DE4015542A1 - Poly(ester) carbonate mixts. with substd. co-poly-p-phenylene(s) - useful in mfr. of films, fibres, filaments and mouldings - Google Patents

Abstract

Mixts. (I) of polycarbonates and/or polyestercarbonates with substd. co-poly-p-phenylenes based on at least two different repeat units of formula (I) are claimed: In (I) R = 1-8C alkyl, 6-14C aryl, 1-6C alkyl, COO(1-18C)alkyl and 3-10C cycloalkyl, COO(6-10C)aryl, phenoxy, 2-10C dialkyl amino, 2-16C diarylamino, diacetyl amino, formyl, cyano, -CO-(1-6C)alkyl, -CO-(6-10C)aryl, -OCO-(1-18C)alkyl, -OCO(6-10C)aryl, -CONR1R2; R1 and R2 = identical or different 1-18C alkyl, 6-10C aryl, 1-18C aryl, 1-18C alkylsulphenyl, 6-10C aryl sulphinyl and 1-18C alkyl sulphonyl; m = 1 or 2, where m = 2, both R gps. can also be -CH=CH-CH=CH-, -CH=CH-CH2-, -CH2CH2CH2CH2-, -OCH2O-, -OCH2-CH2O; n = 3-1000. The novelty is that the ratio of substd. co-poly-p-phenylene to the matrix polymer is 0.01-0.20:0.99-0.80. Also claimed is the mfr. of (I) from soln. or melt by grinding or kneading.

Description

The invention relates to mixtures of substituted copoly-p-phenylenes and polycarbonates and / or polyester carbonates with excellent mechanical properties and good workability, process for their production, and their use in the manufacture of Shaped bodies, filaments, fibers and foils.

Mixtures of thermoplastic polymers with different Rigid-chain polymers are already known, cf. e.g. B. DE-A 32 16 413, GB-A 20 08 598, US-A 46 31 318 and DE-A 28 47 782. Such mixtures have good mechanical properties Properties, mostly in connection with good fluidity on. However, it is disadvantageous that on the one hand the Polymers previously used as rigid-chain mixture partners are not chemically inert. So polyester or polyamides, for example hydrolytically cleaved become undesirable or by transesterification / transamidation React with the matrix material, which is disadvantageous affect the properties of the mixture because they z. B. can go hand in hand with a breakdown, e.g. B. at  Use of polyheterocycles such as polybisbenzoxazoles, Polybisbenzthiazole or Polybisbenzimidazole, which also are difficult to process. They are usually only meltable with decomposition and only in aggressive Solvents such as methanesulfonic acid soluble.

In GB-A 20 08 598 mixtures of thermoplastic Polymers and e.g. B. unsubstituted poly-p-phenylene described. Unsubstituted poly-p-phenylene is due to its poor solubility and its high melting point difficult to disperse in a polymer matrix. Another disadvantage of the unsubstituted Poly-p-phenylene is its strong tendency towards self-association, what the dispersibility in flexible polymer matrices with special needs.

DE-A 28 47 782 describes mixtures of thermoplastics and poly (p-phenylenes) are known poly (p-phenylenes) but not miscible with polycarbonate in a molecular dispersion. The copoly-p-phenylenes according to the invention have a comparison to poly (p-phenylene) a significantly improved Miscibility with polycarbonate.

The object of the present invention was therefore to provide mixtures made of flexible thermoplastics and chemically inert, easily processable, rigid-chain polymers for To make available.

It has now been found that mixtures with substituted Co-poly-p-phenylenes the required combination of properties have and substituted homo-poly-p-phenylene  superior in solubility and dispersibility are. Substituted copoly-p-phenylenes stand out as a mixing partner due to stability against hydrolysis and excellent solubility in various solvents from, so that mixtures with the most varied Polymers are easy to prepare in solution.

Many substituted copoly-p-phenylenes are undecomposed fusible, so that a production of the invention Mixtures also according to known methods in the Melt can take place.

The mixtures according to the invention with substituted copoly-p-phenylenes can z. B. process from the melt.

