DE4237768A1 - New polyarylene ether derivs. with reduced viscosity - used to prepare moulded bodies, foils, fibres and membranes, as matrix resins, adhesives or coating agents or as polymer additives - Google Patents

Abstract

Polyarylene ether derivs. with a reduced viscosity of 0.1-2.0 dl/g, determined by measuring 1g polymers in 100 ml N-methylpyrrolidone (NMP) contains 1-1000 mol. % of a repeating unit of formula (I) and 99-04mol. % of a repeat unit of formula -(Ar2-O-Ar1-O)- (II). In (I), R = H, 1-4C alkyl or Ph; Ar1 = e.g. a gp. of formula (IIa)-(IIf); PpH = para-phenylene X = SO-, SO2 or CO; a = 0-1; b = 2-3; Ar2 = e.g. a gp. of formula (IVa)-(IVd); R1-R4 = each H or 1-4C alkyl; the aromatic rings in (I) are opt. substd. by 1 or more the aromatic rings in (I) are opt. substd. by 1 or more 1-4C alkyl, 1-4C alkoxy, 6-14C aryl or 6-14C arylo gps. and the aromatic rings (IIIa)-(IIIl) and (IVa)-(IVu) are opt. substd. by 1 or more 1-4C alkyl, 1-4C alkoxy, 6-14C aryl, 6-14C aryloxy or halogen gps. Dihydroxy cpds. of formula (VI) are also claimed. USE/ADVANTAGE - The polyarylene-ether can be used for all the normal uses of thermoplastics e.g. in the prepn. of moulded bodies with fibres or membranes, as matrix resins.

Description

The present invention relates to polymers containing aminopyrimidine units Processes for their production and their use as technical materials.

Polyarylene ethers are thermoplastic materials with very good thermal and mechanical properties and versatile uses, such as. B. as Shaped bodies, as exposure materials or as modifiers for thermosets Matrix resins.

Many heterocyclic chain polymers have compared to pure carbocyclic Polymers have a relatively high solubility in many organic solvents on. This is also the case with polyarylene ethers with heterocyclic building blocks Polyarylene ethers which are composed of purely carbocyclic units, one to expect improved solubility, e.g. B. for use as a modifier in Epoxy resins is unavoidable.

Polyarylene ethers with functional groups, for example amino groups along the Main chain, should open up possibilities for subsequent reactions (e.g. polymer analogous implementations or formation of chemical bonds in the modification of thermosetting or thermoplastic polymers).

In J. Pol. Sci. 1965, A 3, S 4285, aromatic polyaminotriazoles are described which are soluble in formic acid and dimethylformamide, but relatively low molecular weight have weights and insufficient thermal stability.

Also in J. Pol. Sci. Part C 22, p. 761 (1969), described poly-4-amino 1,2,4-triazoles with methylene or ethylene ether bridges are not thermally sufficient stable and relatively low molecular weight.

Polyaminotriazoles with aliphatic chains and sulfone groups, for example in the GB Patent 6 76 785 are crystalline materials that are sensitive against thermal crosslinking reactions and are insufficient solubility in  organic solvents.

Polyarylene ethers based on aminopyrimidine units with high Molecular weights are provided, which are characterized by good solubility in common organic solvents, high heat resistance and high stability in terms of thermal decomposition.

The present invention relates to polymers with a reduced viscosity from 0.1 to 2.0 dl / g, determined by measuring 1 g of polymer in 100 ml of N-methyl pyrrolidone (NMP), which 1-100 mol% of a recurring structural element of the Formula (I)

and 99-0 mol% of a recurring structural element of the formula (II)

 Ar₂-O-Ar₁-O (II)

contain in which R is hydrogen, C₁-C₄-alkyl or phenyl,
Ar₁ represents a radical of the formulas (IIIa) - (IIIl),

wherein X is -SO-, -SO₂- or -CO-, Z for

stands, the number 0 or 1 and b the
Number is 2 or 3,
Ar₂ represents a radical of the formulas (IVa) - (IVu)

means Q is a direct bond, -CH₂-, -O- or -CO-, X -SO-, -SO₂- or -CO- means the radicals R₁ to R₄ independently of one another hydrogen or C₁-C₄-alkyl and Y is methyl or phenyl, R₅ and R₆ independently are hydrogen, C₁-C₄ alkyl or phenyl, and wherein the aromatic rings in formula (I) are unsubstituted or by one or several C₁-C₄ alkyl groups, C₁-C₄ alkoxy groups, C₆-C₁₄ aryl groups or C₆-C₁₄ aryloxy groups are substituted, and the aromatic rings in the formulas (IIIa) - (IIIl) and (IVa) - (IVu) unsubstituted or by one or more C₁-C₄-alkyl groups, C₁-C₄ alkoxy groups, C₆-C₁₄ aryl groups, C₁-C₁₄ aryloxy groups or Halogen atoms are substituted.

