total block polymer is in the range of 15 to 50 wt.% In the case of the styrene / butadiene monomer combination. the proportion by weight of the aroma component is 85 to 50 wt. %. Particularly preferred are butadiene-styrene copolymer blocks with a monomer composition of 25 to 50 wt. % diene and 75 to 50 wt. % of aromatic compounds.

For the production of component C) the following is stated:

In a first step, block copolymers are prepared by anionic polymerization in a nonpolar solvent with the aid of potassium, which is soluble in a nonpolar. Solvent compounds are preferably used as solvent, especially cyclohexane or solvents such as cyclopentene, hydrocarbons such as methylcyclohexane. Another suitable decalin, methylcyclopentane or benzene.

Anionic polymerization is initiated by organic compounds, especially organic compounds such as methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl butyl lithium. Metallic organic in a chemically inert hydrocarbon by means of metal compounds lithium propyl and thi, butyllithium, tertiary compound is added as a solution in an amount usually

0.002 to 5 mol. % based on monomers.

compounds as a rule

The potassium compounds which are used for anionic polymerization in addition to the metallic organic compound, in particular organic lithium, in particular tertiary butyl lithium, are the potassium salt of the organic molecule. Potassium alcoholates are particularly suitable, with tertiary alcohol alcohols having at least 7 carbon atoms being particularly preferred.

Particularly preferred are the potassium salts of 3-ethyl-3-pentanol and 2,3-dimethyl-3-pentanediol, and also especially 3,7-dimethyl-3-octanol (tetrahydrolinalool).

also suitable for other metal alkyls, alkylated diarylamides

Further, potassium compounds are salts which behave inert with respect to, for example, potassium dialkylamides.

potassium, and alkylthiolates and alkylated potassium arylthiolates.

Suitable non-polar solvents for the potassium compounds are, for example, cyclohexene and η, methylcyclopentane, cyclohexane, methylcyclohexane, decalin or benzol.

Cyclohexane, preferred.

cyclopentane methylcyclohexane are

Usually, the preparation of potassium alcoholates is carried out by reacting the corresponding sodium-sodium alcohols in cyclohexane, which is reacted under stirring with an excess of inert solvent, preferably ambient temperature, for about 24 hours at the boiling point for several hours.

Alternatively, a small excess of the potassium tertiary solvent, potassium methylate or potassium butylate may be added to the alcohol in the presence of an inert high boiling point such as decalin or ethylbenzene, the low boiling alcohol, here methanol, ethanol or tertiary butanol, distilled off. cyclohexanone and filtered from the excess sparingly soluble alcoholate.

The statistical distribution of the vinylaromatic and diene units in the copolymer can be achieved, not according to the invention, also by using a polar co-solvent, in particular an ether such as tetrahydrofuran (THF). However, the addition of polar cosolvents can significantly increase the ratio of 1,2-bonds to 1,4-bonds. This leads to a changed property profile of the moldings that comprise component C), which may be disadvantageous for the intended use of the moldings.

• ·

The use ratio does not change or change only the specified mechanical component C) according to

However, when this polar cosolvent of the potassium compound is slightly displaced, it exerts a shift outside the properties of the moldings containing the invention.

According to 1, the sum of 1,2 and is usually from 8 to 9

The 1,2-diene bonds in component C), based on the 1,4-bonds, are generally increased by less than 2% and up to 15 with a Li / K ratio greater than 25 to 1 of 11 based on said sum.

In order to achieve a strictly statistical distribution of the monomer units, an alkyllithium compound must be used, as mentioned above, in addition to the potassium compound.

In butyl-lithium-initiated cyclohexanone polymerization, in this strictly statistical case, the molar ratio of lithium to potassium is between 10 to 1 to 40 to 1. If a gradient of composition along the styrene butadiene block is desired, the Li / K ratios are chosen to be greater than 40. at a desired styrene gradient of butadiene, the ratios are less than 10 to 1.

The time at which potassium salt is added to the reaction medium may vary. However, the following procedure is preferred. At least a portion of the polymerization solvent and monomer for the first block are charged into the reaction vessel. It is not advisable to add the potassium compound at this time, as traces of impurities would at least partially hydrolyze to KOH and alcohol. The potassium ions would then be irreversibly inactivated for polymerization.

