DE2245957A1 - THERMOPLASTIC MOLDING COMPOUNDS AND LAMINATES - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: 0.Z.29 4lO Dd / Wn 67OO Ludwigshafen, 18.9.-1-972

Thermoplastic molding compounds and laminates

The invention relates to mixtures of a thermoplastic Polymers having NHg or NH groups and a copolymer from an olefin or styrene with an unsaturated carboxylic acid, its ester or anhydride or a vinyl ester. It also relates to the use of these mixtures as mixing or adhesion promoters for the production of thermoplastic Molding compounds or laminates.

With a few exceptions, they are chemically structured in different ways Polymers incompatible. Incompatible plastics cannot be mixed with one another and cannot be mixed with one another combine to form laminates.

The invention was based on the object of polyolefins and polystyrene to make compatible with those thermoplastics A which have NHp or NH groups.

It has been found that this is possible if the polymer A is a copolymer! Sat of the olefin or styrene with a unsaturated mono- or dicarboxylic acid, its ester or anhydride or a vinyl ester.

The invention accordingly relates to mixtures which

a) 98 to 50 percent by weight of a thermoplastic polymer A, which has NHp or NH groups, and

b) 2 to 50 percent by weight of a copolymer B '

60 to 97 percent by weight of a monoolefin with 2 to 4 carbon atoms or of styrene with 40 to 3 percent by weight an olefinically unsaturated mono- or dicarboxylic acid, its ester or anhydride or a vinyl ester

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As thermoplastic polymers A, which NHp or NH groups mainly polyurethanes and polyamides come in Question, e.g. linearly structured polyurethanes produced by film addition reactions of polyesterols or polyetherols with diisocyanates, or linear structures Polyamides obtained by the polycondensation reaction of diamines and dicarboxylic acids or by self-condensation of aminocarboxylic acids or their lactams were produced. However, polyureas, methylene polyamides, polythioureas, Polytriazoles, polyaminotriazoles, polysulfonamides, polyamido acids and thermoplastic aniline-formaldehyde resins can be used.

^{Copolymers B 1} are used as component b, for example those of ethylene, propylene, butene or styrene with acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid or their anhydrides and their esters, preferably those of alcohols having 1 to 10 carbon atoms or with vinyl esters, preferably those of carboxylic acid having 2 to 6 carbon atoms.

Particularly preferred copolymers B 'may be mentioned: copolymer of styrene with 5 to 20 percent by weight maleic anhydride, copolymer of styrene with 5 to 50 percent by weight of methyl methacrylate or methyl, ethyl or butyl acrylate, copolymer of ethylene with 10 to 10 percent by weight of vinyl acetate, copolymer of ethylene with 10 to JO percent by weight ethyl or butyl acrylate, the terpolymer of 'ethylene having from 3 to 10 weight percent acrylic acid and 3 to 20 percent by weight tert-butyl acrylate.

The homogeneous mixtures A + B 'contain 2 to 50, preferably 5 to 10 percent by weight of the copolymer B ¹ . They are produced by mixing in the melt at 150 to 250 ^° C., for example on extruders, on pairs of rollers that run against one another at different speeds, or on kneaders. But you can also mix solutions of the polymers A and B ¹ , evaporate the solvent and the dry

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Product heating at temperatures above 120 ^0C. It is believed." that at the high temperatures that occur during mixing, the NH ₂ or NH groups of the polymer A react with the carboxyl or acid anhydride groups. This chain linkage enables the polymers A and B ¹ to be mixed homogeneously.

These mixtures are eminently suitable as mixing or adhesion promoters for the corresponding homopolymers B, from which the copolymers B ^{1 are} derived , 94, as low pressure polyethylene with a density of 0.94 to 0.97; Polypropylene; Polystyrene and impact-resistant polystyrene which has been modified with 3 to 15 percent by weight of a rubber, preferably with polybutadiene.

With the mixing agents according to the invention, it is possible, for example, to combine polyurethanes or polyamides with polyolefins or Mixing polystyrene and using it to produce homogeneous thermoplastic molding compounds. It is also possible to use these mixtures still other thermoplastics compatible with A.

