Aliphatic / alicyclic polycarbonate polyol composition

Abstract

The present invention relates to aliphatic / cycloaliphatic polycarbonate polyol compositions obtainable or produced by the reaction of at least one aliphatic / cycloaliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst, followed by neutralization of the catalyst with at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one moderately strong acid having a pKa of greater than 1 to 7 based on the corresponding acid-base pair.

Description

[Technical Field]

[0001] The present invention relates to an aliphatic / cycloaliphatic polycarbonate polyol composition, a method for its preparation, and the use of a specific neutralizing agent as a terminator in the production of polycarbonate polyols. The present invention also relates to aqueous polyurethane dispersions obtainable from the aliphatic / cycloaliphatic polycarbonate polyols, two-component or thermoplastic polyurethanes, and coatings or molded articles obtainable therefrom. [Background technology]

[0002] Oligocarbonate polyols and polycarbonate polyols are important precursors, for example, in the production of plastics, coatings, and adhesives. These polyols are reacted, for example, with isocyanates, epoxides, (cyclic) esters, acids, or acid anhydrides (DE-A 1 955 902, EP-A 0 343 572). These polyols can in principle be prepared from aliphatic polyols by reaction with phosgene (e.g., DE-A-1 595 446, US-A-4 533 729), bischlorocarbonates (e.g., DE-A-857 948), diaryl carbonates (e.g., DE-A-1 915 908), cyclic carbonates (e.g., DE-A-2 523 352, US-A-787 632, DE-A-1 495 299), or dialkyl carbonates (e.g., DE-A-2 555 805, EP-A-0 343 572, EP-A-0 533 275).

[0003] WO 2018 / 114827 describes a method for producing aliphatic / aliphatic polycarbonate polyols, in which an organic sulfonic acid having a molecular weight of 250-1000 g / mol and at least one branched or unbranched alkyl substituent with at least 4 carbon atoms is used as a strong neutralizer of the basic catalyst, particularly to avoid increasing the reactivity of the polyol toward isocyanate groups. The document includes a comparative example for neutralizing the basic catalyst with dibutyl phosphate, but dibutyl phosphate did not provide sufficient neutralization.

[0004] A disadvantage of the method of WO 2018 / 114827 is that the organic sulfonic acid used itself has a catalytic effect, and therefore, although neutralization is achieved, an increase in the reactivity of the aliphatic / cycloaliphatic polycarbonate polyol may occur.

[0005] Since the synthesis of aliphatic / cycloaliphatic polycarbonate polyols involves a polymerization reaction without complex purification steps, the quality of the input materials must be continuously changed, e.g., reaction management must be taken into consideration, and it is not possible to fully predict how the reactivity of individual batches of aliphatic / cycloaliphatic polycarbonate polyols will behave towards further reaction partners (e.g., isocyanates). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] German Patent Application Publication No. 1955902 [Patent Document 2] European Patent Application Publication No. 0343572 [Patent Document 3] German Patent Application Publication No. 1595446 [Patent Document 4] U.S. Patent Application Publication No. 4,533,729 [Patent Document 5] German Patent Application Publication No. 857948 [Patent Document 6] German Patent Application Publication No. 1915908 [Patent Document 7] German Patent Application Publication No. 2523352 [Patent Document 8] U.S. Patent Application Publication No. 787632 [Patent Document 9] German Patent Application Publication No. 1495299 [Patent Document 10] German Patent Application Publication No. 2555805 [Patent Document 11] European Patent Application Publication No. 0533275 [Patent Document 12] International Publication No. 2018 / 114827 Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, an object of the present invention was to provide an aliphatic / aliphatic polycarbonate polyol composition that does not cause coloration or turbidity and does not exhibit improved reactivity, particularly toward isocyanates.A further object of the present invention is to provide a method for producing an aliphatic / aliphatic polycarbonate polyol that does not cause coloration or turbidity in the product and does not improve the reactivity of the aliphatic / aliphatic polycarbonate polyol, particularly toward isocyanates. [Means for solving the problem]

[0008] In view of this need, the present invention provides aliphatic / cycloaliphatic polycarbonate polyol compositions obtainable or produced by the reaction of at least one aliphatic / cycloaliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst, followed by neutralization of the catalyst with at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa in the range of greater than 1 to 7 based on the corresponding acid-base pair.