Therefore, it is preferable to first add and mix the alkyllithium compound and then the potassium compound.

It is recommended to add the potassium compound only briefly «· • · · ·

- 19 4 «• · 4 before polymerization of the statistical block.

The polymerization temperature may be between 30 and 100 ° C.

and 130 ° C.

According to the invention, the volume fraction of the soft phase formed from the diene and vinylaromatic sequences in component C) is in the range of 60 to 99 vol%, preferably 70 to 90 to 90 vol%. The monomer blocks form a hard phase, by volume, and particularly preferably A, formed from vinylaromatic, whose volume fraction is 1 to 40% by volume, preferably 10 to 30% by volume, and particularly preferably 10 to 20% by volume.

It is noted that there is no strict agreement between the aforementioned ratios of the amount of vinylaromatic compound and diene, the aforementioned phase volume limit values and the composition resulting from the vitreous temperature ranges according to the invention. This could only happen by chance.

The volume fraction of both phases is measurable by contrast electron microscopy or NMR spectroscopy. The proportion of vinylaromatic blocks can be determined by the decomposition of osmium from the 1-diene portion by precipitation and balance. The future phase ratio of the polymers can be calculated from the amounts of polymers used, each time they are completely polymerized.

The quotient of the percentage by volume of the soft phase formed from the B / A blocks and the proportion of the diene units in the soft phase is between 25 and 70% by weight for the styrene / butadiene combination. %.

The soft phases (blocks B and B / A) of component C) typically have a glass transition temperature between -50 and +25 ° C, preferably -50 to + 5 ° C. The transition temperature for the vitreous glazing (block A) is preferably above + 50 ° C.

• ·

J · 4 4

- 20 44

4t ···· »» 4 »4 *

The molecular weight of block A is 1000 to 200 000 g / mol, preferably 3000 to 80 000 g / mol. Inside the molecule, A blocks may have different molecular weights.

The molecular weight of the B / A block is usually 2000 to 250 000 g / mol, preferably 5000 to 150 000 g / mol. Also, the block B / A can have, as a block A, different molecular weight values i.

The binding center X is optionally formed by the reaction of the anionic ends of the chain and at least a bifunctional binding agent. Examples of such compounds are in US-PS 3,985,830, 3,280,084, 3,637,554 and 4,091,053. For example, epoxidized glycerins such as linseed oil or soybean oil are preferred, and divinylbenzo1 is also suitable. Particularly suitable for dimerization are dichloromethane and alkyl sulfates, dialdehydes such as terephthaldehyde and an ester such as formic ethyl, ethyl acetate or ethyl benzoate.

The statistical block B / A itself can again be divided into blocks B1 / A 1-B2 / A2-B3 / A3- ... Preferably, the statistical block consists of 2 to 15 statistical sub-blocks, more preferably 3 to 10 sub-blocks.

and starting at block A. Part starts

The polymerization is carried out by a multistage monofunctional initiation, for example by producing hard monomers, it is charged into the reactor and the polymerization by addition of an initiator. To achieve a defined chain construction, it is recommended, but not urgently, to run the process before the second monomer addition to a high turnover (over 99%).

The subsequent second monomer addition depends on the selected block construction. In monofunctional initiation, for example, the aromatic compounds are either initially introduced or directly dosed into the inyl. Subsequently, a solution of the potassium compound in a non-polar solvent is preferably added, preferably cyclohexane.

• · · · · · · · · · · · · · · · · · · · ·

The statistical construction and composition of the B / A block is determined by the ratio of the amount of diene to the vinyl aromatic compound, the concentration and chemical structure of the potassium compound, as well as the temperature.

According to the invention, the proportion by weight of the diene relative to the total weight, including the vinyl aromatic compound, is 25 to 70. Subsequently, block A can be polymerized by the addition of vinylaromates. Instead, the necessary polymer blocks can also be coupled to one another by a coupling reaction. In the case of bifunctional initiation, the B / A block is first formed, followed by the A block.

The reaction is interrupted in a known manner by the addition of a polar compound such as water or an alcohol, preferably ethanol or even sopropanol.

Hydrogenation in the polymer of the still existing olefinic double bonds originating from the diene occurs in the second step when, as just described, a block copolymer was produced by anionic polymerization in the first step.

