KR101546401B1 - Thermoplastic molding composition from abs-polymers and sbs-polymers - Google Patents

Abstract

1.1.1 70-76% vinyl aromatic monomer A1; 1.1.2 24-30% vinyl cyanide monomer component A2; 1.1.3 Copolymer matrix consisting of 0-50% of at least one unsaturated copolymerizable monomer A3 75-99%; 1.2.1 10-95% grafted rubber core B1; 1.2.2 graft rubber B 0-60% consisting of 5-90% graft shell B2; 1.3.1 30-70% of vinyl aromatic monomer C1; 1.3.2 Thermoplastic SBS block copolymer C consisting of 30-70% unsaturated copolymerizable monomer C2. C discloses a thermoplastic molding composition containing 1-10%, odorless at low temperatures and having certain mechanical properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to thermoplastic molding compositions from ABS-polymers and SBS-

The present invention relates to a thermoplastic molding composition comprising an acrylonitrile-butadiene-styrene polymer (ABS) and a styrene-butadiene-styrene polymer (SBS), and a method of making such a molding composition. The present invention also relates to the use of SBS-block copolymers for the production of such molding materials. The invention also relates to the use of molding materials for the production of molded articles, films or fibers. The invention also relates to a molded article, a film or a fiber itself, and in particular a refrigerator part obtainable using the molding material.

Molding compositions containing butadiene- or acrylate-based graft copolymers and styrene / butadiene block copolymers have been known for many years (e.g. WO 2000/36010). Such a molding material is suitable for the production of a soft film used in a vehicle interior. Such a film is excellent in the ratio of flowability to thermoforming property, which is easily thermoformable. The formation of good thermal properties of a thermoplastic material means that the film exhibits a substantially uniform flow at all points when a pressure is applied to a point of the film at some elevated temperature. One of the consequences of good thermoforming is that the polymer film is not thinned at certain points, and is not punctured or ruptured.

WO 2000/58380 and WO 2003/11964 disclose styrene block copolymers as blends with styrene polymers, such as general purpose polystyrenes or high strength polystyrenes (HIPS), which are particularly suitable for molding materials which can be processed into molded articles resistant to impact and stress cracking Can be formed. Such a molded article is suitable for producing, for example, a refrigerator.

DE 44 20 952 describes blends of styrene-acrylonitrile-matrices (SAN) with SBS copolymers mixed in an extruder to obtain highly tough blends. EP-A 0 767 213 describes thermoplastic compositions based on SAN and ASA (acrylonitrile-styrene-acrylonitrile). EP-A 0 800 554 also describes a composition containing a transparent, elastic copolymer based on styrene and butadiene (e.g. Styroflex from BASF, Rudburg-Schaffen, Germany).

WO 2005/005536 discloses that SBS block copolymers enhance the properties of ABS materials for use, for example, as an inliner inside a refrigerator. In particular, mechanical stability, toughness and environmental stress cracking resistance (ESCR) are improved.

However, several blends of ABS and SBS block copolymers are less suitable due to so-called organo-leptic properties. The SBS polymer has the function of enhancing the diffusion of residues and other low volatile organic compounds through the lamellar-type structure from the inside to the outside of the molded or extruded article.

Especially in a high quality refrigerator inner liner material, it is important to have high resistance to stress cracking and excellent impact resistance. It should also be passable, and have a good odor and a pleasant smell.

The composition according to the invention exhibits this excellent property profile. It is a further object of the present invention to provide a molding material based on readily available ABS-graft copolymers and SBS block copolymers, having impact resistance and stress-cracking properties and also resistant to chemical blowing agents . In particular, the molding material should have a thermoforming of less than +/- 150% when measured based on the wall thickness variation of the standard cup at < RTI ID = 0.0 > 120 C. < / RTI >

The molding material according to the present invention should further have excellent melt stability. The melt stability in the context of the present invention is interpreted to mean the stress that the melt between the nozzle and the cooling roll after being discharged from the nozzle by the compressed air can withstand. Melt with high stability exhibits little sagging. Particularly, it is an object of the present invention to enable the molding material to be processed into a film, particularly a large area film, by blow molding without melting sagging during film production.

This object of the invention is achieved by a molding material as defined below.

According to the present invention, the technical problem is solved by a thermoplastic molding composition comprising the following components.

1.1

1.1.1 70-76% of vinyl aromatic monomers A1, for example styrene,

1.1.2 24-30% vinyl cyanide monomer component A2, for example acrylonitrile, and

1.1.3 0-50% of one or more unsaturated copolymerizable monomers A3, for example alpha-methyl-styrene or methyl-methacrylate

75-99% copolymer A consisting of;

1.2

1.2.1

1.2.1.1 80-100% of a rubber type monomer, e.g. rubber type monomer B11 from the group of preferably butadiene, isoprene, butyl acrylate, silicon, and

1.2.1.2 0 to 20% of a polyunsaturated monomer B12 from a group of double unsaturated monomers such as, or preferably divinylbenzene, allyl (meth) acrylate, polyfunctional silicon

Gt; B1 < / RTI >

1.2.2

1.2.2.1 75-85% of a vinyl aromatic monomer B21, for example styrene,

1.2.2.2 15-25% vinyl cyanide monomer component B22, for example acrylonitrile, and

1.2.2.3 0-50% of one or more unsaturated copolymerizable monomers B23

Of graft shell B2 containing 5-90%

0-60% graft rubber B consisting of; And

1.3

1.3.1 30-70% of a vinyl aromatic monomer C1, for example styrene, and

1.3.2 30-70% of one or more unsaturated copolymerizable monomers C2, for example butadiene or isoprene

1-10% thermoplastic SBS block copolymer having at least two glass transition temperatures of from 70 to 100 캜 and from -60 to 0 캜.

