Patent Application
20250075023
Carbodiimides have proven advantageous in many applications, for example as hydrolysis inhibitors for thermoplastics, polyols, polyurethanes, triglycerides and lubricating oils.
These preferably employ highly sterically hindered polycarbodiimides. Highly sterically hindered aromatic polycarbodiimides with long polymer chains (high molar masses) have especially proven advantageous specifically for the stabilization of polyamides, polyethylene or polybutylene terephthalates and copolyesters such as TPE-E, thermoplastic polyurethane elastomers (TPU), rollable polyurethane elastomers and solvent-based polyurethane dispersions for coatings and paints. However, these highly sterically hindered and long-chain polycarbodiimides, for example those based on triisopropylphenyl isocyanate, have the disadvantage of being producible on a large industrial scale only with a considerable investment of time and equipment. Polycarbodiimides based exclusively on diisocyanates have very high viscosities and can still undergo uncontrollable polymerization even after the carbodiimidization step which entails various disadvantages, for example very costly and complex pelletization. Alternative production processes in solvent (crystallization) involve a plurality of process steps, are therefore costly and lead to products in powder form, thus necessitating additional compacting of the thus-obtained powder to avoid dusts in the end applications. Processes in this regard have already been described inter alia in EP176572 or EP2933285.
While end-capped aromatic polycarbodiimides are less difficult to produce, by comparison they do not show the desired high stabilization and are hazardous on account of toxic byproducts.
There was therefore a need for novel polycarbodiimides which do not exhibit the aforementioned disadvantages of the prior art, i.e. are easy and safe to manufacture, have high average molecular masses, are ideally nonhazardous and effect excellent hydrolysis stabilization. It was accordingly an object of the present invention to provide corresponding polycarbodiimides and a process for production thereof.
It has now been found that, surprisingly, the aforementioned object is achieved by polycarbodiimides of formula (I)
In a preferred embodiment RI represents C1-C12-alkyl-substituted C6-C12-aryls, preferably C1-C4-alkyl-substituted C6-C12-aryls, particularly preferably mono- to tri-C1-C4-alkyl-substituted C6-aryls and very particularly preferably di- and/or triisopropylphenyl.
Preference is given to polycarbodiimides of formula (I), wherein R1, R2 and R3 represent i-propyl- and RI represents diisopropylphenyl and/or triisopropylphenyl. Particular preference is given to the embodiment in which the radicals RI in a molecule are identical.
Also preferred are polycarbodiimides of formula (I) having average molar masses of 10 000 g/mol to 20 000 g/mol, preferably 12 000 g/mol to 18 000 g/mol, particularly preferably 14 000 g/mol to 16 000 g/mol. The average molar masses (Mw) are determined by gel permeation chromatography (GPC), preferably by the method described in the exemplary embodiments.
The proportion of polycarbodiimides having a molar mass of 30 000 g/mol or more is preferably less than 15% by weight, particularly preferably less than 12% by weight. The proportion of carbodiimides having a molar mass (M) of 30 000 g/mol is likewise determined by gel permeation chromatography (GPC).
The mass ratio of the radicals R to the radical of the compound of formula (I) is preferably in the range from 1:100 to 1:20.
The carbodiimide content (NCN content measured by titration with oxalic acid) of the carbodiimides according to the invention is typically 14-17% by weight, preferably 14-16% by weight, particularly preferably 14-15% by weight. To determine the NCN content, the NCN groups are reacted with oxalic acid added in excess and the unreacted oxalic acid is then potentiometrically back-titrated with sodium methoxide, taking into account the blank value of the system.
The polycarbodiimides according to the invention are exceptionally suitable for stabilizing ester-based polymers, preferably polymers selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters such as modified polyesters of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and/or PLA derivatives, polybutylene adipate-terephthalates (PBAT), polybutylene succinates (PBS), polyhydroxyalkanoates (PHA) and blends such as preferably PA/PET or PHA/PLA blends, polyurethane elastomers, preferably thermoplastic polyurethane elastomers (TPU), or rollable polyurethane, PU paints and coatings, preferably solvent-based dispersions.
The invention further relates to a process for stabilizing the above ester-based polymers by incorporating the polycarbodiimides according to the invention into the polymers. The abovementioned carbodiimides are preferably added to the ester-based polymers using solids metering units.
Solids metering units in the context of the invention are preferably: single-, twin- and multi-screw extruders, continuous co-kneaders (Buss-type) and discontinuous kneaders, for example Banbury-type.
The polycarbodiimides according to the invention are obtainable by a process for producing polycarbodiimides of formula (I)
by carbodiimidization of aromatic diisocyanates of formula (II)
and monoisocyanates of formula RI—NCO, wherein the radicals R, R1, R2, R3 and RI and n are as defined above,
According to the prior art the synthesis of the polycarbodiimides of formula (I) is carried out by basic or heterocyclic catalysis. The catalysts typically used are alkali metal or alkaline earth metal compounds and also heterocyclic compounds containing phosphorus. Corresponding catalysts are for example described in Angew. Chem. 1962, 74, 801-806 and Angew. Chem. 1981, 93, 855-866.
