Solvent-free compositions based on 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol

Abstract

The invention relates to a solvent-free composition based on 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol, comprising the following components:-2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol,-the ethoxylate thereof, and-polyethylene glycol, the composition comprising water and the concentration of 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol being greater than 40% by weight based on the composition.

Description

[0001] This application is a divisional application of the invention patent application with application number 202110176412.0 and invention name “Solvent-free composition based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol”. Technical Field

[0002] The invention relates to solvent-free compositions based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol and their use and production for reducing the surface tension in aqueous and solvent-containing systems. Background Art

[0003] The ability to reduce surface tension is crucial in the application of water-based formulations because the reduced surface tension has the effect of improving substrate wettability. Examples of such water-based compositions include coatings, inks, wetting agents, cleaning compositions, and agricultural formulations. Typically, surface tension of water-based systems is reduced by adding surfactants to improve surface wettability, reduce defects, and obtain higher leveling. If the system is at rest, it is important to reduce static surface tension. Dynamic surface tension provides a measure of the adaptability of surfactants on newly created surfaces.

[0004] Surfactant additives based on acetylenic diols, such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, are known for their good static and dynamic surface tension reducing capabilities and have few of the negative features of conventional nonionic and anionic surfactant additives.

[0005] The additive 2,4,7,9-tetramethyl-5-decyne-4,7-diol is a waxy solid with low water solubility and volatility and can be obtained, for example, under the trade name 104 (Evonik). Therefore, before the additive can be used as a wetting agent, for example, it must be melted and / or additionally dissolved in an organic solvent at a preferred use concentration of about 50%. For users in the coatings industry, these additional processing steps mean more effort and costs.

[0006] In order to avoid these additional processing steps, products are already available on the market that dissolve 2,4,7,9-tetramethyl-5-decyne-4,7-diol in a suitable organic solvent such as 2-ethylhexanol, 2-butoxyethanol, dipropylene glycol monomethyl ether, ethylene glycol, propylene glycol or 2-propanol at 50% or 75% of the desired solution concentration. Known trade names here are, for example, 104A or 104E.

[0007] Significant restrictions are expected for the use of organic solvents in coating compositions or formulations in the future. These restrictions come, inter alia, from various national and international guidelines for limiting VOC (volatile organic compounds) emissions from coating materials and reducing the health hazards of volatile and semivolatile compounds (VOC and SVOC) for processors and users (EU Decopaint Guideline 2004 / 42 / CE) (see the requirements of the Ausschuss für die gesundheitliche Bewertung von Bauprodukten=AgBB [German Committee for Health-related Evaluation of Building Products (German Committee for Health-related Evaluation of Building Products)]) or building certification according to the Deutsche Gesellschaft für Nachhaltiges Bauen eV (DGNB) [German Sustainable Building Council (German Sustainable Building Council)] or Leadership in Energy & Environmental Design (LEED).

[0008] US Pat. No. 7,018,963 discloses comparative tests of water-soluble wetting agent compositions consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and alcohol alkoxylates or ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol and alcohol alkoxylates and ethylene glycol (Table 1), without information on storage stability. Summary of the invention

[0009] It was therefore an object of the present invention to provide a composition, in particular as a wetting agent and / or defoamer, which, compared to comparable compositions, is substantially free of volatile organic compounds and which is storage-stable.

[0010] Therefore, in order to achieve this object, a solvent-free composition is proposed, comprising the following components:

[0011] -2,4,7,9-tetramethyl-5-decyne-4,7-diol,

[0012] - ethoxylates thereof, and

[0013] - polyethylene glycol,

[0014] The composition comprises water and the concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is greater than 40 wt % based on the composition.

[0015] In the context of the present invention, solvent-free means that no solvents including volatile organic compounds as required according to EU Decopaint directive 2004 / 42 / CE are used.

[0016] The composition according to the invention preferably does not comprise any organic solvents, such as 2-ethylhexanol, 2-butoxyethanol, dipropylene glycol monomethyl ether, ethylene glycol, propylene glycol or 2-propanol.

[0017] Surprisingly, therefore, 2,4,7,9-tetramethyl-5-decyn-4,7-diol can be dissolved in water, making it possible to dispense with the use of organic solvents.