In a preferred embodiment of the present invention, the thermoplastic molding composition comprises

1.3

1.3.1 30-70% of a vinyl aromatic monomer C1, for example styrene, and

1.3.2 15-70% of one or more unsaturated copolymerizable monomers C2, for example butadiene or isoprene

Of a thermoplastic SBS block copolymer C 1-10% having at least two glass transition temperatures of 70 to 100 캜 and -60 to 0 캜.

A further aspect of the invention relates to a thermoplastic molding composition wherein the components A1, B21 and C1 are styrene, the components A2 and B22 are acrylonitrile, and the components B11 and C2 are butadiene and / or isoprene.

In the thermoplastic molding composition according to the present invention, the copolymer A is, for example,

70-76% of vinyl aromatic monomers A1,

24-30% vinyl cyanide monomer component A2, and

0-20% of at least one unsaturated copolymerizable monomer A3.

Preferably, the copolymer A is

70-76% styrene,

24-30% of acrylonitrile, and

0-10% alpha-methyl-styrene and / or methyl-methacrylate.

In certain embodiments of the present invention, the thermoplastic molding composition comprises

80-100% rubber type monomer B11 from the group of butadiene, isoprene, butyl acrylate and silicon, and

0-20% of a polyunsaturated monomer B12 from the group of divinylbenzene, allyl (meth) acrylate and polyfunctional silicon

Gt; B1 < / RTI > And

75-85% of vinyl aromatic monomers B21 from the group of styrene and alpha-methyl-styrene,

15-25% of acrylonitrile B22, and

0-20% unsaturated copolymerizable monomer B23

Of graft shell B2 containing 5-90%

(Preferably in an amount of 1 to 30% by weight).

The graft rubber B is preferably

80-100% of butadiene, isoprene and / or butyl acrylate, and

0-20% of divinylbenzene and / or allyl (meth) acrylate

Gt; B1 < / RTI > And

75-85% styrene and / or alpha-methyl-styrene,

15-25% acrylonitrile, and

0-20% of unsaturated copolymerizable monomers from the group of butyl acrylate, ethyl acrylate and methyl (meth) acrylamide

And a graft shell B2 containing 5-90% of the graft shell B2.

The thermoplastic molding compositions according to the invention preferably contain from 1 to 5% by weight of at least one thermoplastic SBS block copolymer C,

Here, the SBS block polymer C has at least two glass transition temperatures of 70 to 100 캜 and -60 to 0 캜.

A further aspect is a molding composition comprising from 90 to 99% by weight of copolymer A, and preferably from 1 to 10% by weight of a thermoplastic SBS block copolymer made from styrene and butadiene.

A further aspect of the present invention relates to a process for preparing the thermoplastic molding composition, wherein the copolymer A and the thermoplastic SBS block copolymer C, and finally the graft rubber B and other components and additives are mixed.

The invention also relates to the use of thermoplastic molding compositions for the production of fibers, folio and molded articles, in particular for the manufacture of internal liners for refrigerators.

The present invention also relates to molded articles, fibers and polyols comprising the thermoplastic molding composition.

The copolymer matrix A is prepared from the components acrylonitrile and styrene and / or a-methylstyrene, for example, via bulk polymerization or in the presence of one or more solvents. In the present application, and preferably have a molar mass M _w is from 50,000 to 300,000 g / mol in the copolymer A, wherein the molar mass can be determined by the example light scattering in tetrahydrofuran Yes (GPC with UV detection).

The copolymer matrix A is particularly

(Aa) polystyrene-acrylonitrile made from styrene and acrylonitrile, or

(Ab)? -Methylstyrene and poly-? -Methylstyrene-acrylonitrile prepared from acrylonitrile, or

(Ac) copolymer matrix (Aa) and a copolymer matrix (Ab).

The copolymer matrix A can also be obtained through copolymerization of acrylonitrile, styrene and? -Methylstyrene.

The viscosity (Vz) of the copolymer matrix A is, for example, 50 to 120 ml / g (measured at 25 캜 in a solution of 0.5% by weight concentration DMF according to DIN 53726). Copolymer matrix A can be prepared, for example, by the method of Kunststoff-Handbuch [Plastics Handbook], Vieweg-Daumiller, volume V, (Polystyrol) [Polystyrene], Carl-Hanser-Verlag, Munich 1969, pages 122 et seq., Lines 12 et seq.], either by solution polymerization in toluene or ethylbenzene, or by bulk polymerization.

The graft copolymer component B may be used, but it is not necessarily used as a component in the composition. It can have a complex structure and consists essentially of 10 to 95% by weight of graft base (B1) and 5 to 90% by weight of graft shell (B2) based on B, Lt; / RTI >

The graft base B1 can be obtained, for example, through the reaction of 0 to 20% by weight of divinylbenzene and 80 to 100% by weight of butadiene, isoprene or butyl acrylate and also 0 to 5% by weight of auxiliary components Here, the weight% data is based on the graft base B1.

The graft shell B2 is obtained from the reaction of 75 to 85% by weight of styrene and 15 to 25% by weight of acrylonitrile and also 0 to 5% by weight of auxiliary components, for example in the presence of graft base B1 (% By weight is based on graft shell B2).

The molding composition may also comprise two or more different graft polymers.

For the preparation of the graft polymer B, it is preferred to use a redox initiator system comprising a polymerization initiator, for example, an organic peroxide and at least one reducing agent.

The organic peroxides used include preferably compounds selected from the group of di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and p-menthol hydroperoxide, and mixtures thereof. The reducing agent used generally includes one or more water-soluble compounds having a reducing action (e.g., sugar).

It is preferable to carry out emulsion polymerization for the production of the graft polymer B.

For producing the graft base (B1), it is preferable to carry out emulsion polymerization, for example, it is preferable to use potassium peroxodisulfate as an initiator.

As described above, the copolymer A is preferably composed of monomeric styrene and acrylonitrile, or monomeric? -Methylstyrene and acrylonitrile, or monomeric styrene,? -Methylstyrene and acrylonitrile. However, in principle it is also possible to use polymer matrices comprising additional unsaturated monomer units.