Polymers containing structural elements of the formulas (I) and (II) in which R represents hydrogen and the aromatic rings in the formulas (I), (IIIa) - (IIIl) and  (Va) - (IVu) are unsubstituted.

Are there any aromatic rings in formulas (I), (IIIa) - (IIIl) and (Va) - (IVu) substituted by C₁-C₄ alkyl groups or C₁-C₄ alkoxy groups, it is branched or in particular straight-chain residues.

Examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.

Are there any aromatic rings in formulas (I), (IIIa) - (IIIl) and (Va) - (IVu) substituted by C₆-C₁₄ aryl groups, these aryl groups are preferred unsubstituted. However, they can also carry substituents, such as alkyl groups or halogen atoms.

Examples of aryl groups are phenyl, naphthyl, biphenyl or anthryl.

Are there any aromatic rings in formulas (I), (IIIa) - (IIIl) and (IVa) - (IVu) substituted by C₆-C₁₄ aryloxy groups, it is usually about unsubstituted aryloxy groups. However, the aryloxy groups can also Bear substituents, such as alkyl groups or halogen atoms.

Examples of aryloxy groups are phenyloxy, naphthyloxy, biphenyloxy or Anthryloxy.

Are the residues of formulas (I), (IIIa) - (IIIl) and (IVa) - (IVu) by halogen atoms substituted, it is fluorine, iodine or in particular chlorine or Bromine.

Ar₁ in the formulas (I) and (II) is preferably a radical of the formula

Ar 1 is particularly preferably in the formulas (I) and (II)

Ar₂ in the formula (II) is preferably a radical of the formulas

Ar₂ particularly preferably represents a radical of the formulas

The polymers according to the invention preferably contain 10-100 mol% of one recurring structural element of formula (I) and 90-0 mol% of a recurring Structural element of formula (II).

The polymers according to the invention can be produced, for example, by a dihalogen compound of the formula (V)

Hal-Ar₁-Hal (V),

in which Ar 1 has the meaning given above and Hal represents a halogen atom, in particular fluorine or chlorine,
with a dihydroxy compound of formula (VI)

wherein the aromatic rings are unsubstituted or by one or more C₁-C₄-alkyl groups, C₁-C₄ alkoxy groups, C₆-C₁₄ aryl groups, C₆-C₁₄ aryloxy groups or  Halogen atoms are substituted and R has the meaning given above, or with a mixture of a dihydroxy compound of formula (VI) and one therein up to 99 mol% of dihydroxy compound of the formula (VII)

HO-Ar₂-OH (VII)

wherein Ar₂ has the meaning given above, in a manner known per se in the presence of alkaline catalysts in a polar aprotic solvent polycondensed.

In the polycondensation reaction, dihalogen compound and Dihydroxy compound (s) used in approximately equimolar amounts. Under about In this context, equimolar amounts are understood to mean a ratio of 0.8-1.2 mol of dihalo compound to 1.2-0.8 mol of dihydroxy compound. A ratio of 0.9-1.1 mol of dihalogen compound to 1.1-0.9 mol is preferred Dihydroxy compound, particularly preferably a ratio of 0.95-1.05 mol of dihalogen compound to 1.05-0.95 mol dihydroxy compound.

Alkaline catalysts are generally used as alkaline catalysts in this process Alkaline earth carbonates, such as sodium, potassium or calcium carbonate; but can also other alkaline reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide, find use.

Potassium carbonate is preferably used. As a rule, the alkaline reagent is in a stoichiometric excess, based on the dihydroxy compound.

Polar aprotic solvents used in the process of making the Polymers according to the invention can be used, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methyl-2-pyrrolidone and preferably diphenyl sulfone.

The reaction is advantageously carried out at elevated temperature, preferably up to to the reflux temperature of the solvent, i.e. up to about 350 ° C.

Often, the use of an entrainer, such as. B. chlorobenzene, Xylene or toluene, in order to react with the phenolic component alkaline reagent to remove water formed from the reaction mixture azeotropically  can.

The dihalo compounds of the formula (V) are known and some are commercially available available. Suitable compounds of formula (V) are, for example, 4,4'-difluoro benzophenone, 4,4'-dichlorobenzophenone, 1,3-bis (4-fluorobenzoyl) benzene, 2,6-difluoro benzonitrile or compounds with heterocyclic groups, such as. B. 2,7-bis (4-fluorobenzoyl) dibenzofuran, and preferably 4,4'-difluorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone.