Add polymers C. For example, the following polymers C are compatible with polyurethane: Copolymers of styrene with acrylonitrile orMethyl methacrylate, optionally impact-resistant with rubbers based on butadiene or acrylic esters can be modified (ABS or ASA polymers); Polysulfones; Polyester; Polycarbonates; Vinyl chloride or vinylidene chloride polymers.

In this way, for example, by using the invention Mixing agents produce thermoplastic molding compounds, the mixtures of styrene / acrylonitrile copolymers with polyethylene or of polyvinyl chloride with polystyrene. This allows the good qualities of each Plastics are specifically combined with one another.

The mixtures according to the invention are also outstandingly suitable as adhesion promoters for the production of laminates, the

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Structure X-Y (-Z). The polymers B listed above can again be used as the top layer X; Layer Y is that of the invention Mixture A + B '. Preferred two-layer fabrics consist e.g. of impact-resistant polystyrene as layer X and a modified polyamide as layer Y or of polyethylene as layer X and a modified polyurethane as layer Y.

Three layers XYZ can be produced if a layer Z is applied to the layer Y, which consists of a substance which adheres to the polymer A of the layer Y. Preferred three-layer materials are, for example:
X: impact-resistant polystyrene,
Y: modified polyurethane,
Z: aluminum,
or

X: impact-resistant polystyrene,
Y: modified polyurethane,
Z: polyethylene terephthalate,
or

X: polyethylene,
Y: modified polyurethane,
Z: polyvinyl chloride,
or

X: impact-resistant polystyrene,
Y: modified polyurethane,
Z: PVC (hard).

The laminates can be produced by known methods, for example by coating, laminating or coextrusion. They can be used to manufacture foils or thermoformed items for the packaging sector or panels for cladding or used for decoration purposes.

The parts and percentages given in the examples are based on weight.

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example 1

92 parts of a thermoplastic polyurethane consisting of polycaprolactone and 4,4'-diphenylmethane diisocyanate were von.Styrol mixed with 8 parts of a copolymer containing 10% maleic anhydride for 5 minutes in the melt at 190 ⁰ C. A pair of steam-heated rollers were used for mixing.

Example 2

100 parts of homopolystyrene and 100 parts of styrene-acrylonitrile copolymer with an acrylonitrile content of 25 % were mixed together with 100 parts of the mixture obtained according to Example 1 at 190 ^° C. in the melt on a pair of steam-heated rollers. The mixture was tough.

<. . . Example 3

A portion of the mixture obtained according to Example 1 was / compressed in a platen press at 200 ⁰ C between two glass fiber reinforced Polytetrafluoräthylenfolien to a 200 micron thick film.

On one side of this adhesive film was an aluminum foil, placed on the other side of a sheet of impact-resistant polystyrene with 6% polybutadiene, .- At 200 ⁰ C and a specific pressure of about 1 kg / cm, the sheets in the plate press to a have not been pressed more separable laminate.

If pure polyurethane is pressed with impact-resistant polystyrene in the heat, the foils can be separated again with ease.

Example 4

Another 100 µm thick made with a platen press Foil made from a mixture according to Example 1 was produced at 250 ° C. and a specific pressure of about 1 kg / cm in the plate press with a 100 / um thick film made of polycarbonate made of phosgene and 1,4-dioxydiphenylmethane on one side and one 100 / um thick polysulfone film made of 4,4'-dioxydiphenyl-2,2-

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propane and 4,4'-dihydroxydiphenyl sulfone compressed. The layers adhere very tightly to each other.

Example 5

92 parts of a thermoplastic polyurethane made from 1,4-butanediol, adipic acid and 4,4'-diphenylmethane diisocyanate were mixed with parts of a copolymer of styrene with 10% maleic anhydride in the melt at 180 ° C for 5 minutes.

Example 6

Part of the mixture obtained according to Example 5 was dissolved in ethyl acetate. A 5 # solution was made. The solution was spread on a 300 μm thick polyethylene terephthalate film, which was located in a 2 square iron frame that now protruded. The dimensions of the frame were 20 20 cm. After drying in air for 48 hours, a 300 μm thick impact-resistant polystyrene film was placed on the side of the polyurethane mixture. After pre-pressing at 200 ^° C. in a plate press, an inseparable laminate was obtained.