In a further embodiment of the invention, an additional copolymerizable multifunctional coagulation component is used for the preparation of the graft base (B1). In order to change the particle size distribution of the graft base it is possible to use C ₁ -C ₁₂ -alkyl acrylates or C ₁ -C ₁₂ -methacrylic acrylates and acrylamide, methyl acrylamide, ethyl acrylamide, n-butyl acrylamide or One or more copolymers comprising a polar comonomer from the group of maleimide may be used.

Examples of suitable preparation methods for graft copolymer B are emulsion polymerization, solution polymerization, suspension polymerization or bulk polymerization. WO-A 2002/10222, DE-A 28 26 925 and EP-A 022 200.

For example, the graft base (B1) can be prepared by using some of the aqueous reaction medium as the initial packing material and, after the initiation of the free-radical polymerization reaction, adding the remaining remaining amount of monomers in the aqueous reaction medium, Free-radical-initiated aqueous emulsion polymerization. It is also possible to use at least a portion of the free-radical polymerization initiator and, where appropriate, further auxiliaries, as the initial charge, in the aqueous reaction medium, to bring the resulting aqueous reaction medium to the polymerization temperature and to add the monomer to the aqueous reaction medium at this temperature Do. This introduction may also take the form of mixtures, for example in the form of aqueous monomer emulsions.

The reaction is initiated via a water-soluble or lipophilic free-radical polymerization initiator such as an inorganic or organic peroxide (for example, peroxodisulfate or benzoyl peroxide), or with the aid of a redox initiator system. It is preferable to use peroxodisulfate as an initiator in the production of the graft base (B1). The amount of the free-radical initiator to be used is generally 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the monomers.

The thermoplastic molding composition according to the present invention always contains a small amount of at least one SBS-block copolymer (C) as a component. As a minor amount, for example, 1 to 10% by weight, preferably 1 to 5% by weight, for example 3% by weight, can be used.

A linear or star block copolymer can be used as component (C). However, as component (C), two or more different block copolymers may also be suitable. The block copolymers which can be used as component (C) according to the present invention preferably comprise at least two hard blocks S1 and S2 of a vinyl aromatic monomer, and at least one random soft block which is present therebetween and which comprises vinyl aromatic monomers and dienes B / S, and the amount of the hard block is more than 30% by weight, preferably more than 40% by weight, based on the total block copolymer (C). In the preferred block copolymer (C), the 1,2-vinyl content in the soft block B / S is less than 20%.

The vinyl content is interpreted to mean the relative proportion of 1,2-linkages of diene units based on the sum of 1,2-, 1,4-cis and 1,4-trans links. The 1,2-vinyl content of the soft block is preferably not more than 20%, in particular 10-20%, in particular 12-16%.

Styrene, alpha -methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinyltoluene or mixtures thereof may be used as the vinyl aromatic monomers in both the hard blocks S1 and S2 and the soft block B / S. Styrene is preferably used.

Butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene or piperylene or mixtures thereof are preferably used as dienes in the soft block B / S. 1,3-butadiene is particularly preferably used.

The block copolymer (C) preferably comprises only the hard blocks S1 and S2, and at least one random soft block B / S, and does not contain the homopolyadiene block B. Preferred block copolymers contain external hard blocks S1 and S2 having different block lengths. The molecular weight of S1 is preferably from 5,000 to 30,000, especially from 10,000 to 20,000 g / mol. The molecular weight of S2 is preferably greater than 35,000 g / mol. The preferred molecular weight of S2 is 50,000 to 150,000 g / mol.

A plurality of random soft blocks B / S may also be present between the hard blocks S1 and S2. Preferably two or more random soft blocks (B / S) 1 and (B / S) 2 containing different amounts of vinyl aromatic monomers and having different glass transition temperatures are preferred.

The block copolymer (C) may have a linear or star-shaped structure. The structure S1- (B / S) 1- (B / S) 2-S2 is preferably used as a linear block copolymer. The molar ratio of vinyl aromatic monomer to diene S / B is preferably less than 0.25 in block (B / S) 1 and preferably 0.5 to 2 in block (B / S) 2.

A preferred star block copolymer (C) is one having a structure comprising one starburst branch of block arrangement S1- (B / S) and one starburst branch of block arrangement S2- (B / S) - (B / S) -S3 and at least one starburst branch of block arrangement S2- (B / S) -S3. Where S3 is an additional hard block of the vinyl aromatic monomer.

A particularly preferred star block copolymer (C) comprises at least one starburst and block arrangement S2- (B / S) 1- (B / S) 2 having a block arrangement S1- (B / S) 1- (B / S) 2 -S3 with a block arrangement S1- (B / S) 2-S3, (B / S) < RTI ID = 0.0 > 2-S3. ≪ / RTI > The molar ratio of the vinyl aromatic monomer to the diene S / B is preferably 0.5 to 2 in the outer block (B / S) 1 and preferably less than 0.5 in the inner block (B / S) 2. The high content of vinyl aromatic monomers in the outer random block (B / S) 1 makes the block copolymer more ductile without changing the total butadiene content.

The star block copolymer (C) having an additional internal block S3 has comparable ductility with higher stiffness. Thus, block S3 acts as a filler in the soft phase without changing the ratio of hard phase to soft phase. The molecular weight of block S3 is usually significantly lower than that of blocks S1 and S2. The molecular weight of S3 is preferably 500 to 5,000 g / mol.

According to a particularly preferred embodiment, it comprises an outer polystyrene block S with a random styrene / butadiene distribution (S / B) _random and /

15 to 50% by weight of butadiene based on the total weight of C), and

C) < / RTI > based on the total weight of styrene

(C) containing a styrene / butadiene copolymer block having a styrene / butadiene copolymer block having a styrene / butadiene copolymer block having a styrene / butadiene copolymer block is used as the component (C).

