DD271823A3 - PROCESS FOR PREPARING POLYESTERAMIDES - Google Patents

Abstract

The invention relates to a process for the preparation of polyester amides, are used in the polyester for the building reaction, wherein polyalkylene arylendicarbonsaeureester be reacted with aromatic diamines. The result is high-modulus anisotropic polymers that have significance as construction materials, as Faserfoermige reinforcing materials or as compounding agents.

Description

H; Alkyl; -Cx-phenyl; -Cx-aryl; -C _x -CN; -CO-C _{x +} , -H; -CO-Cx-phenyl; -CO-C _x -aryl; -O-alkyl; -OC _x -phenyl; -0-C _x -ArVlJ-OC _{x + 2} -CNj-NO ₂ ; halogen

-CR ₂ R ₃ -; -0-; CO-; -CR ₂ = N-; -SJ-SO ₂ -J-CO-NR ₂ -:

-N = N -; - NR ₆ -; - 0-C _{x +} 2-0-;

-NR ₆ -Cx-NR ₆ -; -CH = CH-

alkyl; -Cx-phenyl; -C _x -aryl; -C _{x + 2} -CN; -CO-C _{x + 1} -H; -CO-C _x -phenyl; -CO-C _x -aryl

Alkylene group with xCH ₂ units and x from 0 to 6

5. The method according to claim 1 to 4, characterized in that are preferably used as the polyester component polyethylene terephthalate and / or polyethylene isophthalate and / or polybutylene terephthalate and / or polyethylene terephthalate-co-isophthalate.

6. The method according to claim 1 to 5, characterized in that the aromatic diamines ortho-phenyldiamine, meta-phenylene-diamine, para-phenylenediamine, 2,4 / 2,6-toluenediamine, 4,4'-diaminediphenyl ether, 4.4 'Methylenebisaniline, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diaminoanthraquinone, 2,2'-dimethoxybenzidine in pure form or as a mixture in a ratio of polyester-base moles to moles of diamine (Mixture) of 100: 1 to 100: 50, preferably 100: 5 to 100: 35 are used.

Field of application of the invention

The present invention relates to a process for the preparation of polyesteramides of the general structure

-J] OR ₁ -O-CO-Ar-CC ^ rrnNF ^ Ar · -NH ₃ -CO-Ar -Coip ^ f

with residual polyester base moles in random distribution without major aramid agglomerates in the melt. These high modulus, anisotropic polymers are important as engineering materials, as fibrous reinforcing materials and as compounding agents.

Characteristic of the known state of the art

The patent literature describes various methods for the synthesis of optically anisotropic polymers. In addition to the construction of liquid-crystalline polymers of low molecular weight compounds, the incorporation of specially derivatized or activated low molecular weight compounds into polymers is carried out especially industrially. Optically anisotropic polymers are obtained via the reaction of polyethylene terephthalate with p-acetoxybenzoic acid and / or p-acetamidobenzoic acid (US Pat. No. 4,182,842). The introduction of acetamidobenzoic acid into the polyester with chain scission proceeds relatively quickly. The subsequent transamidation with elimination of corrosive acetic acid, d. H. the renewed chain structure has a very low reaction rate compared to the urease reaction. This results in a long-term, thermal load on the polymer, which has a negative effect on the material properties.

Object of the invention

The aim of the invention is to develop a novel and at the same time simple process for the preparation of polyesteramides having a random sequence distribution as solid, high modulus polymers from commercial, readily available compounds. The process should be feasible in the stirred (boiler) reactor and / or in the (reaction) extruder.

Explanation of the essence of the invention

The invention has for its object to use for the production of high modulus anisotropic polymers of polyester more suitable starting materials.

According to the invention the object is achieved in that a polyalkylene arylendicarbonsäureester with an aromatic diamine ir.i ratio polyester base molar unit [Fi ₁ -O-CO-Ar-CO-O] to moles of diamine from 100: 1 to 100: 50th reacted at temperatures of 150 ° C to 32O ⁰ C under intensive Durchiischuni} and the melt is condensed under reduced pressure and at temperatures up to 4CO ° C while distilling off the alkylene diol and the product is post-condensed at temperatures up to 35O ⁰ C. In this case, the polyester can be melted together with the diamine in pure form or as a mixture of diamines, solid or liquid, with intensive mixing and under inert gas atmosphere at temperatures of 18O ⁰ C to 29O ⁰ C or the diamine in pure form or as a mixture of diamines , solid, liquid eder as a solution in the molten, intensely mixed polyester mass under inert gas atmosphere added or added slowly. It is advantageous as starting materials polyalkylene-farylendicarbonsäure lester (PAE) with the general structure

withRt ... ethylene; 1,2-propylene;

1,3-propylene; 1,4-butylene

Ar ... 1,3-phenylene and / or 1,3-arylene;

and / or 1,4-phenylene and / or 1,4-arylene and aromatic diamines having the general structures:

unsubstituted and / or substituted ortho, meta and para-phenylenediamines

and or

/ w Ii P unsubstituted and / or substituted diphenylendiamines

and or

unsubstituted and / or substituted Y-bisanilines

and or

unsubstituted and / or substituted diaminonaphthalenes

and or

unsubstituted and / or substituted Diaminoanthrachlnone

with RyR ₃ ... R ₄ , re ...

use.