[0009] Similarly, in view of this need, the present invention provides a method for producing an aliphatic / cycloaliphatic polycarbonate polyol composition according to the present invention, comprising: a) reacting at least one aliphatic / cycloaliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst; and b) a neutralization step by adding at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa of greater than 1 to 7 based on the corresponding acid-base pair. Including, A method of manufacturing is provided, wherein step b) is performed after step a).

[0010] What is particularly surprising is that the addition of a weak acid, such as dibutyl phosphate, reduces the reactivity of very reactive aliphatic / cycloaliphatic polycarbonate polyols, but has little effect (i.e., neither promotes nor deactivates) the reactivity of less reactive, but still sufficiently reactive, aliphatic / cycloaliphatic polycarbonate polyols. This is particularly evident from the examples using, for example, 100 ppm dibutyl phosphate.

[0011] In this case, pKa for the present invention is defined under standard conditions at 25° C. Reference is made to oxonium (also known as oxidanium, hydroxonium, or hydronium), i.e., protonated water (HO + ) The pKa of the oxonium ion is -1.74.

[0012] In the case of polybasic acids, the pKa value is considered to be the lowest value in this case, for example, for phosphoric acid, the pKa value is 2.16 for pKa1, rather than further values ​​such as pKa2=7.20 or pKa3=12.33.

[0013] According to the present invention, the expressions "comprising", "containing" and the like are to be understood to mean preferably "consisting essentially of", particularly preferably "consisting of". The further embodiments described in the claims and in the specification can be combined as desired, unless the context clearly indicates otherwise.

[0014] As used herein, "at least one" refers to one or more species, e.g., 2, 3, 4, 5, 6, 7, 8, 9 or more species. With respect to the components of the compounds described herein, this number does not refer to the absolute number of molecules, but rather to the nature of the component. Thus, "at least one aliphatic / aliphatic polyol" should be understood to mean, for example, that only one aliphatic / aliphatic polyol or two or more different types of aliphatic / aliphatic polyols may be present, without specifying the amount of each compound.

[0015] In this specification, numerical values ​​written without decimal points refer to numerical values ​​with one decimal point. For example, "99%" means "99.0%."

[0016] Numerical ranges given in the format "x to y" are inclusive of the recited values. When two or more preferred numerical ranges are given in this format, it is understood that all ranges resulting from combining the various endpoints are also encompassed.

[0017] In the context of the present invention, the neutralization in step b) is also called termination, and therefore the strong and medium-strength acids are also called termination agents individually or jointly below. The inventive combination of a basic catalyst with a strong and medium-strength acid is also called a catalyst system in the context of the present invention.

[0018] In the context of the present invention, the expressions "subsequent neutralization" and "step b) is carried out after step a)" should be understood to mean that the neutralization with strong acid and medium-strength acid can be carried out substantially after the reaction of at least one aliphatic / aliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst, respectively, and step b) can be carried out substantially after the reaction of step a) in the presence of a basic catalyst.However, this expression should not be understood to mean that step b) must necessarily be carried out immediately after step a). Thus, any desired steps, such as purification steps, can be carried out after step a), followed by step b), but the reaction product obtained in step a) is neutralized (in each case on a molar basis based on the molar amount of base in the basic catalyst from a) and, in the case of polybasic acids, taking into account only the group with the lowest pKa) preferably with a strong acid to a degree of 70% to 110%, preferably to a degree of 90% to 100%, particularly preferably to a degree of 95% to 99%, and with a medium-strength acid to a degree of 1% to 50%, preferably to a degree of 2% to 30%, particularly preferably to a degree of 3% to 20%. The molar amount of acid relates to the original amount of basic catalyst used in step a) (not the amount after the first partial neutralization step).

[0019] It is preferred if the reaction in step a) is followed by a further reaction step which serves to remove the terminal alkyl carbonate groups in the polymer, for which purpose the reaction mixture is subjected to elevated temperatures of 150°C to 250°C, preferably 170°C to 220°C, particularly preferably 180°C to 210°C, preferably under reduced pressure, in order to distill off the alkanol formed.