For example, at least the polymerization of the soft block (B / S) can form the block copolymer (C) by sequential anionic polymerization carried out in the presence of a randomizing agent. The presence of a randomizing agent results in a random distribution of diene and vinyl aromatic units in the soft block (B / S). Suitable randomizing agents are donor solvents such as ethers, such as tetrahydrofuran, or tertiary amines or soluble potassium salts. For an ideal random distribution, in the case of tetrahydrofuran, an amount of more than 0.25% by volume, based on the solvent, is usually used. At low concentrations, a tapered block having a gradient of comonomer composition is obtained.

When the above-mentioned relatively large amount of tetrahydrofuran is used, the relative proportion of the 1,2-linkage of the diene unit also increases to about 30 to 35% at the same time.

On the other hand, when a potassium salt is used, the 1,2-vinyl content in the soft block increases only nonsensically. Thus, the resulting block copolymer (C) is less suitable for crosslinking and has a lower glass transition temperature at the same butadiene content.

The potassium salt is generally used in an amount less than the molar amount based on the anionic polymerization initiator. The molar ratio of the anion polymerization initiator to the potassium salt is preferably selected from 10: 1 to 100: 1, particularly preferably 30: 1 to 70: 1. The potassium salt used should generally be soluble in the reaction medium. Suitable potassium salts are, for example, potassium alcoholates, especially potassium alcohols of tertiary alcohols having 5 or more carbon atoms.

Potassium 2-methylbutanolate, potassium 2,3-dimethyl-3-pentanolate, potassium 2-methylhexanolate, potassium 3, 7-dimethyl-3-octanolate (potassium tetrahydroborate) and potassium 3-ethyl-3-pentanolate are particularly preferably used. The potassium alcoholate can be obtained, for example, by reacting an elemental potassium, potassium / sodium ally or potassium alkylate with an alcohol in an inert solvent.

For convenience, the potassium salt is added to the reaction mixture only after the addition of the anionic polymerization initiator. Then, the hydrolysis of the potassium salt by the trace amount of protic impurities can be avoided. The potassium salt is particularly preferably added immediately after the polymerization of the random soft block B / S.

Conventional monofunctional, difunctional or polyfunctional alkali metal alkyl, aryl or aralkyl may be used as the ionic polymerization initiator. Organo lithium compounds such as ethyl-, propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl-, phenyl-, diphenylhexyl-, hexamethyldi-, butadienyl-, iso Prenyl- and polystylylithium, 1,4-dilithiobutane, 1,4-dilithio-2-butene or 1,4-dilithiobenzene are conveniently used. The required amount of the polymerization initiator depends on the desired molecular weight. It is usually 0.001 to 5 mol% based on the total amount of the monomers.

In the production of the asymmetric star-shaped block copolymer (C), the polymerization initiator is added two or more times. Preferably, the vinyl aromatic monomer Sa and the initiator I1 are simultaneously added to the reactor, and after complete polymerization, the vinyl aromatic monomer Sb and the initiator 12 are added simultaneously. Then, two living polymer chains Sa-Sb-I1 and Sb-I2 are obtained side by side, followed by block addition of the vinyl aromatic monomer and diene to polymerize the block (B / S) 1, The block (B / S) 2 is polymerized by the additional addition of the vinyl aromatic monomer and the diene and, if desired, the block S3 is polymerized by the further addition of the vinyl aromatic monomer Sc. The ratio of initiator I1 to initiator I2 determines the relative proportion of the corresponding starburst branch present after randomization distributed randomly in the individual star block copolymers. Here, the block S1 is formed by the metering addition of the vinyl aromatic monomers Sa and Sb, and the blocks S2 and S3 are formed by the single metering addition of Sb or Sc. The molar ratio of the initiator I2 / I1 is preferably 4/1 to 1/1, particularly preferably 3.5 / 1 to 1.5 / 1.

The polymerization can be carried out in the presence of a solvent. Suitable solvents include, but are not limited to, aliphatic, cycloaliphatic or aromatic hydrocarbons of 4 to 12 carbon atoms customary for anionic polymerization, such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, isooctane, benzene, alkylbenzenes such as toluene, Or decalin or a suitable mixture. Cyclohexane and methylcyclohexane are preferably used.

Polymerization can also be carried out in the absence of a solvent in the presence of a metal organgan, such as magnesium, aluminum or zinc alkyl, which has a retarding effect on the polymerization rate.

After completion of the polymerization, the living polymer chains can be blocked using chain termination. Suitable chain terminators are protic or Lewis acids such as water, alcohols, aliphatic or aromatic carboxylic acids and inorganic acids such as carbonic acid or boric acid.

Instead of adding chain termination after the completion of the polymerization, the living polymer chains may also be connected in a star-like manner by means of polyfunctional coupling agents such as polyfunctional aldehydes, ketones, esters, anhydrides or epoxides. Here, by coupling the same or different blocks, it is possible to obtain a symmetric and asymmetric star-shaped block copolymer in which the arm can have the above-described block structure. Asymmetric star block copolymers can be obtained, for example, by separate preparation of individual star shaped branches, or by double initiating by splitting the initiator at multiple starts, for example, from 2/1 to 10/1.

Additional components of the composition are as follows.

The present invention also relates to a thermoplastic elastomer composition comprising as additional component (K) at least one component selected from the group consisting of a dispersant (DA), a buffer material (BS), a molecular weight modifier (MR), a filler (F) Thereby providing a molding composition.

The molecular weight modifier (MR) used may comprise, for example, tert-dodecyl mercaptan (TDM), which can be added continuously or at various times during the production of the rubber latex. The mode of addition of the modifier may affect the properties of the final product.

For the purposes of the polymerization process described above, a dispersant (DA) is also used which is capable of maintaining polymer particles formed in an aqueous medium as well as monomer droplets as a dispersion and stably ensuring the resulting aqueous polymer dispersion. Dispersants (DA) that may be used include not only protective colloids commonly used in performing free-radical aqueous emulsion polymerization but also commercially available emulsifiers.