The dihydroxy compounds of formula (VII) are also known. Suitable Compounds of the formula (VII) are, for example, hydroquinone, bisphenol-A, Bisphenol-F, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, phenyl hydroquinone, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy naphthalene, 9,9-bis (4-hydroxyphenyl) fluorene, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxy biphenyl, 4,4'-dihydroxybenzophenone, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl 1,1'-spirobiindan, phenolic derivatives of heterocyclic compounds, such as. B. 2,6-dihydroxyquinoline and preferably 4,4'-dihydroxydiphenyl sulfone.

The dihydroxy compounds of the formula (VI)

wherein the aromatic rings are unsubstituted or by one or more C₁-C₄-alkyl groups, C₁-C₄ alkoxy groups, C₆-C₁₄ aryl groups, C₆-C₁₄ aryloxy groups or Halogen atoms are substituted and R has the meaning given above, are new and form a further subject of the invention.

The compounds of the formula (VI) can be prepared by methods known per se be, for example by using a methoxy-substituted acetophenone Formula (VIII)

wherein R is hydrogen, C₁-C₄ alkyl or phenyl,
condensed in the presence of a strong base with a methoxy-substituted benzaldehyde of the formula (IX)

and the α, β-unsaturated ketone of the formula (X) thus obtained

where R has the meaning given above, reacted with guanidine nitrate at elevated temperature in the presence of bases, where a 4,6-bis (methoxyphenyl) -2-aminopyrimidine of the formula (XI) is obtained.

The analogous synthesis of 4,6-bisphenyl-2-aminopyrimidine from 1,3-diphenylpropen-1-one is described for example in J. Heterocyclic Chem. 22, p. 1551 (1985).

By reacting the aminopyrimidine of the formula (XI) with pyridine hydrochloride Finally, the 4,6-bis (hydroxyphenyl) -2-aminopyrimidine is exposed to high temperatures Obtain formula (VI).  

Examples of compounds of the formula (VI) according to the invention are 4,6-bis (2-hydroxy phenyl) -2-aminopyrimidine, 4,6-bis (3-hydroxyphenyl) -2-aminopyrimidine and especially 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine.

In the synthesis of the polymers according to the invention, instead of dihydroxy Compounds of the formulas (VI) and (VII) in a manner known per se also the corresponding alkali or alkaline earth metal salts are used.

In addition to the very good thermal properties, the unexpectedly high solubility of the polymers according to the invention in a number of conventional organic solvents. Examples of suitable solvents are polar aprotic solvents such as dimethyl sulfoxide, dimethylacetamide, dimethyl formamide and especially N-methyl-2-pyrrolidone, cyclic ethers or ketones, such as Tetrahydrofuran, dioxane, 1,3-dioxolane, cyclohexanone and cyclopentanone, fluorinated or chlorinated aliphatic and aromatic hydrocarbons, such as tri- or Tetrachloroethane, fluoro-dichloroethane and methylene chloride.

The invention therefore also relates to a solution containing about 1 to 75% by weight, preferably 5 to 50% by weight, based on the total solution, of an invention contemporary polymer dissolved in an organic solvent.

The polymers according to the invention can be used in the usual for thermoplastics Areas of application are used and z. B. to moldings, films, fibers or Membranes are processed, or as matrix resins, adhesives or coating agents or used as additives to other polymers.

Before processing the, for example, as press powder, melt or in particular as Solution-present polymers can be conventional additives, such as, for example Fillers, pigments, stabilizers or reinforcing agents, such as carbon, boron, Metal or glass fibers can be added. The polymers of the invention can can also be processed together with other thermoplastics or thermosets.

The polymers according to the invention are preferably suitable as matrix resins for the Manufacture of fiber composite systems, with the usual as reinforcing fibers can use fibers used in the reinforcement of technical materials. These can be organic or inorganic fibers, natural fibers or synthetic fibers, and  as fiber bundles, as oriented or non-oriented fibers or as continuous fibers available.

Another preferred application for the polymers according to the invention consists in the modification of other plastics. In principle, these can Thermoplastics or thermosets.

A particularly preferred application is the modification of maleimide and Epoxy resins.

Such systems are of particular importance as matrix resins which are used for the production of composite components are used.

I. Preparation of starting compounds I.1. 1,3-bis (4-methoxyphenyl) propen-1-one

To a suspension of 180.24 g (1.2 mol) of 4-methoxyacetophenone and 163.44 g (1.2 mol) of 4-methoxybenzaldehyde in 1.8 l of ethanol are taken at room temperature Nitrogen 55 g sodium hydroxide added. The green solution thus obtained is over Stirred at room temperature overnight, the product gradually precipitating. The The precipitate is filtered off, washed with a little ethanol and dried. It will 287 g (89%) 1,3-bis (4-methoxypenyl) propen-1-one with a melting point of 101-102 ° C receive.