H; Alkyl; -QR-phenyl;

H; alkyl; -C "-phenyl;-C-aryl; -C _x -CNj-CO-C _{x + 1} -H; -CO-Cx-phenyl; -CO-C _x -ArVl; -O-alkyl; -OC _x -phenyl; -OC-aryl; -O-C _{x + 2} -CN; NO ₂ ; Haiogen

-CR ₂ R ₃ -; -O-; CO-; -CR ₂ = N-; -S - SO ₂ -; - CO-NR ₂ -; -N = N -; - NR ₉ -; - 0-C _{x + 2} -O-;

-NR ₈ -C _x -NR ₉ -J-CH = CH-;

alkyl; -C _x -phenyl; -C _x -aryl; -C _{x + 2} -CN; -CO-C _{x + 1} -H; -CO-Cx-phenyl; -CO-C _x -aryl

Alkylene group with χ CH ₂ units and χ from O to β

The aromatic diamines are used in pure form or as a mixture. The starting materials PAE and the diamine or diamine mixture are in the ratios PAE-base molar unit [R ₁ -O-CO-Ar-CO] to Dismin (-Gomisch) of 100: 1 to 100: 50, preferably 100: 5 to 100 : 35, implemented. Via a first reaction step in solution or preferably in substance, the diamines are introduced under PAE chain cleavage. This is advantageously done by melting in an inert gas atmosphere, the substances with good mixing or by the diamine (mixture) solid or geschrr.oizen or added as a solution in the molten PAE mass with thorough mixing. The temperature is increased up to 320 ° C, preferably to 290 ° C, increased. As low proved the Tinsatz well known oxidation stabilizers in the transamidation reaction at high temperatures.

In the second Reaktionsstjfe, which must be run from rier first not separated, under reduced pressure, the resulting in the condensation Älylenendiol at temperatures up to 400 ⁰ C, preferably to 350 ⁰ C, separated or distilled off. For the surprisingly good to very good statistical distribution of the groups in the polyester amide, the quality of the mixing of the reactants is responsible as the most important reaction-technical parameter. The reaction products are preferably polyethylene terephthalate and / or polyethylene isophthalate and / or polybutylene terephthalate and / or polyethylene terephthalate-co-isophthalate with ortho-, and / or meta- and / or para-phenylenediamine and / or 4,4'-diaminodiphenyl ether and / or 4 / .'-methylenebisaniline and / or 2,4 / 2,6-toluenediamine and / or 2,2'-dimethoxybenzidine and / or 1,4-diaminonaphthalene and / or 1,5-diaminonaphthalene and / or 2,6-diaminonaphthalene and / or reacted 1,4-diaminoanthraquinone.

-5- 271323

Depending on the composition and degree of condensation, solid, high modulus polymers having the general structural unit:

/ v GO-Ar t CO-NR ₂ -Ar - NR ₃ -CO-Ar - CO a /

obtained with residual PAE repeat units in random distribution in the polymer. The properties are adjustable above the reaction parameters.

embodiments

The invention will be explained in more detail below with reference to several exemplary embodiments.

Comparative Example (according to US-PS 4182842)

0.75 mole of polyethylene terephthalate and 0.25 mole of p-acetamidobenzoic acid are stirred under inert gas atmosphere at 275 ⁰ C1 hour. After distilling off acetic acid is condensed at 275 ⁰ C for 4 hours under vacuum (0.5 Torr) z <j an amber-colored resinous product. In the solid phase, the powder is postcondensed for 1 hour at 180 ⁰ C, 3 hours at 22O ⁰ C and 10 hours at 23O ⁰ C.

It takes more than 10 hours to produce the polyesteramide. Furthermore, a thermal load of the final product occurs.

example 1

19.2 g of polyethylene terephthalate powder (0.1 mol, TX = 29,000) and 2.16 g of p-phenylenediamine are slowly melted together under N ₂ inert gas atmosphere and good mixing at 26O ⁰ C to 27O ⁰ C. After 5 min under reduced pressure (p <1 torr), the ethylene glycol formed during the condensation is distilled off and the amber-colored melt is postcondensed for 0.5 hours to 28O ⁰ C to 290 ⁰ C.

