KR20010033975A - Biodegradable Polyester Amides With Block-Shaped Polyester and Polyamide Segments - Google Patents

Abstract

The present invention

Aliphatic dialcohols or alicyclic diols and / or,

Aliphatic dicarboxylic acids and ester forms thereof and / or,

Aromatic dicarboxylic acids and ester forms thereof and / or,

Hydroxycarboxylic acids and lactones and / or,

Aminoalcohols and / or,

Cyclic lactams and / or,

- Aminocarboxylic acids and / or,

A mixture of dicarboxylic acids and diamines (1: 1 salt)

It can be obtained by polycondensation of an ester block containing a monomer of and having an hydroxyl-, acid- or ester-terminal group and an amide block having an amino-, acid- or ester-terminal group, having an ester content of 20 to A blocky polyesteramide having an amide structure or an ester structure, which is 80% by weight and has an amide content of 80 to 20% by weight.

Description

Biodegradable Polyester Amides With Block-Shaped Polyester and Polyamide Segments}

Rotting aliphatic polyesteramides are known (eg European Patent Publication No. 641,817). Rotting aliphatic-aromatic polyesteramides are also described (WO 92/21689, WO 96/21690, WO 96/21691, and WO 96/21692).

The structure described in this document is purely statistical and has no segmented block structure at all.

Blockamide polyesteramides are also known. Block amides obtained by transesterification / amide exchange reaction of high molecular weight polyamide and high molecular weight polyester are disclosed in European Patent Publication No. 717 064, Japanese Patent No. 0 430 6229, and Japanese Patent No. 0 701 0988 And Japanese Patent No. 0 715 7557. Such a reaction is difficult to reproduce because the degree of the reaction depends very much on the implementation conditions. However, polyesteramides having such a block structure are not sufficiently biodegradable.

It is an object of the present invention to provide segmented polyesteramides in block form that are completely biologically and enzymatically degraded.

Short oligomers having an amide or ester structure, molecular weight of 3,000 or less, and acid-, ester-, hydroxyl-, or amine-terminal groups react with each other under mild conditions such that this segmented structure is preserved.

Therefore, the present invention

Aliphatic dialcohols having 2 to 12 carbon atoms, for example ethylene glycol, diethylene glycol, 1,4-butanediol, 1,3-propanediol, and 1,6-hexanediol; And cycloaliphatic diols such as cyclohexanedimethanol and / or,

Aliphatic dicarboxylic acids preferably having 2 to 12 carbon atoms, for example oxalic acid, succinic acid, adipic acid and the like; And ester types thereof (such as methyl, ethyl and the like), and / or

Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and the like; And ester types thereof (such as methyl, ethyl and the like), and / or

-Preferably hydroxycarboxylic acids having 2 to 12 carbon atoms, for example caprolactone and the like and / or,

Preferably amino alcohols having 2 to 12 carbon atoms, for example ethanolamine, propanolamine and the like, and / or

Cyclic lactams, eg ε-caprolactam or lauryl lactam and the like and / or,

- Aminocarboxylic acids such as aminocaproic acid and the like and / or,

Preferably dicarboxylic acids having 2 to 12 carbon atoms, for example adipic acid, succinic acid, terephthalic acid and the like, preferably diamines having 2 to 10 carbon atoms in the alkyl group, for example hexamethylenediamine, diaminobutane and the like. (1: 1 salt) can be synthesized from the monomers of the mixture, by polycondensation of ester blocks having hydroxyl-, acid- or ester-terminal groups with amide blocks having amino-, acid- or ester-terminal groups A block having an amide structure or ester structure, obtainable, having an ester content of 20 to 80% by weight, preferably 30 to 70% by weight and an amide content of 80 to 20% by weight, preferably 70 to 30% by weight. It provides a type polyesteramide.

Caprolactam or AH salts for synthesizing polyesteramides; Or a mixture of butanediol and / or diethylene glycol and terephthalic acid (ester) and adipic acid (ester).

Prepared short blocks of amide units or ester units are prepared from monomers according to methods known in polymer chemistry by selecting monomeric compositions. For example, a polyamide block of molecular weight 598 having acid end groups can be prepared from 3 moles of adipic acid and 2 moles of hexamethylenediamine.