Elemental analysis calculated for C₁₇H₁₆O₃:

Calc .: C 76.10; H 6.01,
Found: C 75.96; H 6.01.

I.2. 4,6-bis (4-methoxyphenyl) -2-aminopyrimidine

To a refluxing solution of 107.2 g (0.4 mol) 1,3-bis (4-methoxy phenyl) propen-1-one according to Example I.1. and 97.6 g (0.8 mol) guanidine nitrate in 3 l Ethanol slowly becomes a solution of 89.9 g (1.6 mol) of potassium hydroxide in 1 liter of ethanol dripped. After a short time, a yellow precipitate forms. After 7 hours of cooking under The reflux is cooled to room temperature and the suspension is filtered. The Fitrat is concentrated in a rotary evaporator and the solid residue from 1 l of ethanol recrystallized. There are 64.1 g (52%) 4,6-bis (4-methoxyphenyl) -2-aminopyrimidine  obtained from the melting point 176-177 ° C.

Elemental analysis calculated for C₁₈H₁₇N₃O₂:

Calc .: C 70.34; H 5.58; N 13.67.
Found: C 68.47; H 5.54; N 13.48.

I.3. 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine

A mixture of 37 g (0.12 mol) of 4,6-bis (4-methoxyphenyl) -2-aminopyrimidine according to Example I.2. and 185 g (1.6 mol) pyridine hydrochloride is heated to 200 ° C and at 4 h kept at this temperature. The hot melt is then poured into 3 l of water poured. The precipitate is filtered off, washed with water and dried. It 33.6 g (100%) of 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine are obtained.

Elemental analysis calculated for C₁₆H₁₃N₃O₂:

Calculated: C 68.81; H 4.69; N 15.05,
Found: C 68.28; H 4.73; N 14.67.

II. Polymer Examples II.1. Polyether sulfone copolymer of 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine, 4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone

A mixture of 13.98 g (0.0501 mol) of 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine according to Example I.3., 38.07 g (0.1521 mol) of 4,4'-dihydroxydiphenyl sulfone, 30.93 g (0.2238 mol) anhydrous potassium carbonate, 168.40 g diphenyl sulfone and 103.00 g xylene is in a flat-bottomed flask with a stirrer under nitrogen to a bath temperature heated from 200 ° C, distilling off a xylene / water mixture. The distillation The process is started after about 40 min by briefly (about 10 min) applying a vacuum of approximately 1 mbar.

57.45 g (0.2001 mol) of 4,4′-dichlorodiphenyl sulfone are now added under nitrogen added. The reaction mixture is heated to 225 ° C and 1 h at this Leave temperature. The temperature is then raised to 255 ° C for one hour finally raised to 283 ° C for 3 hours. The reaction mixture also shows progressive reaction time a significant increase in viscosity.

After cooling briefly, the reaction mixture is removed from the flask and after Freeze powdered. To isolate the polymer, the mixture is submerged with water Add acetic acid, then several times with water and finally with one Water / acetone mixture (1: 4) extracted. The polymer thus purified is then in the Vacuum drying cabinet dried up to a temperature of 180 ° C.  

A polyarylene ether sulfone copolymer produced in this way Aminopyrimidine units have a reduced viscosity (1 g polymer in 100 ml N-methyl-2-pyrrolidone at 25 ° C) of 0.43 dl / g. The one determined by DCS Glass transition temperature is 214 ° C. The polymer is 25% by weight in N-methyl 2-pyrrolidone, dimethylacetamide, dimethyl sulfoxide and γ-butyrolacetone and at least too 10% by weight soluble in cyclohexanone and 1,3-dioxolane.

II.2. Polyethersulfone from 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine and 4,4'-dichlorodiphenyl sulfone

Analogous to example II.1. a polyether sulfone is prepared from 0.0502 mol of 4,6-bis (4-hydroxyphenyl) -2-aminopyrimidine, 0.0500 mol of 4,4'-dichlorodiphenyl sulfone and 0.0535 mol of potassium carbonate (reaction conditions: 1 h / 230 ° C. , 1 h / 251 ° C., 1.5 h / 284 ° C. The polymer obtained is more than 25% by weight in N-methylpyrrolidone, dimethyl acetamide, γ-butyrolactone and more than 5% by weight in The amino group is detected by IR spectroscopy (v = 3501 cm ^-1 , 3391 cm ^-1 ) and 1 H-NMR spectroscopy (δ (NH₂) = 6.78 ppm). The thermogravimetric Examination (TGA) under air (heating rate: 10 ° C / min) shows a weight loss of 0.55% to 400 ° C.