It is hydrogenated in a known manner, in a homogeneous phase with hydrogen, using a soluble, acting hydrogenation catalyst such as nickel acetylacetonate and aluminum triisobutyl solvent such as hexane. The hydrogenation temperature is 20 to 200 ° C, particularly preferably 100 to 170 ° C, and a hydrogen range of 6 to 30 bar, preferably bar, is recommended.

preferably selectively the mixture is inert preferably at a pressure of 10 to 20

Complete hydrogenation of the non-aromatic double bonds is not required, a hydrogenation degree of at least 80%, preferably at least 95%, is sufficient.

Hydrogenation is exemplified by the following exemplary embodiment.

• · ·

The hydrogenation catalyst is usually produced separately as a solution as follows: To a 1N solution of nickel acetylacetonate in toluene is added 20 room solution of aluminum triisobutyl in hexane at room temperature, the weight ratio of nickel acetylacetonate to aluminum triisobutyl being in the range 1: 4. After the slightly exothermic reaction subsided, the fresh catalyst solution was added to the polymer solution and the reactor was sprayed with hydrogen. 1.5 g of nickel acetylacetonate is generally sufficient per kg of polymer, but under 0.15 g under particularly inert conditions it is generally sufficient. The hydrogenation rate depends, in addition to the catalyst concentration, on hydrogen pressure and reaction temperature. Preferably, the required hydrogenation step of at least 95 ° C is achieved at a hydrogen partial pressure of 15 bar and temperatures between 180 and 200 ° C, usually already after 30 to 120 minutes.

However, at hydrogenation temperatures above 170 ° C, unexpected partial hydrogenation of the phenyl groups may occur, therefore it is particularly preferred not to hydrogenate above 170 ° C.

to 16

At temperatures around 120 hours.

° C hydrogenation usually takes place in terms of space and time is hydrogen. Therefore, preferably by vertical mixing. Very much h a h.

For optimum yield from the advantageous good gas mixing it uses an efficient mixer with good so-called gasification

After completion of the hydrogenation, the colloidal nickel, which stains the polymer solution in black, can be oxidized upon decolourisation, for example with a mixture of hydrogen peroxide, acetic acid.

The hydrogenation can of course also be carried out by other homogeneous and heterogeneous hydrogenation catalysts. Particular mention is made here of hydrogenation on a solid catalyst bed. By carrying out the hydrogenation, the polymer contamination is prevented. 9 9

C) residues of the catalyst, making the plastics materials particularly resistant to atmospheric agents. The component C) thus produced is therefore completely colorless, which may be advantageous in accordance with the field of application for films made from moldings.

The treatment to the desired hydrogenated polymers C), the molar mass of which is preferably set to 50,000 to 300,000, in particular 70000 to 180000, is carried out as usual. As a rule, the solvent is first removed and the polymer is extruded and granulated.

The hydrogenated soft phase (block B / A) then consists essentially of copolymers of ethene, butene and styrene, wherein the ratio of ethene and butene is determined by using a 1,4- to 1,2- bond ratio. those formed with potassium salts, have a crystallizing fraction on the basis of the polyethylene sequences. They are stiffer than polymers with the same block structure, which were made using a polar co-solvent such as THF and therefore have a high butene ethene ratio.

In addition to components A), B) and C), the thermoplastic plastics materials may contain additional materials such as lubricants and release agents, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdered fillers, and reinforcing agents and anitistatics. in amounts customary for such compositions. Especially when foils are produced from the plastics materials according to the invention, plasticizers are used, for example copolymers having an average molecular weight of 2000 to 8000 from 30 to 70% by weight. % of ethylene oxide and 70 to 30 wt. X 1,2-propylene oxide in amounts of 0.5 to 10 wt. % based on the sum of components A), B) and C).

The production of the plastics materials according to the invention can be carried out by a known mixing process, for example, by melting in a mold.

However, it is also possible to mix the blend or the blend consisting of homogenization only with an extruder, a Branbury mill or a calender. Without cold melting of the granules, processing can be carried out.

components and powder melt and

Moldings can be made from materials of all types, in particular foils, by rolling, calendering, and plastic production. Foil production can be accomplished by extrusion, and other methods known to those skilled in the art. The plastics materials according to the invention are then pressed onto the processable film by heating and / or friction alone or using softening or other additives. The processing of such films into finished products takes place, for example, by hot pressing or deep drawing.