Substituted copolyphenylene can be advantageous e.g. B. by the method described in DE-A 40 00 048 produce. Different substitutions are made aromatic dichloro compounds, optionally in Presence of an anhydrous aprotic solvent with metallic zinc, manganese or magnesium Temperatures from 0 to 250 ° C in the presence of a suitable one Catalyst system implemented.

Also the polymerization of benzene and some substituted ones Benzenes in the presence of Lewis acids, one Cocatalyst and an oxidizing agent is possible (e.g. J. Polym. Sci. Part D [Macromolecular Reviews] 5 [1971] 385 to 430).  

Other methods of making polyarylenes are e.g. B. the Wurtz-Fittig reaction, in which, for. B. p-dichlorobenzene with metallic sodium or sodium-potassium alloys is implemented. You can also by Ullmann synthesis, in the dibromo, preferably diiodaryl compounds, polymerized by the action of metallic copper will be manufactured.

Another possibility is the transition metal catalyzed Polymerization of Mono-Grignard compounds of dihaloaromatic compounds, e.g. B. the polymerization of p-dibromobenzene with magnesium in the presence of 2,2′- Bipyridyl-nickel (II) chloride (e.g. JP-A 52-1 549 000) or the polymerization of 1,4-dibromonaphthalene with Magnesium in the presence of nickel (II) acetylacetonate as Catalyst (e.g. Makromol. Chem. 184 [1983] 2241 bis 2249).

The invention therefore relates to mixtures of thermoplastic Polymers with substituted copolyphenylenes based on at least two different ones recurring units of the formula (I)

wherein

for C₁-C₁₈-alkyl radicals, C₆-C₁₄-aryl radicals, C₁-C₆-alkoxy radicals, COOC₁-C₁₈-alkyl, C₃-C₁₀-cycloalkyl radicals, COOC₆-C₁₀-aryl radicals, optionally substituted phenoxy radicals, C₂-C₁₆-dialkylamino radicals, C₂-C₁ C -Diarylamino residues, diacetylamino residues, formyl residues, cyano residues, -CO-C₁-C₆-alkyl residues, -CO-C₆-C₁₀-aryl residues, -OCOC₁-C₁₈-alkyl residues, -OCOC₆-C₁₀-aryl residues, -CONR¹R² residues with R¹ and R² independently identical or different from one another C₁-C₁₈-alkyl, C₆-C₁₀-aryl, C₁-C₁₈-aryl, C₁-C₁₈-alkylsulphenyl, C₆-C₁₀-arylsulfinyl, C₁-C₁₈-alkylsulfonyl, and
m can be 1 and 2 on each ring, where in the case of m = 2 both radicals R together also -CH = CH-CH = CH-, -CHE = CH-CH₂-, -CH₂CH₂CH₂CH₂-, -OCH₂O-, -OCH₂ -CH₂O- can mean and
n is a number from 3 to 1000,

characterized in that the ratio of substituted copoly-p-phenylene to matrix polymer 0.01 to 0.20: 0.99 to 0.80.

In formula (I), the open-chain and cyclic, aliphatic, saturated and unsaturated  Residues and aromatic residues optionally simple or preferred several times with halogen such as fluorine, chlorine, bromine Fluorine.

Furthermore, the radicals mentioned can optionally be substituted be with C₁-C₄ alkoxy, cyano, C₁-C₄ dialkylamino etc.