Examples of suitable protective colloids include polyvinyl alcohol, polyalkylene glycols, alkali metal salts of polyacrylic acid and polymethacrylic acid, and gelatin derivatives. Examples of suitable protective colloids include copolymers and their alkali metal salts including acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid, and / or 4-styrenesulfonic acid.

Other suitable protective colloids include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2- vinylpyridine, 4-vinylpyridine, , Methacrylamide, homopolymers and copolymers comprising amino group-containing acrylates, methacrylates, acrylamides and / or methacrylamides. Other suitable protections for Houben-Weyl, Methoden der organischen Chemie, Methods of Organic Chemistry, volume XIV / 1, Makromolekulare Stoffe, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411-420 A detailed description of the colloid is provided.

Of course, it is also possible to use a mixture of a protective colloid and / or an emulsifier. Dispersants used often contain only emulsifiers which, unlike protective colloids, usually have a molecular weight of less than 1000. They may be anionic, cationic or nonionic. When a mixture of surfactants is used, the individual components must, of course, be compatible with each other. Anionic emulsifiers are generally compatible with each other and with nonionic emulsifiers.

This applies equally to cationic emulsifiers, but most of the anionic and cationic emulsifiers are not compatible with each other. The emulsifiers suitable for the method of Houben-Weyl, Methoden der organischen Chemie, Methods of organic chemistry, volume XIV / 1, Makromolekulare Stoffe, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192-208 An overview is provided. In accordance with the present invention, emulsifiers are used in particular as dispersants, examples of which are anionic, cationic or nonionic surfactants. Examples of familiar non-ionic emulsifiers include ethoxylated mono-, di- and trialkylphenols, and also ethoxylated fatty alcohols. Examples of typical anionic emulsifiers include alkyl sulfates (alkyl radicals: C ₈ -C ₁₂ ), ethoxylated alkanols (alkyl radicals: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (alkyl radicals: C ₄ -C ₁₂ ) And alkali metal salts and ammonium salts of alkylsulfonic acids (alkyl radicals: C ₁₂ -C ₁₈ ).

Suitable cationic emulsifiers generally include C ₆ -C ₁₈ -alkyl- or alkylaryl-containing or heterocyclic-radical-containing primary, secondary, tertiary or quaternary ammonium salts, pyridinium salts, imidazoli Ammonium salts, oxazolinium salts, morpholinium salts, tropylium salts, sulfonium salts and phosphonium salts.

For example, dodecylammonium acetate, or the corresponding sulfates, disulfates or acetates of various 2- (N, N, N-trimethylammonium) ethylparaponate, N-cetylpyridinium sulfate and N-laurylpyridinium Sulfate can be mentioned. Emulsifiers and protective colloids can also be used in the form of mixtures.

For the sake of convenience, the total amount of the emulsifier preferably used as the dispersing agent is 0.005 to 5% by weight, preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, all based on the concentration of the entire monomer. The total amount of protective colloid used as a dispersant in place of or in addition to the emulsifier is often from 0.1 to 10% by weight, frequently from 0.2 to 7% by weight, all based on the concentration of the whole monomer. However, the dispersant used preferably comprises an anionic and / or nonionic emulsifier, particularly preferably an anionic emulsifier.

Additional polymerization auxiliaries that may be used in the polymerization include conventional buffer substances (BS) (e.g., sodium bicarbonate and sodium pyrophosphate) capable of setting a pH value of preferably 6 to 11, and 0 to 3% Molecular weight modifiers (MR) (such as mercaptans, terpinol or dimeric alpha-methylstyrene). The buffer material may also have a complexing action.

The polymerization reaction of the components can be carried out in the range of 0 to 170 캜. The temperatures used are generally from 40 to 120 占 폚, often from 50 to 110 占 폚, and frequently from 60 to 100 占 폚.

Auxiliary and processing additives which can be added to the molding composition of the invention include various additives (D) in an amount of 0 to 10% by weight, preferably 0 to 5% by weight, especially 0 to 4% by weight.

Additive (D) that can be used is any of the materials commonly used in the processing or modification of polymers. Examples that may be mentioned include dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving thermal stability, stabilizers for increasing light fastness, stabilizers for improving hydrolysis resistance and chemical resistance, And, in particular, lubricants, which are advantageous for the production of moldings. These additional additives may be metered in at any stage of the manufacturing or production process, but preferably metered at an earlier time so that the stabilizing effect (or other specified effect) of the additive is utilized at an early stage. With regard to additional customary auxiliaries and additives, see, for example, "Plastics Additives Handbook ", Ed. Gaechter and Mueller, 4th edition, Hanser Pub., Munich, 1996].

Examples of suitable pigments are titanium dioxide, phthalocyanine, ultramarine blue, iron oxide or carbon black, and also all of the organic pigment series

Examples of suitable colorants are any dyes which can be used for the transparent, translucent or opaque coloring of the polymer, and are particularly suitable for the coloration of styrene copolymers.

Examples of suitable flame retardants that may be used are known to those skilled in the art and include halogen or phosphorus containing compounds, and other examples include magnesium hydroxide and also other familiar compounds or mixtures thereof.

Examples of suitable antioxidants include sterically hindered mononuclear or polynuclear phenolic antioxidants which may have various types of substituents and may also have cross-linking via substituents. Among these are oligomeric compounds which can be made up of a plurality of phenolic as well as monomeric compounds. Hydroquinone and hydroquinone-analogs, substituted compounds can also be used, and tocopherol and its derivatives based antioxidants can also be used. Mixtures of various antioxidants may also be used. In principle, a compound suitable for any commercially available compound or styrene copolymer can be used, for example Irganox. Co-stabilizers, especially those known as phosphorus or sulfur-containing co-stabilizers, can be used in conjunction with the phenolic antioxidants mentioned above as examples. Those skilled in the art are aware of such P- or S-containing co-stabilizers.