Foils have many applications, especially in the automotive industry to equip the interior of cars for decorative purposes, such as the furniture surface of furniture.

leather substitute in the manufacturing industry as coating cases and bags and in the laminating material

The thermoplastic is free of halogens, and of the migrating components, and no disadvantageous changes are made in the materials of the present invention. They also have good mechanical properties. In particular, the films made from the plastics materials according to the invention have good deep-drawing properties (high tensile to cracking and high tear resistance) as well as a skin-like surface (soft-touch).

Examples ....... embodiments ......... yynáj .e z u

The following components were produced or used, respectively. All data are in wt. %

- 25

Component A): 1y-n-butyl acrylate graft polymer of a nitrile particle (core) and a cross-linked styrene copolymer and coated with a mixture of 3 g of 1-butyl acrylate, potassium persulfate were added over 4 hours a mixture of 98 g of n-butyl acrylate and 2 g of dienylacrylate, as well as from this mixture of Na-C12-C18-paraffinate in 50 g of water, was continued for 3 hours. = 0.1).

nm at narrow

100 g water and 0.2 gn at 60 ^° C dihydrodicyclopenta separately solution 1 g Polymerization then diameter d 50 of particle size distribution

150 g of this latex was mixed with 60 g of water, 0.03 g of potassium persulfate and 0.05 g of 1auroyl peroxide, whereupon the latex particles were grafted for 3 hours at 65 ° C first with 15 g of styrene and then for a further 4 hours with the mixture. 15 g of styrene and 5 g of acrylonitrile. Subsequently, the polymer was precipitated at 95 ° C with a calcium chloride solution, separated, washed with water and dried in a stream of warm air. The grafting rate of the polymer was 35% and the particles had an average diameter d 50 of 510 nm.

The grafted polymer had the following composition (values are rounded):

wt. 1-butylacrylate-grafted core, consisting of an (w / w% wt% styrene polymer inner graft envelope and 20 wt% styrene / acrylonitrile outer graft envelope in a S / AN ratio of 3: 1).

The initially used polymer was produced according to the method of EP-B 6503 (column 12, line 55 to column 13, line 22) by polymerizing n-butyl acrylate and tricyclo-ocetylene acrylate in aqueous. The emulsion had a solids content of 40%.

The mean particle size reported in component A) is a weighted average particle size.

The mean diameter d 50 corresponds to a value of 50 wt.

For all particles having a smaller diameter and a larger diameter than the mean particle size distribution, the diameter d 50 is given the value of the diameter d 90. in this case, the wt. % of all particles have a d 50 diameter. For characterization often in addition to the mean diameter d 10 and also a value of 10 wt. % of all particles is smaller and 90 wt. Similarly, it has 90 wt. % of all particles smaller and 10 wt. diameter dgo. The quotient Q = (d 90 -di 0) / d 50% larger diameter than the measure for particle size distribution. The smaller the Q, the narrower the distribution.

Component B):

A copolymer of styrene and acrylonitrile was made an acrylonitrile copolymer such as Hrg. R. Ví eweg and G.

Continuous polymerization of the 65 wt. % styrene and 35 wt. % described in the Kunststoff Handuch,

Danmiller, Volume V Polystyrene, Car 1-Hanser-Ver 1 ag Miinchen 1969, pp. 122-124. Viscosity number VZ (determined according to DIN 53 726 at 25 ° C, 0.5 wt.%) in dimethyl form 1dehyde) was 80 mt / g.

Component C) (according to the invention) Rubber-elastic block copolymer

Simultaneously made of stainless steel by flushing with butyllithium nitrogen and heated and with cross and boiling m

1,1-diphenylethylene in cyclohexane and drying.

cooled with a solution was a solution (a secondary ratio of 1: 1 was prepared by the autoclave).

Charge 22.8 L of cyclohexane, then add 87.3 mmol of secondary butyllithium, then add the monomers needed for the first step, followed by 10 wt. % solution of 4.37 mmol of tetrahydrofuran on potassium oxalate in cyclohexane. The molar ratio of Li: K was 20: 1. Table 1 summarizes the different degrees of polymerization.

At each stage, the monomer feed interval was shorter relative to the polymerization interval. The indicated start and end temperatures were adjusted by heating or cooling the reactor jacket.