The isocyanates used are particularly preferably 1,3,5-triisopropylphenyl diisocyanate (TRIDI), 2,6-diisopropylphenyl isocyanate (DIPI) or 2,4,6-triisopropylphenyl isocyanate (TRIPI).
In one embodiment of the invention the catalysts preferred for the carbodiimidization of the isocyanates to carbodiimides of formula (I) are strong bases or phosphorus compounds. Preference is given to using phospholene oxides, phospholidines or phospholine oxides and also the corresponding sulfides. Further catalysts that may be used are tertiary amines, basic metal compounds, alkali metal and alkaline earth metal oxides, hydroxides, alkoxides or phenoxides, metal carboxylates and non-basic organometallic compounds. Preferred catalysts particularly include alkylphospholene oxides such as for example methylphospholene oxide.
The reaction (carbodiimidization) is preferably conducted in a temperature range from 140° C. to 200° C., particularly preferably from 160° C. to 180° C.
In a preferred embodiment of the invention the isocyanates (diisocyanates and monoisocyanates) are first mixed together and then carbodiimidized as a mixture.
In a further embodiment first the diisocyanates of formula (II) are partially carbodiimidized in the presence of catalysts and optionally solvent and then the monoisocyanates of formula RI—NCO are added to the reaction mixture to complete the carbodiimidization.
In a preferred embodiment the reaction mixture is stirred at elevated temperature, preferably at reaction temperature, under reduced pressure after the carbodiimidization and the residual content of isocyanates reduced to <0.1% by weight.
In a preferred variant of the invention the final reaction mass is finished into pellets or flakes in a pelletizing apparatus from Sandvik Holding GmbH for example or via a flake roller from GMF Gouda for example.
The present invention further provides compositions containing the polymeric carbodiimides according to the invention and ester-based polymers, preferably polymers selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), copolyesters such as modified polyesters of cyclohexanediol and terephthalic acid (PCTA), thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and/or PLA derivatives, polybutylene adipate-terephthalates (PBAT), polybutylene succinates (PBS), polyhydroxyalkanoates (PHA) and blends such as preferably PA/PET or PHA/PLA blends, polyurethane elastomers, preferably thermoplastic polyurethane elastomers (TPU), or rollable polyurethane, PU paints and coatings, preferably solvent-based dispersions. The weight ratio of polymeric carbodiimides to ester-based polymers is typically from 0.1:100 to 5:100, preferably from 0.5:100 to 4:100 and most preferably from 1:100 to 3:100.
The examples which follow serve to elucidate the invention but have no limiting effect.
Pure 1,3,5-triisopropylphenyl diisocyanate (TRIDI) for CDI 1 or a mixture of 1,3,5-triisopropylphenyl diisocyanate (TRIDI) and 2,6-diisopropylphenyl iisocyanate (DIPI) for CDI 2, 4, 5 and 6 or a mixture of 1,3,5-triisopropylphenyl diisocyanate (TRIDI) and cyclohexanol was carbodiimidized at 160° C. in the presence of about 0.1% methylphospholene oxide until an NCO content of <1% was achieved.
The results are listed in Table 1 below.
Tests were carried out on:
As is apparent from Table 1 only the inventive polycarbodiimide is capable of relatively easy and reliable production and finishing (no risk of runaway polymerization in the reactor or in the conduits to and in the finishing region such as a flake roller or pelletizing belt) and simultaneously shows the desired molar mass (Mw>10 000 g/mol) and a reduced proportion of toxic monomeric carbodiimide below the relevant limit of 0.1% by weight. The emission characteristics are moreover reduced with longer polymer chains and a low proportion of monomeric carbodiimide.
To evaluate the hydrolysis inhibition in PET 2.5% by weight respectively of the carbodiimides investigated were dispersed into PET using a ZSK 25 laboratory twin screw extruder from Werner & Pfleiderer prior to the measurement described below. F3 standard test specimens for measurement of breaking strength were then produced from the resultant granulates in an Arburg Allrounder 320 S 150-500 injection-moulding machine.
For the hydrolysis test, these F3 standard test specimens were stored in water at a temperature of 120° C. and the breaking strength thereof was measured in MPa. Table 2 shows the relative breaking strengths=(breaking strength after x days of storage/breaking strength after 0 days)×100. A lower limit for relative breaking strength is usually 70-75%.
The results are shown in Table 2:
Table 3 shows the results of the compatibility tests in DMF/polyurethane dispersions and in rollable polyurethane elastomer (Urepan®, LANXESS Deutschland GmbH)
As is apparent from Table 3, compared to the polycarbodiimide from the prior art the inventive polycarbodiimide invention leads to stable and homogeneous polyurethane formulations due to better dispersibility and solubility. It is also apparent that a lower proportion of higher molecular weight polymer chains of more than 30 000 g/mol in the inventive polycarbodiimide significantly improves compatibility in many applications and formulations.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21217323.1 | Dec 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/086838 | 12/20/2022 | WO |