Examples of suitable light stabilizers include various substituted resorcinol, salicylate, benzotriazole and benzophenone. Extinguishers that can be used include inorganic materials such as talc, glass beads or metal carbonates (e.g., MgCO ₃ , CaCO ₃ ), as well as inorganic materials such as methyl methacrylate, styrene compounds, acrylonitrile, (Especially spherical particles having a diameter d ₅₀ (weight-average) of more than 1 mm). It is also possible to use polymers comprising copolymerized acidic and / or basic monomers.

Suitable mujeokje polytetrafluoroethylene Examples of (antidrip agent) (Teflon; Teflon) polymer and ultra high molecular weight polystyrene (molecular weight M _w More than 2,000,000).

Illustrative examples of fibrous or powdery fillers include carbon fibers or glass fabrics, glass mat or glass silk roving, glass fibers in the form of cut glass or glass beads, or wollastonite, particularly preferably glass fibers . If glass fibers are used, the glass fibers may be provided with a sizing agent and a coupling agent to improve compatibility with the components of the blend.

The incorporated glass fibers may take the form of short glass fibers or continuous-filament strands (conditioned).

Examples of suitable particulate fillers include carbon black, amorphous silica, magnesium carbonate (chalk), powdered quartz, mica, bentonite, talc, feldspar or especially calcium silicates such as wollastonite and kaolin.

Examples of suitable antistatic agents include, but are not limited to, copolymers of amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters, ethylene oxide glycols and propylene oxides And 2-block or 3-block copolymers consisting of propylene oxide blocks) glycols, and glycerol mono- and distearates and also mixtures thereof.

Examples of suitable stabilizers include hindered phenols, also vitamin E and compounds similar in structure to it, and also the butylated condensates of p-cresol and dicyclopentadiene. HALS stabilizers (hindered amine light stabilizers), benzophenone, resorcinol, salicylate and benzotriazole are also suitable. Examples of other suitable compounds include thiocarboxylic acid esters. It is also possible to use C ₆ -C ₂₀ fatty acid esters of thiopropionic acid, in particular stearyl esters and lauryl esters. It is also possible to use dilauryl thiodipropionate, distearyl thiodipropionate or a mixture thereof. Examples of additional additives include HALS absorbents such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, or UV absorbers such as 2H-benzotriazol-2-yl ). Typical use of such additives is from 0.01 to 2% by weight (based on the total mixture).

Suitable lubricants and release agents include stearic acid, stearyl alcohol, stearic acid esters, amide wax (bisstearyl amide), polyolefin waxes, and generally higher fatty acids, derivatives thereof, and corresponding fatty acid mixtures of 12 to 30 carbon atoms . Another particularly suitable material is ethylene bis stearamide (e.g., Irgawax, producer: Ciba, Switzerland). The amount of such additives ranges from 0.05 to 5% by weight.

Silicone oil, oligomer isobutylene, or similar materials may be used as additives. If used, its typical usage is from 0.001 to 3% by weight. It is also possible to use pigments, dyes and optical brighteners such as ultramarine blue, phthalocyanine, titanium dioxide, cadmium sulfide, and derivatives of perylene tetracarboxylic acid. Processing aids and stabilizers such as UV stabilizers, thermal stabilizers (e.g., the butylated reaction product of p-cresol and dicyclopentadiene; Wingstay L; Goodyear; When ethylene oxide-propylene oxide copolymers such as Pluronic (produced by BASF) are used, lubricants, and antistatic agents such as ethylene oxide-propylene oxide, Its typical usage is from 0.01 to 5% by weight, based on the total molding composition.

The amount of the individual additives to be used is generally in each ordinary amount. The graft polymer may be blended with other components in any desired manner by any known method to provide a molding composition. However, it is preferred to blend the components by extrusion, kneading or rolling at a temperature in the range of, for example, 180 to 400 ° C, and these components are pre-isolated from the aqueous dispersion or solution obtained during polymerization if desired. The graft copolymerization product obtained in the aqueous dispersion can be precipitated using, for example, magnesium sulfate. This is preferably only partially dehydrated and can be mixed in the form of wet crumbs (for example the residual water content is from 1 to 40%, in particular from 20 to 40%), after which the complete drying of the graft copolymer during the mixing process . The particles can also be dried according to DE-A 19907136.

The molding compositions of the present invention can be prepared from components A and C (and, if desired, B and additional polymers, fillers and conventional additives D) by any known method.

However, it is preferred, for example, to blend the components by extruding, kneading or rolling the components together and mixing them in the melt. This is carried out at a temperature ranging from 160 to 400 캜, preferably from 180 to 280 캜.

In one preferred embodiment, component (B) is isolated to some extent or completely in advance from the aqueous dispersion obtained during each step of the preparation. For example, graft copolymer B may take the form of wet or dry crumb / powder when mixing pellets of thermoplastic copolymer matrix A and SBS-polymer (C) in an extruder.

The present invention also provides the use of the molding compositions for the production of shaped articles such as sheets or semi-finished products, foils, fibers, or foams, and also corresponding shaped articles such as sheets, semi-finished products, foils, fibers or foams. These shaped bodies can be used for the production of inner liner for refrigerator.

The processing can be performed by a known method of processing a thermoplastic material. Particularly, manufacturing processes that can be used include thermoforming, extrusion, injection molding, calendering, blow molding, compression molding, pressure sintering or other types of sintering, Molding is preferred.

Molding compositions have outstanding melt stability, good colorability, low intrinsic color, and also excellent mechanical properties such as toughness, stiffness and ESCR. Surprisingly, it has also been found that the molding compositions of the present invention have improved low temperature toughness and improved fluidity.

The polymer has a high degree of crosslinking of the polymer particles, which can be recognized from the relaxation time (T2).