[0018] Completely unexpectedly, the compositions of the invention did not show phase separation in the storage stability test even under extreme temperature fluctuations after thawing. Any crystals formed during the storage stability test could be easily reincorporated, i.e. without high shear forces and / or heating.

[0019] The concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol in the composition according to the invention is preferably not more than 80% by weight, preferably not more than 70% by weight and particularly preferably not more than 60% by weight, based on the composition.

[0020] It was also completely unexpected that the concentration of the 2,4,7,9-tetramethyl-5-decyne-4,7-diol could be adjusted. The user can use the solvent-free composition according to the present invention without changing the formulation.

[0021] The molar mass of the polyethylene glycol is preferably 200 g / mol to 1000 g / mol, preferably 300 g / mol to 800 g / mol, particularly preferably 400 g / mol to 600 g / mol.

[0022] The composition according to the invention preferably contains ethoxylates of 2,4,7,9-tetramethyl-5-decyne-4,7-diol in an amount of 1 to 10 mol, preferably 3 to 10 mol, of ethylene oxide. These are available, for example, under the product name 465, 440 or 420 (Evonik) is known.

[0023] In this context, ethoxylated derivatives or ethoxylates of 2,4,7,9-tetramethyl-5-decyne-4,7-diol are used synonymously.

[0024] According to a preferred embodiment of the composition of the present invention, the composition comprises

[0025] 40 to 80% by weight, preferably 41 to 70% by weight, particularly preferably 42 to 60% by weight, of 2,4,7,9-tetramethyl-5-decyne-4,7-diol,

[0026] 0.5 to 15% by weight, preferably 1.0 to 10.0% by weight, particularly preferably 2.0 to 8.0% by weight, of ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol,

[0027] 35-55% by weight, preferably 38-50% by weight, particularly preferably 40-45% by weight of polyethylene glycol and

[0028] 1.0 to 15% by weight, preferably 2.0 to 12.0% by weight, particularly preferably 3.0 to 10.0% by weight, of water,

[0029] The amounts of the components mentioned therein add up to 100% by weight and are based on the composition.

[0030] The present invention further preferably relates to the use of the composition according to the invention as wetting agent, defoamer or dispersing aid in coating compositions.

[0031] The coating compositions can be used in the fields of varnishes, paints and inks.

[0032] The compositions according to the invention can preferably be used as auxiliaries in formulations in the fields of agriculture, building materials, plant protection, textile finishing, hydrophobization and electroplating, latex dipping processes, metalworking fluids and printed circuit board coatings.

[0033] The present invention also relates to a method for producing the composition, comprising the following steps:

[0034] a. Provide polyethylene glycol,

[0035] b. Add water,

[0036] C. Add ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol,

[0037] d. Add molten 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

[0038] By taking these steps, it is possible to ensure that 2,4,7,9-tetramethyl-5-decyne-4,7-diol can be better incorporated without worrying about a reduction in its concentration in the composition according to the invention (for example, due to its adhesion to the container). As for the industrial production of the composition according to the invention, this reduction of 2,4,7,9-tetramethyl-5-decyne-4,7-diol will be much greater than in the laboratory scale.

[0039] The composition according to the invention thus offers numerous advantages. The composition is storage-stable and can be easily incorporated into aqueous preparations and water. The system thus produced has low surface tension and reduced foaming behavior.

[0040] With respect to being free of solvents including volatile organic compounds, the compositions according to the present invention represent reduced VOC and / or nearly VOC-free compositions.

[0041] The following examples are provided only to illustrate the present invention to those skilled in the art and in no way constitute any limitation to the claimed subject matter or the claimed method. DETAILED DESCRIPTION

[0042] instrument

[0043] -Circulating air oven from Binder

[0044] - Dissolver / cog disk model CA20M1 from VMA Getzmann

[0045] 1. Preparation of the composition

[0046] First, the 104 (Evonik) was melted. PEG400 (Dow) was initially charged into a 180 ml plastic beaker. Water was slowly added while stirring at 500 revolutions per minute (rpm) and the mixture was stirred at 400 °C. Then, add 440 (Evonik), finally add the previously melted 104. The composition was then stirred at 500 rpm for another 15 minutes.

[0047] Table 1 lists the weight % of each component.

[0048] 2. Storage stability test

[0049] In order to test the storage stability of the composition according to the invention, a number of experiments were carried out. For this purpose, different conditions that may prevail in the storage of the composition were simulated.