Equally, a polyester block of molecular weight 490 can be prepared from 2 moles of adipic acid and 3 moles of butanediol. Reaction of these two blocks with each other in stoichiometric ratios results in blocky polyesteramides containing short amide segments and ester segments that do not interfere with the biodegradation process.

In the preparation of short blocks and polyesteramides, suitable catalysts can be used to catalyze the esterification or amidation reactions. Examples of these catalysts include titanium compounds for esterification and phosphorus compounds for amidation. These catalysts are according to the prior art. However, these catalysts should not restrict the use of degradable polymers in subsequent degradation and should not interfere with biodegradability. For this reason, catalysts based on heavy metals such as, for example, antimony or lead are completely excluded.

The polyesteramides thus prepared are fully biodegradable and completely rotting according to DIN 54 900 and have very good mechanical properties.

The resolution of the polymer rotting by the enzyme is called the enzyme resolution. Upon decomposition, the bonds to which the structural units of the polymer are linked together are broken. The resulting crushed product is a monomer of the polymer and its oligomers. The polymer is degraded by enzymes, resulting in a decrease in the molecular weight of the polymer. Enzymatic degradation differs from biodegradation in that it generally does not generate naturally occurring metabolites.

In principle, all enzymes capable of breaking the bonds present in the polymer can be used as enzymes that degrade the biodegradable polymer. When selecting enzymes, carefully check whether these enzymes can degrade the polymer quickly and completely. The degradation is carried out in an aqueous solution that can be buffered. The pH may be 3 to 11, preferably 5 to 9, particularly preferably 6 to 8. The temperature at which enzymatic degradation is carried out can be 5 ° C. to 95 ° C., preferably 20 ° C. to 70 ° C., particularly preferably 30 ° C. to 50 ° C.

Examples of buffers that can be used according to the invention include citrate, acetate, phosphate, formate, carbonate, tris (hydroxymethyl) aminomethane, triethanolamine, imidazole, oxalate, tartrate, fumarate, maleate, Phthalates, succinates, ethylenediamine, as well as mixtures of these species. Preferably acetate, phosphate and citrate are used as buffers.

This procedure involves adding enzymes and polymers to the aqueous solution. Biodegradable polymers may be added in the form of films, sheets or granules. Molding may be added or crushed intact. As the painted or bonded material, or the material to which the paint has been applied or the bond has been produced using a biodegradable polymer, for example paper or cardboard, as well as painted paper or painted cardboard, are intact or It can be added to the enzyme containing solution as a ground form.

In addition, an aqueous solution containing enzyme is applied or sprayed onto the paint or molding to decompose the paint or molding.

The enzymes used may be lipolytic and / or proteolytic enzymes.

For the purposes of the present invention, lipases, lipases, cutinases, esterases, phospholipases and lysophospholipases may be mentioned. Lipolytic enzymes are preferably produced from microorganisms. They are especially derived from bacteria, fungi or yeasts. Lipolytic enzymes can also be derived from plants or animals.

For the purposes of the present invention, proteases may be mentioned as proteases. They are preferably derived from bacteria of Bacillus species. Particular preference is given to proteases of the organisms Bacillus alcalophilus and Bacillus licfheniformis. They can also be derived from fungi or plants.

According to the present invention, synergistic effects can be brought about by the use of lipolytic and proteolytic as well as lipolytic enzymes of various species together. In addition, according to the present invention, decomposition by enzymes is accelerated by adding metal ions such as sodium ions or calcium ions, for example. Also in accordance with the invention, auxiliary substances, for example anionic or nonionic surfactants such as secondary alcohol ethoxylates, are added.

Decay is the ability of the polymerizable material to biodegrade during the rot process. Polymerizable materials that are considered to be perishable should be determined by standard methods of biodegradability in the decay system and the generation of complete quality decay (according to DIN 54 900).

The biodegradation process of a material is a process that results from metabolism and changes the chemical structure of the material, resulting in the final natural product by metabolism (according to DIN 54 900).

The polymeric material is biodegradable (according to DIN 54 900) if all organic components are found to be fully biologically degraded by standard methods.