II.3.-II.12. Polyether sulfone copolymers of 4,6-bis (4-hydroxypenyl) -2-aminopyrimidine, 4,44'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone

Analogous to example II.1. Polyether sulfone copolymers are prepared from 4,6-bis (4-hydroxy phenyl) -2-aminopyrimidine and various aromatic dihydroxy and dihalogen compounds. The compositions and properties of the polymers obtained are summarized in Tables 1, 2 and 3.

Claims (12)

1. Polymers with a reduced viscosity of 0.1 to 2.0 dl / g, determined by measuring 1 g of polymer in 100 ml of N-methylpyrrolidone (NMP), which 1-100 mol% of a recurring structural element of the formula (I ) and contain 99-0 mol% of a recurring structural element of the formula (II) Ar₂-O-Ar₁-O (II), in which R is hydrogen, C₁-C₄-alkyl or phenyl,
Ar₁ represents a radical of the formulas (IIIa) - (IIIl), stands, the number 0 or 1 and b the
Number is 2 or 3,
Ar₂ represents a radical of the formulas (IVa) - (IVu) means, Q is a direct bond, -CH₂-, -O- or -CO-, X is -SO-, -SO₂- or -CO-, the radicals R₁ to R₄ independently of one another are hydrogen or C₁-C₄-alkyl and Y represents methyl or phenyl, R₅ and R₆ independently of one another are hydrogen, C₁-C₄-alkyl or phenyl,
and wherein the aromatic rings in formula (I) are unsubstituted or substituted by one or more C₁-C₄ alkyl groups, C₁-C₄ alkoxy groups, C₆-C₁₄ aryl groups or C₆-C₁₄ aryloxy groups, and the aromatic rings in the formulas (IIIa) - (IIIl) and (IVa) - (IVu) are unsubstituted or substituted by one or more C₁-C₄-alkyl groups, C₁-C₄-alkoxy groups, C₆-C₁₄-aryl groups, C₆-C₁₄-aryloxy groups or halogen atoms. 2. Polymers according to claim 1, wherein R is hydrogen and the aromatic Rings in the formulas (I), (IIIa) - (IIIl) and (IVa) - (IVu) are unsubstituted.   3. Polymers according to claim 1, wherein Ar₁ in the formulas (I) and (II) for a radical of the formula stands. 4. Polymers according to claim 1, wherein Ar₁ in the formulas (I) and (II) for a radical of the formula stands. 5. Polymers according to claim 1, wherein Ar₂ for a radical of the formulas stands. 6. Polymers according to claim 1, wherein Ar₂ for a radical of the formulas stands, 7. Polymers according to claim 1, containing 10-100 mol% of a recurring Structural element of the formula (I) and 90-0 mol% of a recurring structural element of formula (II). 8. A process for the preparation of polymers according to claim 1, characterized in that a dihalo compound of the formula (V) Hal-Ar₁-Hal (V), wherein Ar₁ has the meaning given in claim 1 and Hal for a halogen atom, in particular fluorine or Chlorine stands
with a dihydroxy compound of formula (VI) wherein the aromatic rings are unsubstituted or substituted by one or more C₁-C₄-alkyl groups, C₁-C₄-alkoxy groups, C₆-C₁₄-aryl groups, C₆-C₁₄-aryloxy groups or halogen atoms and R has the meaning given in claim 1, or with a mixture of a dihydroxy compound of the formula (VI) and a dihydroxy compound of the formula (VII) HO-Ar₂-OH (VII) in which Ar₂ has the meaning given in Claim 1, up to 99 mol% therein, in a manner known per se in The presence of alkaline catalysts polycondensed in a polar aprotic solvent. 9. Compounds of the formula (VI) wherein the aromatic rings are unsubstituted or substituted by one or more C₁-C₄-alkyl groups, C₁-C₄-alkoxy groups, C₆-C₁₄-aryl groups, C₆-C₁₄-aryloxy groups or halogen atoms and R has the meaning given in claim 1. 10. Solutions containing about 1-75% by weight, based on the total solution, of one Polymers according to claim 1 dissolved in an organic solvent. 11. Use of the polymers according to claim 1 for the production of moldings, Films, fibers or membranes, as matrix resins, adhesives or coating agents or as Additives to other polymers.   12. Use of the polymers according to claim 1 for modifying maleimide and epoxy resins.