The method for analyzing the degree of crosslinking of the crosslinked polymer particles is a measurement of the swelling index (SI) for measuring the swelling property of a polymer having a certain degree of crosslinking by a solvent. An example of a conventional swelling agent is methyl ethyl ketone or toluene. The swelling index (SI) of the molding composition of the present invention is generally in the range of 10 to 60, preferably 15 to 55, particularly preferably 20 to 50. [ Another means of analyzing the graft base and its degree of crosslinking used in the ABS molding composition is the gel content, i. E. The percentage of product cross-linked and insoluble in a particular solvent.

The solvent used for measuring the gel content is preferably the same as that used for measuring the swelling index. Typical gel content of the graft base ranges from 50 to 90%, preferably from 55 to 90%, and particularly preferably from 60 to 85%.

An example of a method for measuring the swelling index is to use toluene in an amount of, for example, 50 g, to swell about 0.2 g of a solid of the film-formed graft base dispersion through evaporation of water. After 24 hours, for example, toluene is removed by suction and the specimen is weighed. The specimen is dried in vacuum and weighed again. The swelling index is consequently the ratio of final weight after swelling to final dry weight after re-drying.

The gel content is calculated correspondingly from the ratio of the dry weight after swelling to the initial weight before swelling (x 100%).

The test methods used to characterize the polymer are briefly summarized below.

a) Charpy Notch Impact resistance (ak) [kJ / m ² ]:

Notch impact resistance was measured according to ISO 179-2 / 1eA (F) for specimens (80 x 10 x 4 mm, melt temperature of 250 ° C and manufactured according to ISO 294 in an assembly mold at a molding temperature of 60 ° C) Or -40 캜.

b) Penetration (Multiaxial Toughness) [Nm]:

The penetration is measured in accordance with ISO 6603-2 for platelets (60 x 60 x 2 mm, melt temperature of 240 ° C and manufactured according to ISO 294 in an assembly mold at a molding temperature of 50 ° C).

c) Flowability (MVR [ml / 10 ']):

The flowability is measured according to ISO 1133 B for a polymer melt at 220 캜 with a load of 10 kg.

d) Elastic modulus (modulus of elasticity [MPa]):

The modulus of elasticity is tested according to ISO 527-2 / 1A / 50 for specimens (prepared according to ISO 294 at a melting temperature of 250 ° C and a molding temperature of 60 ° C).

e) Firing volume:

The amount of clay dried at 80 ° C for 17 hours under nitrogen (200 mbar) is measured on a grafted rubber after filtering through a sieve having a mesh width of about 1 mm.

f) Particle size:

The data for the average particle size (d) is the weight average particle size, which is described in W. Maechtle, S. Harding (eds.), Analytische Ultrazentrifuge (AUC) in Biochemistry and Polymer Science, Royal Society of Chemistry Cambridge, UK 1992, pp. 1447-1475]. ≪ tb > < TABLE > The ultracentrifuge measurement provides an accumulated weight distribution of the specimen particle diameter. From this, it is possible to deduce the weight percentage of the particles whose diameters are below a certain size.

The particle size can also be measured by hydrodynamic fractionation (HDF). The HDF measurement utilizes the flow of liquid carrier material through a column packed with a polymeric carrier material. Small particles that can penetrate even relatively small gaps pass through the column at low flow rates, while particles with relatively large diameters move faster. The particle size is measured by a UV detector (at wavelength 254 nm) at the end of the column. The specimen to be tested is preferably diluted to a concentration of 0.5 g per liter of liquid carrier material, followed by a filtration step and then filling the column. Commercially available HDF devices are available from, for example, Polymer Laboratories. The HDF value is based on the volume distribution. The weight average particle size diameter d ₅₀ is smaller than the particle diameter of 50% by weight of the whole particles and is larger than the particle diameter of 50% by weight of the whole particles.

g) swelling index and gel content [%]:

Water was evaporated from the graft base aqueous dispersion to prepare a film, and 0.2 g of this film and 50 g of toluene were mixed. After 24 hours, the toluene was removed from the swollen specimen by inhalation and the final weight of the specimen was determined. After drying the specimen under vacuum at 110 캜 for 16 hours, the final weight of the specimen was measured again.

The following were calculated:

Swelling index (SI) = weight of swollen specimen after removal of solvent by inhalation / weight of dried specimen under vacuum

Gel content = (weight of dried specimen under vacuum / initial weight of specimen before swelling) × 100%

h) Viscosity

The viscosity value (V _z ) of a 0.5% strength solution of the polymer in DMF was determined according to DIN 53726.

i) Gloss (gloss sensitivity)

In order to measure the gloss, rectangular platelets of dimensions 40 mm x 60 mm x 2 mm were produced from the polymer melt using an injection molding machine. The temperatures used here were 230, 255 and 280 ° C. The molding temperature was 30 DEG C and the injection time was 0.1 to 0.5 seconds. Using the apparatus of BYK Mikroglass, the gloss was determined by measuring the reflected light according to standard ISO 2813 at an angle of 45 ° to each of the 10 test platelets in each case.

j) Crosslinking degree

The method of analyzing the polymeric crosslinking is a measurement of the NMR relaxation time of an unstable proton known as T ₂ time. The larger the degree of crosslinking of a particular polymer, the smaller the T ₂ time.

The typical T ₂ time for the graft base of the present invention is from 1 to 50 ms, preferably from 2.5 to 40 ms, particularly preferably from 2.5 to 30 ms, measured for film-formed specimens at 80 ° C in each case. T ₂ time is measured by dehydration of the graft base dispersion and measurement of NMR relaxation of the film-formed specimen. For this purpose, for example, the specimens are dried in air, dried overnight under vacuum, and then tested with suitable testing equipment. Since relaxation is highly temperature-dependent, it can only be compared between specimens tested by the same method. The effective transverse relaxation time of the material is in the range of 1 to 50 ms as measured at a proton resonance frequency of 20 MHz and a temperature of 140 캜. The relaxation time is measured using a magnetization decay curve, which consists of a solid echo and a plurality of spin-echo measurements. The effective relaxation time is defined as the time after the magnetization decay curve collapses to a factor of 1 / e compared to the initial amplitude measured by the solid echo.