[0020] Aliphatic / cycloaliphatic polycarbonate polyols are understood here to mean that cycloaliphatic and / or branched and / or unbranched aliphatic structural units are present, with the presence of unbranched aliphatic structural units being preferred.

[0021] Suitable basic catalysts are, for example, substances whose pKb based on the corresponding acid-base pair is less than 7, preferably less than 2, and very particularly preferably less than 0. Specific examples include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium acetate, potassium acetate, titanium tetraisopropoxide, titanium tetrabutoxide, further titanium alkoxides, ytterbium acetylacetonate, other rare earth acetylacetonates, zinc acetylacetonate, tin acetylacetonate, sodium acetylacetonate, stannous octoate, technical mixtures thereof, aluminum isopropoxide, further aluminum alkoxides, but also strong amine bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

[0022] In a further preferred embodiment, the basic catalyst is a basic salt from the series of alkali metals, which should be understood to mean lithium, sodium, potassium, rubidium and cesium, particularly preferably lithium, sodium and potassium, very particularly preferably sodium and potassium, and especially preferably sodium.

[0023] Suitable anions of basic catalysts are preferably those that are basic or can exhibit basic properties under the reaction conditions. Examples include hydroxides, oxides, carbonates, bicarbonates, phosphates, silicates, alkoxides such as methoxides, ethoxides, and propoxides, and salts of organic acids such as formates, acetates, and propionates. These salts can also be generated in situ, for example, by reacting an alkali metal metal with the corresponding alcohol or acid.

[0024] Examples of particularly preferred suitable basic catalysts are sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium acetate, potassium acetate, sodium methoxide or potassium methoxide being particularly preferred.

[0025] According to the invention, it is also possible to use a mixture of two or more basic catalysts.

[0026] The basic catalyst used in accordance with the present invention can be used either as a solid or as a solution.

[0027] The concentration of the catalyst and / or mixture used according to the invention is preferably 1 ppm to 10,000 ppm, preferably 5 ppm to 500 ppm, particularly preferably 20 ppm to 150 ppm, in each case based on the total weight of the aliphatic / cycloaliphatic polyol and dialkyl carbonate used.

[0028] The reaction temperature for the transesterification of an organic carbonate with an aliphatic polyol using the catalyst according to the present invention to produce an aliphatic oligocarbonate polyol having a molar mass of 500 to 5000 g / mol is preferably 40°C to 250°C, preferably 60°C to 200°C, particularly preferably 90°C to 170°C, and in particular 110°C to 160°C.

[0029] The alkyl carbonate that can be used includes, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate, propylene carbonate.It is preferable to use dialkyl carbonate, dimethyl carbonate or diethyl carbonate.It is very particularly preferable to use dimethyl carbonate.

[0030] Reaction partners that can be used in the transesterification of organic carbonates using the catalysts according to the invention to produce aliphatic oligocarbonate polyols include aliphatic / cycloaliphatic polyols (linear, cyclic, branched, unbranched, saturated or unsaturated) having 2 to 25 carbon atoms and an OH functionality of at least 2, which OH functionality can be primary, secondary, or tertiary, preferably primary or secondary, although any desired mixtures of these OH functionalities can also be present. Primary OH functionality is particularly preferred.

[0031] Examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethylhexanediol, 2-methyl-1,3-propanediol, cyclohexanedimethanol, dimer diol, diethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, trimethylolpropane, pentaerythritol, hydrogenated bisphenol A, and tricyclodecyldimethanol.

[0032] Also usable according to the invention are polyols resulting from the ring-opening reaction of lactones with aliphatic alcohols (linear, cyclic, branched, unbranched, saturated or unsaturated) having an OH functionality of at least 2 (primary, secondary or tertiary), such as adducts of ε-caprolactone with 1,6-hexanediol or ε-caprolactone with trimethylolpropane, and mixtures thereof.

[0033] Short-chain polyethers, preferably polyethylene glycol, polypropylene glycol, or polybutylene glycol, can also be used. The molecular weight of such short-chain polyethers is 800 g / mol or less, preferably less than 500 g / mol. Such short-chain polyethers are preferably difunctional.

[0034] Finally, it is also possible to use mixtures of different aliphatic / cycloaliphatic polyols as reactants.