Table 1

Degree 1 2 3 4 5 Butadiene feed (g) - 1 172 1 172 1 1 72 - Styrene supply (g) 1048 1477 1477 1477 1048 Tpocatscni (° C) 40 52 55 54 70 Tk oncova (®C) 70 75 76 75 72 Polymerization interval (min.) 30 13 13 1 7 40

After completion of the reaction (monomer consumption), the polymerization was interrupted by titrating the mixture to colorless with ethanol and acidifying with a 1.5-fold excess of formic acid. Subsequently, 34 g of 2- (1,1-dimethyl-ethyl) -6- ((3- (1,1-dimethylethyl) -2-hydroxy-5-methylphenyl) methyl-4-methylphenyl acrylate ester (Irganox 3052 from the company) was added. Ciba-6igyl) and 82 g of trisnonylphenyl phosphite.

The ratio of 1,2-diene bonds is 10.4%, based on the sum of 1,2- and 1,4-bonds, as determined by FTIR spectroscopy.

<»· ·

To produce the hydrogenation catalyst was to 250 ml

1.136 wt. % toluene at room temperature of the triisobutyl solution of nickel acetylacetate solution at a temperature of 50 ml of 20 wt. % of aluminum in hexane (the ratio by weight of nickel acetylacetonate: triisobutyl aluminum was 1: 4). After the slightly exothermic reaction subsided, the pure catalyst solution was added to 13.3 kg of 15 wt. The hydrogenation step was determined by Wijs titration of the test at a hydrogen ratio of 15 bar hydrogenated to 38 to the non-hydrogenated test and temperature.

After completion of the hydrogenation at 70 ° C the mixture of 12 was added to the black solution at ml of hydrogen peroxide, 2.5 ml of formic acid and the reactor colorless.

ml of water, which quickly became the content

Working up of the reaction mixture to a hydrogenated polymer was carried out as usual, the solvent being preferably separated at 200 ° C in a degassing extruder to obtain a granulate.

The obtained polymer C) had a structure

AB / AA, wherein the soft phase B / A is divided into three blocks according to the following expression (B / A) i - (B / A) ₂ - (B / A) 3. A and B / A here are characterized by the polymer blocks already defined. Block A is a block of homogeneous polystyrene, block B / A is a block of statistically polymerized units of styrene and hydrogenated butadiene. The proportion of butylene units in the soft phase B / A was 20 wt. %, the proportion of styrene units was 80 wt. Ϊ.

• ·

The proportion of styrene in the total polymer C) was 65 wt. %.

The proportion of both solid phases A in polymer C) was 10.4 wt. % soft phase B / A ratio was 79.2 wt. %.

The average molecular weight (g / mol of polymer C) obtained was as follows: number average Mn 131 000, viscosity average (peakmaximum) Mp 1 50 000, weight average Mw 166 000 (all molecular weights were determined by gel permeation chromatography, calibrated with respect to polystyrene).

The transition temperatures Tg to vitreous were -45 to 0 ° C for the soft phases (B / A blocks) and 50 to 90 ^° C for the hard phases (blocks A), and after hydrogenation -17 to 7 ° C for the soft phases, for the hard phases remained unchanged.

To determine the mechanical properties of component C), 2 cm thick plates (3 min at 200 ° C) were pressed from the granulate and subjected to routine tests.

Tests and their results are summarized in Table 2.

Table 2

component C exam DIN before hydrogenation after hydrogenation i elongation (N / mm ² ) 43504 1.5 5.0 stress at breaking strength (N / mm ² ) 43504 2 1,4 31.0 elongation (%) 43504 80 1 352 stress (N / mm ² ) at elongation of 200%, 400% and 600% L 43504 2.9 / 6.4 / 11.4 17.5 / - / -

The strength due to hydrogenation increased, as can be seen from the higher values of elongation and yield strength.