The preferred substituted copoly-p-phenylenes are called Poly (p- (carboxyalkyl) phenylene-co-p- (carboxyalkyl) phenylene, Poly- (p- (carboxyalkyl) phenylene-co-p- (aryloxy) phenylene, poly- (p- (aryloxy) phenylene-co-p- (aryloxy) phenylene), poly- (p- (carboxyaryl) phenylene-co- p- (carboxyalkyl) phenylene), poly- (p- (carboxyaryl) -phe nylene-co-p- (carboxyaryl) phenylene), poly- (p- (carboxy alkyl) phenylene-co-p- (alkyl) phenylene, poly- (p- (carb oxyaryl) phenylene-co-p- (alkyl) phenylene), poly- (p- (aryl oxyl) phenylene-co-p- (alkyl) phenylene), poly- (p- (alkyl) - phenylene-co- (alkyl) -phenylene), poly- (p- (carboxyalkyl) - phenylene-co-p- (fluoroalkyl) phenylene), poly- (p- (carboxy aryl) phenylene-co-p- (fluoroalkyl) phenylene), poly- (p- (aryloxy) phenylene-co-p- (fluoroalkyl) phenylene), poly- (p- (alkyl) phenylene-co-p- (fluoroalkyl) phenylene), poly- (p- (carboxyalkyl) phenylene-co-p- (fluoroalkoxy) phenylene), Poly (p- (carboxyalkyl) phenylene-co-p- (aryl) phenylene), Poly- (p- (carboxyalkyl) phenylene-co-p- (alkoxy) phenylene), Poly (p- (carboxyaryl) -phenylene-co-p- (aryl) -phenylene), Poly (p- (carboxyaryl) -phenylene-co-p- (aryl) -phenylene), Poly- (p- (carboxyaryl) phenylene-co-p- (alkoxy) phenylene), Poly- (p- (carboxyaryl) phenylene-co-p- (aryloxy) phenylene).  

Are particularly preferred Poly (p- (carboxymethyl) pheny len-co-p- (carboxy (methoxydiethyl ether) phenylene), poly (p- (carboxymethyl) phenylene-co-p- (carboxy-tert-butyl) - phenylene), poly- (p- (carboxymethyl) phenylene-co-p- (carb oxyoctadecyl) phenylene), poly - (- (carboxyoctadecyl) phe nylene-co-p- (carboxy-tert-butyl) phenylene), poly- (p- (carboxyoctadecyl) phenylene-co-p- (carboxy-tert-butyl) - phenylene), poly- (p- (carboxyphenyl) phenylene-co-p- (carb oxymethyl) phenylene, poly (p- (carboxyphenyl) phenylene- co-p- (carboxy-tert-butyl) phenylene), poly- (p- (carboxy methyl) -phenylene-co-p- (methyl) -phenylene), poly- (p- (carb oxymethyl) -phenylene-co-p- (carboxy-tert-butyl) -phenylene- co-p- (carboxyoctadecyl) phenylene).

The mixtures according to the invention can be prepared according to known ones Methods in the melt z. B. by grinding at higher temperatures, mix in a suitable Solvent and solvent removal e.g. B. spray drying or evaporation, or by precipitation from co-solution in a suitable solvent or produce from a dispersion. It is the same possible that matrix polymer in situ in the presence of a Poly-p-phenylene in solution, dispersion and / or in the To produce melt. With this method one can chemical reaction with the substituents of poly-p-phenylene while maintaining the degree of polymerization of Poly-p-phenylene can be brought about.

The mixtures according to the invention show in comparison to improved the unmixed thermoplastics  Flowability and improved mechanical properties. Compared to mixtures of thermoplastics and substituted homo-poly-p-phenylene they show a finer distribution of the dispersed phase. The invention Mixtures are transparent in certain cases.

The substituted copoly-p-phenylenes can be used as end groups Chlorine or hydrogen or from chain terminators wearing leftovers.

As flexible thermoplastic polymers that act as blend partners Examples include polyacrylonitrile, Polyamides such as polyamide 6, 66, polyesters such as Polyethylene terephthalate or polybutylene terephthalate, Polyurethanes, polyalkylenes such as polyethylene or polypropylene, Polycarbonates, polyacetals, polysulfones, polysulfides such as polyphenylene sulfide, vinyl polymers such as polyvinyl chloride, Polyvinylidene chloride or polyvinyl pyrolidone, Polymethyl methacrylate, polystyrene, polyvinyl alcohol, Styrene-butadiene block copolymers.

Copolymers and derivatives of the above can also be used Polymers are used.

Also the mixing of several flexible thermoplastics substituted copoly-p-phenylenes is possible.

The mixtures according to the invention can be conventional additives such as flow and mold release agents, fillers and reinforcing agents such as talc, chalk and glass fiber, organic  Fibers, pigments such as titanium dioxide and soot, fire retardants such as halogen compounds, antimony trioxide and Stabilizers such as low molecular weight phosphites contain.