[0035] Aliphatic or cycloaliphatic, branched or unbranched, primary or secondary polyols having an OH functionality of at least 2 are preferred. Aliphatic, branched or unbranched, primary polyols having a functionality of at least 2 are particularly preferred. Very particular preference is given to the use of 1,6-hexanediol and / or 1,5-pentanediol.

[0036] The transesterification reaction between organic carbonates and aliphatic polyols using the catalysts of the present invention can be carried out at atmospheric pressure or at 10 -3 ~10 3 The process can be carried out either under reduced pressure or under elevated pressure of 1 bar, preferably 1 to 10 bar.

[0037] The addition of a terminator to the aliphatic / alicyclic polycarbonate polyol, preferably after removal of the terminal alkyl carbonate groups, is essential to the present invention. According to the present invention, at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa of greater than 1 to 7 based on the corresponding acid-base pair are used as the terminator.

[0038] In a more preferred embodiment, the at least one strong acid has a pKa of −1 or less, preferably −2 or less, based on the corresponding acid-base pair.

[0039] In a further preferred embodiment, the at least one strong acid is an organic sulfonic acid, preferably an alkyl or aryl sulfonic acid, particularly preferably an aryl sulfonic acid having at least one alkyl substituent. Very particularly preferred are organic sulfonic acids having a molecular weight of 250 to 1000 g / mol, preferably 300 to 500 g / mol, and having at least one branched or unbranched alkyl substituent with at least 4 carbon atoms. The organic sulfonic acid preferably has a molecular weight of 300 to 500 g / mol and has at least one branched or unbranched alkyl substituent with at least 8 carbon atoms. Examples of such organic sulfonic acids are tetrapropylene benzene sulfonic acid or dodecyl benzene sulfonic acid, or isomers thereof. Preferably, the organic sulfonic acid is tetrapropylene benzene sulfonic acid, dodecyl benzene sulfonic acid, and / or a technical isomeric mixture of dodecyl benzene sulfonic acid. Dodecyl benzene sulfonic acid or a technical isomeric mixture thereof is particularly preferred.

[0040] In a more preferred embodiment, the at least one medium-strength acid has a pKa of 2 to 5 based on the corresponding acid-base pair.

[0041] In a further preferred embodiment, the at least one medium strength acid is hydrogen phosphate, preferably dibutyl phosphate, or phosphoric acid, especially dibutyl phosphate.

[0042] The terminator, which is composed of a strong acid and a medium-strength acid, serves to neutralize the basic catalyst, and in a further preferred embodiment, the terminator is used in such a way that the neutralization of the basic catalyst (in each case on a molar basis based on the molar amount of base, taking into account only the group with the lowest pKa in the case of polybasic acids) is carried out to an extent of 70% to 110%, preferably to an extent of 90% to 100%, particularly preferably to an extent of 95% to 99% by the strong acid, and to an extent of 1% to 50%, preferably to an extent of 2% to 30%, particularly preferably to an extent of 3% to 20% by the medium-strength acid.

[0043] The present invention further provides an aliphatic / cycloaliphatic polycarbonate polyol composition comprising at least one aliphatic / cycloaliphatic polycarbonate polyol, 10 to 200 ppmw of sulfur based on the total weight of the aliphatic / cycloaliphatic polycarbonate polyol composition, and 0.1 to 10 ppmw of phosphorus based on the total weight of the aliphatic / cycloaliphatic polycarbonate polyol composition, wherein the sulfur and phosphorus contents are based on the chemically bonded proportions of the elements and are determined by elemental analysis after microwave digestion.

[0044] The aliphatic / alicyclic polycarbonate polyol and / or the aliphatic / alicyclic polycarbonate polyol composition according to the present invention has a number average molecular weight (Mn) of 250 g / mol to 5000 g / mol, preferably 500 g / mol to 3000 g / mol, particularly preferably 800 g / mol to 2500 g / mol. The number average molecular weight is determined by the combination of the OH functionality and the OH number.

[0045] The OH functionality of the aliphatic / cycloaliphatic polycarbonate polyols according to the invention and / or the aliphatic / cycloaliphatic polycarbonate polyol compositions according to the invention is 1.8 to 3.0, preferably 1.9 to 2.5, very particularly preferably 1.94 to 2.00. 1 It can be determined by 1 H NMR spectroscopy.