Example 2

19.2 g of polyethylene terephthalate powder (0.1 mol, M - 29,000) and 2.16 g of p-phenytendiamine are melted under N ₂ -Innertgasatmosphäre and thorough mixing at 28O ⁰ C quickly. Subsequently, the ethylene glycol formed in the condensation is distilled off under reduced pressure (p <1 Torr) and the amber!) Melt by increasing the temperature to 320 ° C and / or briefly up to a maximum of 35O ⁰ C nachkondensiert.

Example 3

19.2 g of polyethylene terephthalate granules (0.1 mol, M = 29,000) are at 28O ⁰ C under N ₂ -nnertgasatmosphäre. melted. 2.16 g of p-phenylenediamine are metered in with thorough mixing of the melt. Then, under reduced pressure (p <1 Torr), the resulting in the condensation of ethylene glycol distilled off and the amber melt by raising the temperature to 32O ⁰ C nachkondensiert.

Examples 1 and 2 are carried out in a stirred reactor and J Examples 1 to 3 in each case in a reactor with screw mixing device (intensive mixing, extruder). A Nachampern in vacuum or under inert gas atmosphere at 260 ⁰ C to 290 ⁰ C improved the material properties. The following approaches were realized:

No. PAE diamine Remarks In base mol InMoI 1. 0.1 0.005 Second 0.1 0,010 Third 0.1 0,015 4th 0.1 0,020 5th 0.1 0,025 6th 0.1 0,030 7th 0.1 0,035 viscous melt 8th. 0.1 0,040 solid product

Runs 7 and 8 were carried out only in the stirred reactor according to Example 1 and 2. In the reactor with screw mixing device, the batch sizes were changed proportionally.

Compared with the prior art (see comparative example), the proposed reaction is completed after 30 minutes at the latest. Due to the short reaction time, thermal stress on the end product is avoided.

The polyester amide melts show an optically anisotropic behavior. The products have IR spectrum depending on the approach, i. Amine, amide and ester absorptions with different intensities.

Analogous to the polyethylene terephthalate are used as the polyester component:

a) Polyethylene isophthalate

b) polybutylene terephthalate

c) polyethylene terephthalate-co-isophthalate

According to the above reactions, the following diamines are used as the diamine component:

d) o-phenylenediamine

e) m-phenylenediamine

f) 2,4 / 2,6-toluenediamine>

g) 4,4'-diaminodiphenyl! ether

h) 4,4'-methylenebisaniline

i) 1,4-diaminonaphthalene

j) 1,5-diaminonaphthalene

k) 2,6-diaminonaphthalene

I) 1,4-olaminoanthraquinone

m) 2,2'-dimethoxybenzidine

In addition to the pure diamine component, mixtures of diamine components in the corresponding batch ratio PAE to diamine are also used.

Claims (4)

claims: 1. A process for the preparation of polyesteramides of the general structure are used in the polyester to building reactions, characterized in that a polyalkylene arylendicarbon acid ester with an aromatic diamine in the ratio of polyester base molar unit [R ₁ -O-CO-Ar-CO-O] to moles of diamine in pure form or reacted as a mixture of diamines from 100: 1 to 100: 50 at temperatures of 15O ⁰ C to 32O ⁰ C under intensive mixing and inert gas atmosphere and the melt condensed under reduced pressure and temperatures up to 400 ⁰ C with distilling off the alkylene diol and the product at Temperatures to 35O ⁰ C is condensed after. 2. The method according to claim 1, characterized in that the polyester together with the diamine solid or liquid, is melted under intensive mixing and under inert gas at temperatures of 18O ⁰ C to 29O ⁰ C. 3. The method according to Anspr.ich 1, characterized in that the diamine is added in pure form or as a mixture of diamines, solid, liquid or Is solution in the molten, intensely mixed polyester mass under an inert gas atmosphere. 4. The method according to claim 1 to 3, characterized in that the starting materials Polyalkylena'rylendicarbonsäureester having the general structure ₍ -0H with R ₁ ... ethylene; 1,2-propylene; 1,3-propylene; 1,4-butylene Ar ... 1,3-phenylene and / or 1,3-arylene and / or 1,4-phenylene and / or 1,4-arylene and aromatic diamines having the general structures: unsubstituted and / or substituted ortho, meta and para-phenylenediamines ^ Uk _a λ is unsubstituted and / or substituted ^NJ diphenylenediamines and or Ν irr-3 unsubstituted and / or substituted Y-bisanilines and or and or unsubstituted and / or substituted diaminonaphthalenes unsubstituted and / or substituted diaminoanthraquinones with R ₂ , R ₃ ... R4, R5 ... Rg ... C _x ... be used. H; alkyl; -Cf-Phenylj-Cx-aryl; -C _{x + 2} -CN;