The usual additives are mixed in one for sufficient and effective amount for the respective purpose added.

The mixtures according to the invention can be used for the preparation of shaped bodies, foils, fibers, filaments etc. be used.

Examples Example 1

15 g of bisphenol A polycarbonate were dissolved in 100 ml of methylene chloride solved. A solution of 3 g of poly (p- (carboxymethyl) phenylene-co-p- (carboxy-tert-butyl) phenylene) given. The combined solutions were based on a Volume of approx. 10-20 ml concentrated. On a film drawing bench a transparent film could be drawn.

In a comparative experiment, a film made of bisphenol-A Polycarbonate drawn.

The tensile modulus of elasticity of the film from the mixture was 2120 MPa.

The tensile modulus of elasticity of the comparison film was 1480 MPa.

Examples 2-4

15 g of matrix polymer were in 100 ml of methylene chloride solved. A solution of 1.5 g poly (p-carboxymethyl) phenylene-co-p- (carboxy-tert-butyl) - phenylene). The combined solutions were based on a volume of about 10-20 ml is concentrated. On a film drawing bench could be mechanically resilient, tearproof films can be obtained.  

The following substituted matrix materials were used:

Example 2: Polystyrene
Example 3: Polyester carbonate (transparent film)
Example 4: Polyvinyl pyrolidone

Examples 5-7

15 g of polystyrene were dissolved in 100 ml of methylene chloride. A solution of 1.5 g of co-poly-p-phenylene was added to each given. The combined solutions were based on a Volume of approx. 10-20 ml concentrated. On a film drawing bench could be mechanically resilient, tear-resistant films can be obtained.

The following substituted copoly-p-phenylenes were: used:

Example 5: Poly- (p- (carboxymethyl) phenylene-co-p- (car boxy-tert-butyl) phenylene
Example 6: Poly (p- (carboxymethyl) phenylene-co-p- (car boxy (methoxydiethyl ethyl ether)) phenylene)
Example 7: Poly (p- (carboxymethyl) phenylene-co-p- (carboxy-tert-butyl) phenylene-co-p- (carboxy octadecyl) phenylene)

Claims (5)

1. Mixtures of polycarbonates and / or polyester carbonates with substituted copoly-p-phenylenes based on at least two different repeating units of the formula (1) wherein
R for C₁-C₁₈ alkyl residues, C₆-C₁₄ aryl residues, C₁-C₆ alkyl residues, COOC₁-C₁₈ alkyl and C₃-C₁₀ cycloalkyl residues, COOC₆-C₁₀ aryl residues, phenoxy residues, C₂-C₁₆ dialkylamino residues, C₂-C₁₆- Diarylamino residues, diacetylamino residues, formyl residues, cyano residues, -CO-C₁-C₆-alkyl residues, -CO-C₆-C₁₀-aryl residues, -OCOC₁-C₁₈-alkyl residues, -OCOC₆-C₁₀-aryl residues, -CONR¹R² residues with R¹ and R² independently the same or different C₁-C₁₈-alkyl, C₆-C₁₀-aryl, C₁-C₁₈-aryl, C₁-C₁₈-alkylsulphenyl, C₆-C₁₀-arylsulfinyl, C₁-C₁₈-alkylsulfonyl, and
m can be 1 and 2 on each ring, where in the case of m = 2 both radicals R together also -CH = CH-CH = CH-, -CH = CH-CH₂-, -CH₂CH₂CH₂CH₂-, -OCH₂O-, -OCH₂ -CH₂O- can mean and
n is a number from 3 to 1000, characterized in that the ratio of substituted copoly-p-phenylene to matrix polymer is 0.01 to 0.20: 0.99 to 0.80. 2. Mixtures according to claim 1, characterized in that the ratio of poly-p-phenylene to matrix polymer 0.01 to 0.2: 0.99 to 0.80. 3. Mixtures according to claim 1, characterized in that a polycarbonate is used as the matrix polymer becomes. 4. A process for the preparation of the mixtures according to claim 1 from solution or from the melt Grinding / kneading. 5. Use of the mixtures according to claim 1 for Manufacture of foils, fibers, filaments and Molded parts.