[0046] The present invention further provides the use of at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa in the range of greater than 1 to 7 based on the corresponding acid-base pair as terminators in the production of an aliphatic / aliphatic polycarbonate polyol composition to reduce the reactivity and / or increase the haze stability of the polycarbonate polyol.

[0047] The aliphatic / cycloaliphatic polycarbonate polyols according to the present invention and / or the aliphatic / cycloaliphatic polycarbonate polyol compositions according to the present invention are suitable, for example, as components for producing aqueous polyurethane dispersions. These polyurethane dispersions are used, for example, as coating materials for paint coatings, where a combination of hydrolysis resistance, chemical resistance, and high elasticity and impact resistance is particularly important. Another application of these polyurethane dispersions containing the aliphatic / cycloaliphatic polycarbonate diols according to the present invention and / or the aliphatic / cycloaliphatic polycarbonate polyol compositions according to the present invention is textile coatings. Here, too, the combination of hydrolysis resistance, chemical resistance, and high elasticity is important.

[0048] Therefore, the present invention further provides an aqueous polyurethane dispersion comprising at least one aliphatic / cycloaliphatic polycarbonate polyol according to the present invention reacted with at least one isocyanate-containing compound, and / or comprising at least one aliphatic / cycloaliphatic polycarbonate polyol composition according to the present invention reacted with at least one isocyanate-containing compound. The aqueous polyurethane dispersion according to the present invention is produced in a manner known per se to those skilled in the art, for example, from U.S. Patent No. 7,452,525, by reacting a polyol according to the present invention with at least one isocyanate-containing compound. Here, a hydrophilic compound is used, and a chain extender may also be used, and other short- or long-chain polyols may also be used.

[0049] The present invention further provides a two-component system comprising component A) containing at least one aliphatic / cycloaliphatic polycarbonate polyol according to the present invention and / or at least one aliphatic / cycloaliphatic polycarbonate polyol composition according to the present invention, and component B) containing at least one polyisocyanate. The aliphatic / cycloaliphatic polycarbonate polyol according to the present invention and / or the aliphatic / cycloaliphatic polycarbonate polyol composition according to the present invention can also be used in a two-component polyurethane casting resin system, where light resistance, resistance to yellowing at high temperatures, and chemical resistance are important.

[0050] The aliphatic / cycloaliphatic polycarbonate polyols according to the present invention and / or the aliphatic / cycloaliphatic polycarbonate polyol compositions according to the present invention can also be used to produce thermoplastic polyurethanes and polyesters. Such plastics are particularly impact-resistant, abrasion-resistant, chemical-resistant, and, depending on the composition, light-resistant. Thus, the present invention further provides thermoplastic polyurethanes comprising at least one aliphatic / cycloaliphatic polycarbonate polyol according to the present invention reacted with at least one isocyanate-containing compound and / or comprising at least one aliphatic / cycloaliphatic polycarbonate polyol composition according to the present invention reacted with at least one isocyanate-containing compound.

[0051] The present invention further provides a molding or coating which is obtainable or which is obtained from at least one thermoplastic polyurethane according to the invention or by curing at least one aqueous polyurethane dispersion according to the invention or by curing at least one two-component system according to the invention.

[0052] The isocyanate-containing compound may be any desired compound known to those skilled in the art. The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0053] [Example] Unless otherwise stated, all percentages are by weight.

[0054] The determination of the NCO content (%) was carried out by back titration with 0.1 mol / l hydrochloric acid after reaction with butylamine according to DIN EN ISO 11909:2007.

[0055] The OH number was determined according to DIN 53240-1:2013.

[0056] Viscosity measurements of the polycarbonate polyols were carried out at 23°C using a plate-type rotational viscometer RotoVisko 1 (Haake, Germany) at a shear rate of 47.94 / s according to DIN EN ISO 3219:1990.

[0057] The sulfur and phosphorus contents are determined by elemental analysis after microwave digestion.

[0058] Polycarbonate diol was prepared according to Example 7 of WO 2018 / 114827. All of the resulting products were partially neutralized. That is, 0.61 g of 4-dodecylbenzenesulfonic acid was added per 1000 g of polycarbonate diol prepared according to Example 7, and the mixture was stirred at 100°C for about 1 hour.