[0050] 2a) At room temperature

[0051] The prepared compositions were visually evaluated after one day and one week at room temperature. The visual results are shown in Table 1.

[0052] - Compositions Z1 and Z2 according to the invention were clear and liquid after one day and after one week.

[0053] - Comparable compositions VZ1 and VZ2 demonstrate 104 has low solubility in water, which is known in the prior art.

[0054] -Comparable compositions VZ3-VZ6 demonstrate 104 is insoluble in PEG 400 at concentrations >40 wt %.

[0055] - The comparable compositions VZ7 and VZ8 can be converted to a liquid state by using water. However, VZ8 exhibits phase separation and is also partially solid after one week. Even without adding 440, VZ7 also seemed to be storage stable, but further experiments proved this to be false (see below).

[0056] 2b) at -5°C for 1-4 days, followed by thawing for 5 hours

[0057] The resulting compositions were stored at -5°C and visually evaluated after one day in each case, then thawed for 5 hours (h) after the fourth day and finally evaluated.

[0058] For this experiment, only VZ1, VZ2, VZ7 and Z1, Z2 were selected because they were considered suitable under the "mild" conditions described in 2a). Other comparable compositions were not considered because they were not storage stable.

[0059] It was shown here that VZ7 is unstable at a temperature of -5°C for a short period of time (4 days).

[0060] Under these conditions, the compositions Z1 and Z2 according to the invention and also VZ1 are stable.

[0061] 2c) Under extreme conditions

[0062] The resulting composition was stored for 4 days in a cycle of 16 hours storage at -20°C and then 8 hours of thawing at room temperature (RT). After each step, it was visually inspected. The results are listed in Table 3.

[0063] The same composition as in 2b) was chosen for this experiment.

[0064] It has been shown that even under these extreme conditions, the compositions Z1 and Z2 according to the invention are stable. In the case of VZ1, the user must thaw the composition. In the case of the composition according to the invention, it is not necessary to observe the waiting time for thawing. Thus, the user saves time and therefore costs.

[0065] Table 1

[0066]

[0067] Table 2

[0068]

[0069] Table 3

[0070]

Claims

1. A solvent-free composition comprising the following components: -2,4,7,9-tetramethyl-5-decyne-4,7-diol, - ethoxylates thereof, and - polyethylene glycol, Features The composition comprises water, and the concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is greater than 40 wt % based on the composition.

2. The composition according to claim 1, characterized in that The composition does not contain any organic solvents.

3. A composition according to any one of the preceding claims, characterized in that The concentration of 2,4,7,9-tetramethyl-5-decyne-4,7-diol is not more than 80% by weight, preferably not more than 70% by weight, particularly preferably not more than 60% by weight, based on the composition.

4. A composition according to any one of the preceding claims, characterised in that The molar mass of the polyethylene glycol is 200 g / mol to 1000 g / mol, preferably 300 g / mol to 800 g / mol, particularly preferably 400 g / mol to 600 g / mol.

5. A composition according to any one of the preceding claims, characterised in that The ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol contains 1 to 10 mol, preferably 3 to 10 mol, of ethylene oxide.

6. A composition according to any one of the preceding claims, characterised in that The composition comprises 40 to 80% by weight, preferably 41 to 70% by weight, particularly preferably 42 to 60% by weight, of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 0.5 to 15% by weight, preferably 1.0 to 10.0% by weight, particularly preferably 2.0 to 8.0% by weight, of ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 35-55% by weight, preferably 38-50% by weight, particularly preferably 40-45% by weight of polyethylene glycol and 1.0 to 15% by weight, preferably 2.0 to 12.0% by weight, particularly preferably 3.0 to 10.0% by weight, of water, The amounts of the components therein total 100% by weight and are based on the composition.

7. Use of a composition as claimed in any one of the preceding claims as a wetting agent, defoamer or dispersing aid in a coating composition.

8. Use of the composition according to any of the preceding claims in varnishes, paints, ink formulations, as an auxiliary in the fields of agriculture, building materials, plant protection, textile finishing, hydrophobization and electroplating, latex dipping processes, metalworking fluids and printed circuit board coatings.

9. A method for producing a composition according to any one of claims 1 to 6, comprising the following steps: a. Provide polyethylene glycol, b. Add water, C. Add ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, d. Add molten 2,4,7,9-tetramethyl-5-decyne-4,7-diol.

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