The mixtures according to the invention also contain customary additives, for example inorganic fillers, reinforcing agents (for example glass fibers, carbon fibers) and mineral fillers (for example talc, mica, chalk, kaolin, wollastonite, gypsum, quartz , Dolomite, etc.), US stabilizers, antioxidants, pigments, dyes, nucleating agents, crystallization promoters or inhibitors, flow enhancers, lubricants, mold release agents, flame retardants 0 to 80% by weight.

The polyesteramides according to the invention may further contain 0.05 to 5% by weight, preferably 0.1 to 1% by weight of branching agents. This branching agent may be, for example, a trihydric alcohol such as trimethylolpropane or glycerol, a tetrahydric alcohol such as pentaerythritol, a trihydric carboxylic acid such as citric acid, or a trivalent or tetravalent hydroxycarboxylic acid.

Example

Example 1

Preparation of the oligoester block which has a hydroxyl terminal group of molecular weight 490.

292 g (2 mol) of adipic acid and 270 g (3 mol) of butanediol were heated together at 250 ° C. under nitrogen. An aqueous jet vacuum was applied after 1 hour and an oil pump vacuum after 2.5 hours. The water was distilled off. After polycondensation for 4 hours, a colorless wax having a hydroxyl number of 21 was obtained.

Example 2

Preparation of the oligoester block which has ester terminal group of molecular weight 1038.

696 g (4 mol) of dimethyl adipate and 270 g (3 mol) of butanediol were heated together at 250 ° C. under nitrogen. An aqueous jet vacuum was applied after 1 hour and an oil pump vacuum after 2.5 hours. The water was distilled off. After polycondensation for 4 hours, colorless wax was obtained.

Example 3

Preparation of an amide block having an ester end group with a molecular weight of 626

522 g (3 mol) of dimethyl adipate and 180 g (2 mol) of hexamethylenediamine were heated together at 250 ° C. under nitrogen. An aqueous jet vacuum was applied after 1 hour and an oil pump vacuum after 2.5 hours. The water was distilled off. After polycondensation for 3 hours, colorless wax was obtained.

Example 4

Preparation of an amide block having an amino end group with a molecular weight of 568

292 g (2 mol) of adipic acid and 348 g (3 mol) of hexamethylenediamine were heated together at 250 ° C. under nitrogen. An aqueous jet vacuum was applied after 1 hour and an oil pump vacuum after 2.5 hours. The water was distilled off. After polycondensation for 3 hours, colorless wax was obtained.

Example 5

Preparation of Polyesteramides from Each Block

626 g (1 mole) of amide block having the ester-terminal group of Example 3 and 490 g (1 mole) of the ester block having the hydroxyl-terminal group of Example 1 were heated together at 190 ° C. under nitrogen. An aqueous jet vacuum was applied after 1 hour and an oil pump vacuum after 2.5 hours. The water was distilled off. After polycondensation for 7 hours, a colorless polymer with a melting point of 136 ° C. was obtained. The polymer obtained has good mechanical properties and is biodegradable according to DIN 54 900.

Claims (4)

Aliphatic dialcohols or cycloaliphatic alcohols and / or Aliphatic dicarboxylic acids and ester forms thereof and / or, Aromatic dicarboxylic acids and ester forms thereof and / or, Hydroxycarboxylic acids and lactones and / or, Aminoalcohols and / or, Cyclic lactams and / or, - Aminocarboxylic acids and / or, A mixture of dicarboxylic acids and diamines (1: 1 salt) It can be obtained by polycondensation of an ester block containing a monomer of and having an hydroxyl-, acid- or ester-terminal group and an amide block having an amino-, acid- or ester-terminal group, having an ester content of 20 to Blocked polyesteramides having an amide structure or an ester structure, having 80% by weight and an amide content of 80 to 20% by weight. The poly of claim 1, wherein the poly is formed by polycondensing a mixture of two or more ester blocks having hydroxyl-, acid- or ester-terminal groups and a mixture of two or more amide blocks having amino-, acid- or ester-terminal groups. Esteramides. Use of the polyesteramides according to claims 1 and 2 for the production of sheets, injection molded articles, nonwovens, fibers or foams. Films, sheets, injection molded articles, nonwovens, fibers and foams made from the polyesteramides according to claim 1.