[0059] It was clear that the reactivity of the individual polycarbonate diol batches varied considerably. Four batches of polycarbonate diol (Batch A, B, C, and D) were further analyzed below. Reactivity tests were performed so that the batches could be classified with respect to reactivity.

[0060] Testing the reactivity of polycarbonate diols To test the reactivity of the polycarbonate diols, they were dissolved in butyl acetate at a concentration of 66% and reacted with twice the amount (in terms of NCO-OH ratio) of tolylene diisocyanate (Desmodur T80, Covestro AG, Leverkusen, NCO:OH = 2.0) at 80 °C. The reaction was carried out while periodically checking the isocyanate content, determined by titration.

[0061] [Table 1]

[0062] Batch A is too reactive for most applications. Despite the high molar excess of isocyanate components, the test batch gels after 120° C., thus indicating a high degree of side reactions.

[0063] [Table 2]

[0064] Batch B is significantly less reactive than Batch A, but is still too reactive for some applications.

[0065] [Table 3]

[0066] Batch C corresponds to a typical range of desired reactivities.

[0067] In each of the following inventive examples, 0.1 g of dibutyl phosphate per 1000 g of polycarbonate diol from the above batch was further added with stirring, and the resulting mixture was stirred at 100° C. for 1 hour. After subsequent cooling, reactivity measurements were carried out as appropriate.

[0068] Furthermore, 500 g in each case was filled into clear glass bottles, which were sealed and stored in a recirculating air oven at 70°C for 17 hours prior to direct optical evaluation. None of the dibutyl phosphate spiked samples showed any discernible turbidity or discoloration of the product.

[0069] [Table 4]

[0070] [Table 5]

[0071] [Table 6]

[0072] All three batches with dibutyl phosphate added were found to have good to moderate reactivity. The reaction rate significantly decreased in the very reactive and reactive batches. Therefore, the reaction is controllable. The reaction rate of the moderately reactive batch was already in an easily manageable range before the addition of dibutyl phosphate and was barely affected by the addition of dibutyl phosphate. This is a very good result because it allows for convergence of reactivity despite the addition of the same amount of lower strength acid, given the different initiation levels.

[0073] The reactivity of the three products after the addition of dibutyl phosphate was almost the same in all cases, so promotion could be achieved by adding catalyst as needed, without the need to check the reactivity of each individual batch or adapt the amount of catalyst depending on the batch.

[0074] To test the reactivity of the polycarbonate diol with aliphatic isocyanates, a further sample of the polycarbonate diol described above was dissolved in butyl acetate at a concentration of 67% and reacted with twice the amount (in terms of NCO-OH ratio) of hexamethylene diisocyanate (Desmodur H, Covestro AG, Leverkusen, NCO:OH=2.0) at 80° C. The reaction was carried out with periodic checking of the isocyanate content, determined by titration.

[0075] [Table 7]

[0076] In each of the following examples of the present invention, 0.01 g of phosphoric acid (85% aqueous solution) was further added per 1000 g of polycarbonate diol from the above batch with stirring, and the resulting mixture was stirred for 1 hour at 100° C. After subsequent cooling, reactivity measurements were carried out as appropriate.

[0077] [Table 8]

[0078] It is readily apparent that the addition of phosphoric acid also results in a decrease in reactivity, and this effect also occurs with aliphatic isocyanates, which are more inert than aromatic isocyanates.

Claims

1. An aliphatic / cycloaliphatic polycarbonate polyol composition obtainable or produced by the reaction of at least one aliphatic / cycloaliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst, followed by neutralization of the catalyst with at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa in the range of from greater than 1 to 7 based on the corresponding acid-base pair.

2. 2. The aliphatic / cycloaliphatic polycarbonate polyol composition according to claim 1, wherein the basic catalyst is a substance having a pKb based on the corresponding acid-base pair of less than 7, preferably less than 2, and very particularly preferably less than 0.

3. 3. The aliphatic / cycloaliphatic polycarbonate polyol composition according to claim 1 or 2, characterized in that the basic catalyst is a basic salt from the series of alkali metals, preferably sodium alkoxide or potassium alkoxide.