Component C ^x ) for comparison hydrogenated styrene-butadiene copolymer

To a solution of 529 g of styrene tetrahydrofuran in 4 L was slowly added secondary active impurities. After

480 g of butadiene and 20 ml of cyclohexane were initially added at 0 ° C butyllithium to deactivate the protonation of the polymerization reaction, as seen by an increase in temperature of 0.2 ° C, and 0.8 g of secondary butyllithium was quickly added. The polymerization heat was removed by distillation cooling. The cooling capacity was set so that the temperature rose to 120 ° C within 30 min. This temperature was maintained for 10 min and the polymerization was interrupted by the addition of 1 g of ethanol.

polymer solution of nickel in 30 ml

For hydrogenation, a suspension of 1.5 g of toluene acetyl acetate and 34 ml of 20 wt. % solution of aluminum triisobutyl in hexane was then subjected to a hydrogen pressure of 15 bar at 60-110 ° C for 60 min.

Working up of the reaction mixture to a hydrogenated polymer was carried out as usual, the solvent being preferably removed in a direct degassing apparatus.

The polymer obtained consisted of a block that starts with butadiene, without styrene, and ends with styrene, but without butadiene, so that a gradient is available, and a block of homogeneous polystyrene that was attached at the styrenic end of the first block.

The styrene content of the polymer obtained, which is commercially referred to as G 1 isov isca 1 ^R SG (from BASF), was 52 wt.

-31% based on the total weight of the polymer. Podí! The homogeneous polystyrene end block in the polymer was 13 wt. The average molar mass of the product produced by the method described was 80000, as determined by gel permeation chromatography.

Material according to the invention and its properties

Compositions A), B) and C) or C ^x ) were used to produce mixtures which were processed at 200 ° C on a 1 mm thick film mill.

The following foil properties were found:

- Tensile strength: The tensile test was carried out according to DIN 53 504 on an S2 tensile rod which is made of foil.

- Ductility to cracking: Ductility was determined in the tensile test according to DIN 53 504 when applying force to cracking and is given as a percentage of the dimension of the original S2 tensile bar.

- Tear resistance Graves DIN DIN (V-shaped).

- Shore Hardness: The Shore hardness was with the D and A test equipment.

It was carried out by test 43 515 on notched strips according to DIN 43 505

- Thermal shape stability: Measured according to Vicat's number by measurement procedure A.

DIN 53- 460 as

A summary of the films produced and the test results is given in Table 3.

• 4 · · · · · · · · · · · · · · · · · ·

- 32 Table 3

exam no. 1 VX) 2 3 wt. % AND 80 80 70 (B) 10 1 0 1 5 C - 10 1 5 C* 10 - - Properties tensile strength (N / mm ² ) 1 4 1 7 20 May elongation (%) 1 40 170 176 Shore A hardness 93 87 88 Shore D hardness 47 44 47 resistance to further tearing (N / mm ² ) 46 5 1 52 thermal shape stability Vicat A 50 ° C 89 86 90

^χ / to compare

Films of plastics material containing a hydrogenated polymer ( ^x ) instead of polymers C) (block containing butadiene with a styrene gradient and homogeneous polystyrene block attached thereto) have a considerably lower ductility as well as a significantly lower tear resistance (test) 1 V ^x )). In addition, these films are harder.

In addition, films containing polymer C) according to the invention (polystyrene block-3 statistical polymer blocks of styrene and hydrogen butadiene-polystyrene block) combine good tensile strength, high ductility, good tear resistance, low hardness and high heat shape stability.

pV 314-17

Claims (16)