Example 7

Part of the mixture obtained according to Example 5 was in a platen press between Teflon film at 180 ° C to form a 100 μm thick film. On one side there was one 100 / um thick impact-resistant polystyrene film placed on the the other side is a rigid PVC film. At 180 ° C a practically inseparable bond was created in a plate press.

Example 8

255 parts of polycaprolactam having a melting point of 220 C were contained in the melt at 25O ⁰ C with 45 parts of styrene / maleic anhydride copolymer containing 18% maleic anhydride, mixed on a laboratory extruder. It was extruded five times. The polymer strands emerging from the nozzle were each cooled under nitrogen.

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Example 9

A portion of the mixture prepared according to Example 8 was pressed at 250 ⁰ C to a 200 mm thick film and processed at 25O ⁰ C in a platen press with a sheet of impact-resistant polystyrene containing 8% of polybutadiene into an inseparable two-layer composite.

Pure polycaprolactam can be removed from the polystyrene film in the heat after pressing with impact-resistant polystyrene separate again effortlessly.

Example 10

80 parts of thermoplastic polyurethane made from polycaprolactone and 4,4'-diphenylmethane diisocyanate and 20 parts of a copolymer made from 89 % ethylene, 7 % tert-butyl acrylate and 4 % acrylic acid were mixed in the melt at 190 ^° C. for 20 minutes. A pair of steam-heated rollers were used for mixing.

Example 11

A part of the mixture according to Example lö produced a Laborzweischichtbreitschlitzdüse at 220 ⁰ C with a polyethylene of density 0.92 was koextrudieft using. The resulting laminate was practically inseparable after cooling.

Pure polyurethane can easily be peeled off the polyethylene film after coextrusion with polyethylene.

Example 12

100 parts Styrolacrylnitrilcopolymerisat having an acrylonitrile content of 35% and 100 parts of polyethylene of density .0,918 were together with- 50 parts of the mixture obtained according to Example 9 in the melt mixed at 190 ⁰ C. The mixture obtained was impact-resistant.

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Example 13

90 parts of thermoplastic polyurethane from Polyeaprolacton and h, 4'-diphenylmethane diisocyanate and 10 parts of a copolymer of 86% ethylene and 14% vinyl acetate were mixed 30 minutes in the melt at 19O ⁰ C for. A pair of steam-heated rollers were used for mixing.

Example 14

A portion of the mixture prepared according to Example 13 was / pressed at 23O ⁰ C to a 200 .mu.m thick film and at 200 ⁰ C in a platen press with a sheet of polyethylene of density O, and 9l8 the other side with a foil of a " ABS polymer processed into a three-layer material that adheres well.

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Claims (4)

Claims 1. Homogeneous mixtures containing -. .. a) 98 to 50 percent by weight of a thermoplastic polymer A, which has NHp or NH groups, and b) 2 to 50 percent by weight of a copolymer B ¹ of 60 to 97 percent by weight of a monoolefin with 2 to 4 Carbon atoms or of styrene with 40 to 3 percent by weight of a monoolefinically unsaturated mono- or Dicarboxylic acid, its ester or anhydride or a vinyl ester. 2. Use of the mixtures according to claim 1 as mixing or adhesion promoters between the polymers A and a Polyolefin or optionally impact-resistant modified polystyrene B and optionally others compatible with A. thermoplastic polymers C. 3 · Thermoplastic molding compounds, containing x) 5 to 95 percent by weight of a polyolefin or one possibly impact-resistant modified polystyrene B, y) 5 to 95 percent by weight of the mixing agent A + B ^f according to claim 1, z) 0 to 90 percent by weight of a compatible with the polymer A. thermoplastic polymers C. 4. Laminates of the structure X - Y (-Z), consisting of a layer X made of polyolefin or optionally impact-resistant modified polystyrene B, a layer Y from the mixture according to claim 1 and optionally a further layer Z made of a thermoplastic polymer C, made of a thermoset, made of metal or wood. Badische Anilin- & Soda-Pabrik AG 4 0 9 8 13/1013