The following examples are used to further illustrate the present invention.

Example

Example  1: General Preparation of Copolymer Matrix A

Various embodiments of the copolymer matrix A can be prepared by solution polymerization, for example, in an organic solvent such as toluene or ethylbenzene. For example, in general in Kunststoff-Handbuch [Plastics Handbook], Vieweg-Daumiller, volume V, Polystyrol [Polystyrene], Carl-Hanser-Verlag, Munich 1969, pages 122 et seq., Lines 12 et seq. Can be used as the basis for the practice in this embodiment. It is also possible to prepare the matrix in the form of two (or more) matrix mixtures.

1a) In a specific embodiment, the copolymer matrix (A-1) is prepared starting from 76% by weight of styrene and 24% by weight of acrylonitrile, at a temperature of 150 to 180 DEG C and a ratio of 10.5 to 20.5% And a viscosity V _{z of} 65 ml / g

Example  2: Graft  General manufacture of rubber B

General description of possible preparation methods:

The rubber latex (B1) was generally prepared starting from 0 to 10% by weight of styrene (B11) and 90 to 100% by weight of butadiene (B12).

The aqueous emulsion is polymerized at about 67 ° C, at which time the temperature can rise to below 80 ° C. The reaction was allowed to proceed until the monomer conversion was> 90%. For example, tert-dodecyl mercaptan (TDM) is used as the molecular weight regulator, preferably 3 to 5 parts. This resulted in rubber particles generally having the following properties.

Particle size distribution:

d ₅₀ (weight average, ultracentrifugation) 90 ± 25 nm,

d ₅₀ (number average, ultracentrifugation) 80 ± 25 nm;

Swelling index (SI): 25 to 75 (measured in toluene);

Gel content: 65 ± 20%.

The rubber could then be reacted with styrene and acrylonitrile in an emulsion polymerization to form a graft copolymer (B).

Example  3: Preparation of thermoplastic molding composition

In the following examples, the following commercially available ingredients were used.

Component A: Terluran (graft ABS copolymer, BASF);

Component C1: Styrolux (SBS copolymer with a butadiene content of 26% by weight ("Rigidity"), BASF product);

Component C2: Styroflex (SBS copolymer ("elastomer" with 33% by weight butadiene content, BASF product).

The thermoplastic compositions according to the present invention were tested using the following method.

" LG  How to "explain:

The environmental stress cracking resistance (ESCR) was measured.

1. Specimen Manufacturing

- cut from the extrusion sheet base direction and the transverse direction.

- Specimen size: 200 mm × 20 mm

2. The specimen was fixed on the deforming jig.

3. Immerse the jig in the cyclopentane for 30 seconds, immerse the jig completely and leave as such for 2 minutes.

4. After 2 minutes, remove the specimen and turn it 180 °.

5. The specimen was checked for cracks and the test was repeated according to the strain.

Explanation of "odor" detection:

1. Cut 2 g of the molding material into small pieces of 1-3 mm and place it in a 100 ml beaker with cover.

2. Boil water (10 ml) into a beaker and cover the top.

3. I waited 5 seconds.

4. Open the cover and evaluate the odor: 0 = no detectable odor, 1 = slight odor, 2 = definite odor, 3 = strong odor, 4 = odorless odor.

 The thermoplastic composition and its components (% by weight) Example A Example B Example C Example D  A 100 90 90 97  C1 10  C2 10 3  Modulus of elasticity 2300 2100 1900 2200  Notch impact resistance 26 28 35 30  ESCR (LG method) 0.2 0.9 > 1.8 1.8  smell 0 2 2 0

It was confirmed that the toughness and the environmental stress cracking resistance (ESCR) of the compositions of Example C and Example D of the present invention were improved. Example D, which contained only 3% by weight of stiroflex and 97% by weight of terrulans, had the desired properties.

Claims (11)

1.1
1.1.1 70-76% by weight of styrene as monomer A1,
1.1.2 24-30% by weight of acrylonitrile as monomer A2, and
1.1.3 0-6% by weight of alpha-methyl-styrene, methyl-methacrylate, or mixtures thereof as monomer A3
75-98% by weight of copolymer A;
1.2
1.2.1
1.2.1.1 80-100% by weight of rubber type monomer B11 selected from the group consisting of butadiene and isoprene, and
1.2.1.2 0 to 20% by weight of a polyunsaturated monomer B12 selected from the group consisting of divinylbenzene and allyl (meth)
By weight of graft rubber core B1 containing 10-95% by weight of graft rubber; And
1.2.2
1.2.2.1 75-85% by weight of vinyl aromatic monomers B21 selected from the group consisting of styrene and alpha-methyl-styrene,
1.2.2.2 15-25% by weight of acrylonitrile B22, and
1.2.2.3 0-10% by weight unsaturated copolymerizable monomer B23 selected from the group consisting of butyl acrylate, ethyl-acrylate and methyl (meth) acrylamide
By weight of a graft shell B2
1 to 24% by weight of graft rubber B; And
1.3
1.3.1 30-70% by weight of styrene as vinyl aromatic monomer C1, and
1.3.2 30-70% by weight of butadiene or isostyrene as the at least one unsaturated copolymerizable monomer C2
By weight of thermoplastic SBS block copolymer C having at least two glass transition temperatures of from 70 to 100 DEG C and from -60 to 0 DEG C,
And a thermoplastic molding composition. A process for producing a thermoplastic molding composition according to claim 1, wherein copolymer A, thermoplastic SBS block copolymer C, and graft rubber B are mixed. An article selected from the group consisting of a molded article, a fiber and a foil, comprising the thermoplastic molding composition according to claim 1. The article of claim 3, wherein the article is selected from the group consisting of a shaped body, fiber and foil used as an innerliner for a refrigerator. delete delete delete delete delete delete delete