PATENTOVÉ Claims Thermoplastic materials for the manufacture of plastics from A) 30 to 98 wt. % of the graft polymer of ax) 30 to 90 wt. % rubber-elastic graft core comprising a copolymerization and (i) 80 to 99.99 wt. % of at least one (C1-C1- and 1-alkyl) acrylic ester, if / 2) 0.01 to 20 wt. % crosslinked monomers and ak / 3) 0 to 40 wt. % of at least one additional monomer, and) 10 to 70 wt. % of the grafted envelope of as / i) 50 to 100 wt. % styrene compound of formula R ² _R X> C-CH ₂ wherein R ¹ and R ² represents hydrogen or Ci-Cs-alkyl and 1 1, or (Ci-Ce-a 1kyl) ester of acrylic or methacrylic acid and a mixture of styrenic compounds or alkyl methacrylic acid ester and (C 1 -C ₈ acrylic acid) B) and (2) 0 to 50 wt. % of at least one additional monomer, 1 to 50 wt. % of a thermoplastic polymer of% styrene or α-methylstyrene (bi) 50 and ž 100 wt or je j i ch mixture i b? ) 0 to 50 h t t% b3) 0 to 50 wt. % • First rubber elastic 1 to 70 wt. % of a rubber-elastic block copolymer produced by anionic polymerization of monomers with the participation of a potassium compound that is soluble in non-polar solvents (step 1) and subsequent complete or almost complete hydrogenation of the olefinic double bonds of the polymers contained in step 1) (step 2) and is substantially formed of at least one hard phase forming block A having single polymer units of vinylaromatic monomer, or block B forming a (soft) phase and having a diene monomer, or block A and block B and at least one elastomeric block B / A forming a soft phase (optionally two or more) and having statistically one polymer units of vinylaromatic monomers as well as diene, wherein the transition temperature Tg for the glazing of block A is above 25 ° C and of block B / A before hydrogenation is below 25 ° C and the volume ratio block A to block B / A is such that the hard phase fraction of the whole block % of the copolymer is 1 to 40 volumes. % and the mass fraction of tm n. %. diene is less than 50 The thermoplastic plastics material of claim 1, wherein the potassium compound for the production of component C) is a potassium salt of a tertiary alcohol with at least seven carbon atoms. The plastics thermoplastic materials of claim 2, wherein the tertiary alcohol is 3-ethyl-3-pentan-1-ol, 2,3-dimethyl-3-pentan-1-ol or 3,7-dimethyl-3-octanol. 9 «* w w 9 w * w w w w w w w w w w w w w w w w w w w ·· · * 9 9 · «·· - 35 Thermoplastic plastics materials according to claims 1 to 3, which contain, in addition to the potassium compound, an alkyllithium compound for the production of component C) in step 1). Thermoplastic plastics materials according to claims 1 to 4, in which component C) has a proportion of 8 to 15% of 1,2-diene bonds, based on the sum of 1,2- and 1,4-diene bonds. Thermoplastic plastics materials according to claims 1 to 5, characterized in that for the anionic polymerization of soft phases (blocks B and B / A) contain a potassium compound. Thermoplastic plastics materials according to claims 1 to 6, wherein an alkyllithium compound and then a potassium compound are introduced to produce component C) in step 1) during anionic polymerization. Thermoplastic plastics materials according to claims 1 to 7, wherein in the block copolymer C) the transition temperature Tg for the vitrification of the hard phase (block A) is above 50 ° C and the temperature Tg for the vitrification of the soft phases (blocks B and B / A). ) lies below 5 ° C before hydrogenation. Thermoplastic plastics materials according to claims 1 to 8, wherein in the block copolymer (C), the vinylaromatic monomer is styrene, thermoplastic, vinyltoluene or mixtures thereof and the diene is butadiene and isoprene or their mixtures. Thermoplastic plastics materials according to claims 1 to 9, wherein in the block copolymer (C), the soft phase (block B / A), optionally second and further, consists of a diene-based vinyl aromatic copolymer. Thermoplastic materials for the production of plastics according to claim 1 36 to 10, wherein the hydrogenated block copolymer C) is formed according to formula (AB / A) n-A wherein A denotes a vinylautomatic block, B / A statistical block formed from diene and vinylaromatic units and n denotes natural number 1 to 10. Thermoplastic plastics materials according to claims 1 to 11, wherein the soft phase (block B / A) of the hydrogenated block copolymer C) is divided into blocks (1) (B / A) i- (B / A) of (2). ) (B / A) i - (B / A) ₂ - (B / A) i (3) (B / A) i - (B / A) z - (B / A) 3, whose vinylaromate / diene ratio it is different in the individual B / A blocks or varies continuously within the interface at the interface (B / A) i -> (B / A) 3, the glass temperature Tg for each sub-block being below 25 ° C. Thermoplastic plastics materials according to claims 1 to 12, wherein the hydrogenated block copolymer C) is formed according to the formula A-B / A-A, wherein A denotes vinyl aromatic block and B / A statistical block formed from diene and vinylaromatic units. Thermoplastic plastics materials according to claims 1 to 13, wherein component B) is a copolymer of 60 to 95 wt. % styrene and 5 to 40 wt. % acrylic 1u. Use of thermoplastic materials for the production of plastics according to claims 1 to 14 for the production of films and moldings. Foils and moldings of thermoplastic materials for the production of plastics according to claims 1 to 14.