4. The aliphatic / alicyclic polycarbonate polyol composition according to any one of claims 1 to 3, wherein the at least one strong acid has a pKa of -1 or less, preferably -2 or less, based on the corresponding acid-base pair.

5. The aliphatic / alicyclic polycarbonate polyol composition according to any one of claims 1 to 4, wherein the at least one medium-strength acid has a pKa of 2 to 5 based on the corresponding acid-base pair.

6. 5. The aliphatic / cycloaliphatic polycarbonate polyol composition according to any one of claims 1 to 4, characterized in that the at least one strong acid is an organic sulfonic acid, preferably an alkylsulfonic acid or an arylsulfonic acid, particularly preferably an arylsulfonic acid having at least one alkyl substituent, very particularly preferably an organic sulfonic acid, and / or the at least one medium-strength acid is hydrogen phosphate, preferably dibutyl phosphate or phosphoric acid, in particular dibutyl phosphate.

7. A method for producing the aliphatic / alicyclic polycarbonate polyol composition according to any one of claims 1 to 6, comprising: a) reacting at least one aliphatic / cycloaliphatic polyol with at least one alkyl carbonate in the presence of at least one basic catalyst; and b) a neutralization step by adding at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa of greater than 1 to 7 based on the corresponding acid-base pair. Including, A method of manufacture wherein step b) is carried out at least in part after step a).

8. 8. The method for producing an aliphatic / cycloaliphatic polycarbonate polyol composition according to claim 7, characterized in that the basic catalyst is present in a concentration of 1 ppm to 10,000 ppm, preferably 5 ppm to 500 ppm, particularly preferably 20 ppm to 150 ppm, based in each case on the total weight of the aliphatic / cycloaliphatic polyol and the alkyl carbonate used.

9. 8. The method for producing an aliphatic / cycloaliphatic polycarbonate polyol composition according to claim 7, characterized in that the neutralization of the basic catalyst is carried out by the strong acid to an extent of 70% to 110%, preferably to an extent of 90% to 100%, particularly preferably to an extent of 95% to 99%, and by the medium-strength acid to an extent of 1% to 50%, preferably to an extent of 2% to 30%, particularly preferably to an extent of 3% to 20%, in each case on a molar basis based on the molar amount of base, taking into account in the case of polybasic acids only the groups with the lowest pKa.

10. An aliphatic / alicyclic polycarbonate polyol composition comprising at least one aliphatic / alicyclic polycarbonate polyol, 10 to 200 ppmw of sulfur based on the total weight of the aliphatic / alicyclic polycarbonate polyol composition, and 0.1 to 10 ppmw of phosphorus based on the total weight of the aliphatic / alicyclic polycarbonate polyol composition, wherein the sulfur and phosphorus are chemically bonded to each other.

11. 1. Use of at least one strong acid having a pKa of 1 or less based on the corresponding acid-base pair and at least one medium-strength acid having a pKa in the range of greater than 1 to 7 based on the corresponding acid-base pair as terminators in the production of an aliphatic / aliphatic polycarbonate polyol composition, wherein the use of at least one organic sulfonic acid having a molecular weight of 250 to 1000 g / mol and at least one branched or unbranched alkyl substituent having at least 4 carbon atoms reduces the reactivity of the polycarbonate polyol and / or increases the haze stability.

12. 11. An aqueous polyurethane dispersion comprising at least one aliphatic / cycloaliphatic polycarbonate polyol composition according to any one of claims 1-6 or claim 10 reacted with at least one isocyanate-containing compound.

13. A two-component system comprising component A) comprising at least one inventive aliphatic / cycloaliphatic polycarbonate polyol composition according to any one of claims 1 to 6 or claim 10, and component B) comprising at least one polyisocyanate.

14. 11. A thermoplastic polyurethane comprising at least one aliphatic / cycloaliphatic polycarbonate polyol composition of the present invention according to any one of claims 1-6 or claim 10 reacted with at least one isocyanate-containing compound.

15. 15. A molding or coating obtainable or obtainable from at least one thermoplastic polyurethane according to claim 14, or by curing at least one aqueous polyurethane dispersion according to claim 12, or by curing at least one two-component system according to claim 13.

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