HK1127075B - Use of low-viscosity aqueous hot-cure flexible polyurethane foam stabilizer solutions containing polyethersiloxanes in the production of polyurethane foams - Google Patents
Use of low-viscosity aqueous hot-cure flexible polyurethane foam stabilizer solutions containing polyethersiloxanes in the production of polyurethane foams Download PDFInfo
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Description
Technical Field
The subject matter of the present patent application relates to low-viscosity aqueous solutions of heat-curing flexible polyurethane foam stabilizers comprising polyether siloxanes and their use in the preparation of heat-curing flexible polyurethane foams, and also to heat-curing flexible polyurethane foams prepared by means of said heat-curing flexible polyurethane foam stabilizer solutions.
Background
Flexible polyurethane foams are currently used in different applications in the manufacture of mattresses, upholstered furniture or car seats. They are prepared by the reaction of isocyanates with polyols. The foam stabilizer is used to stabilize foaming during the preparation of the heat-cured flexible polyurethane foam. In the absence of these stabilizers, the surface tension of the reaction mixture during the preparation of the heat-cured flexible polyurethane foam is too high, meaning that the heat-cured flexible polyurethane foam will collapse during the preparation process.
Polyether siloxanes are used in particular for stabilizing thermally cured flexible polyurethane foams.
EP-A10520392 describes surface-active compositions for flexible polyurethane foams, which are mixtures comprising: component A) contains from 90 to 99.98% by weight of a surface-active "non-hydrolyzable" silicone polyether which can be used in conventional flexible polyurethane foams and which comprises a silicone chain having at least 26 Si atoms and no endcapping groups; and component B) contains 0.02 to 10% by weight of a compound of the formula AaMmA salt of an organic acid of (a); the weight values are based on the total weight of the silicone polyether and the organic acid salt.
Very high concentrations of polyether siloxanes in foam stabilizer mixtures typically lead to an increase in viscosity. A disadvantage is that a high viscosity is detrimental to the good flow behavior of the foam stabilizer mixture fraction during processing. A further disadvantage is that a rapid and at the same time homogeneous distribution of this foam stabilizer mixture in the thermally curing flexible polyurethane foam reaction mixture is not very possible.
The high viscosity of the foam stabilizer mixture containing polyether siloxanes is particularly disadvantageous in the production of thermally curing flexible polyurethane foams because it prevents or even makes impossible pumping in the mixing head. In the art, a viscosity of 5000 mPas is considered as an upper limit. Thus, this foam stabilizer mixture is mixed with an organic solvent, for example a low molecular weight diol, such as ethylene glycol, dipropylene glycol or diethylene glycol. In some cases, short-chain polyethers, vegetable oils or industrial solvents, such as propylene carbonate or phthalate compounds, are also used. All of these solvents have the disadvantage of introducing foreign substances into the thermally cured flexible polyurethane foam which are practically undesirable for foam production. Furthermore, these substances are to a greater or lesser extent environmentally hazardous and flammable.
Disclosure of Invention
It is an object of the present invention to provide a low-viscosity foam stabilizer mixture comprising high concentrations of polyether siloxanes which avoids at least one of the abovementioned disadvantages.
The object of the present invention is achieved by a low viscosity aqueous solution of a heat-curable flexible polyurethane foam stabilizer which can be used in the preparation of a heat-curable flexible polyurethane foam, wherein the low viscosity aqueous solution of a heat-curable flexible polyurethane foam stabilizer comprises the following components:
polyether siloxane of more than or equal to 40 weight percent and less than or equal to 70 weight percent,
more than or equal to 0.5 weight percent and less than or equal to 20 weight percent of organic surfactant,
not less than 10% by weight of water,
not less than 0% by weight of an organic solvent,
wherein the polyether siloxane has the following general formula (I)
R1-Si(CH3)2O-[Si(CH3)(OSi(CH3)2R0)O-]u-[Si(OSi(CH3)2R0)2O-]v-[Si(CH3)2O-]w-[SiCH3R2O-]x-[SiCH3R3O-]y-[SiCH3R4O]z-[SiR3R4O]t-Si(CH3)2-R5 (I)
Wherein
R0＝-O-[Si(CH3)2O-]w-[SiCH3R2O-]x-[SiCH3R3O-]y-[SiCH3R4O]z-Si(CH3)2-R5，
R1、R2、R3、R4And R5Are in each case identical to or different from one another, are alkyl or aryl radicals of 1 to 12 carbon atoms, or are-CH2-R6or-CH2-CH2-R6Or polyalkylene oxide polyethers of the general formula (II)
-CmH2mO(C2H4O)a(C3H6O)b(C4H8O)c(C6H5-C2H3O)d(C12H24O)gR7 (II)，
R6＝H、-C6H5-CN having C1-C10Alkyl, epoxy ring-CH of2O, -alkyl-OH, -aryl-OH, -Cl, -OH, -R8-O-R9、-R8-O-CO-R9Or a divalent bridging group linked to other siloxane groups, selected from alkylene groups, -R8-O-R9-、-R8-COO-R9-、-R8-O-R9-O-R8-、-R8-COO-R9-OOC-R8-、-R8-OOC-R9-COO-R8-，
R7H, alkyl, acyl, acetyl or aryl groups, alkyl-or aryl-urethane groupsA group or a divalent bridging group linked to other siloxane groups, selected from alkylene groups, -R8-O-R9-、-R8-COO-R9-、-R8-O-R9-O-R8-、-R8-COO-R9-OOC-R8-、-R8-OOC-R9-COO-R8-，
R8Either an alkylene group or an arylene group,
R9alkyl-, aryl-, alkylene or arylene,
u＝0-5，
v＝0-5，
t＝0-15，
w＝15-130，
x＝0-15，
y＝0-15，
z＝0-15，
m＝0-4，
a is more than or equal to 0 and less than or equal to 160,
b is more than or equal to 0 and less than or equal to 140,
c is more than or equal to 0 and less than or equal to 50,
g is more than or equal to 0 and less than or equal to 50,
d is more than or equal to 0 and less than or equal to 50, in the case that a + b + c + d + g is more than or equal to 10,
with the proviso that x + y + z + t.gtoreq.3 and at least one substituent R1、R2、R3、R4And R5Is a polyether of the general formula II, the weight fractions of the above-mentioned components being selected such that the total weight fraction of the components does not exceed 100% by weight, based on the heat-curing flexible polyurethane foam stabilizer solution.
The polyethers of the formula II can be random, block-wise or gradient-wise in their distribution of monomer units to the polymer chains.
The polyether siloxane component of the heat-curable flexible polyurethane foam stabilizer solution may also be comprised of two or more polyether siloxanes of the general formula I.
Unless otherwise specified, the weight fractions of the above components are selected so that the total weight fraction of the components does not exceed 100% by weight, based on the heat-curable flexible polyurethane foam stabilizer solution.
Unless otherwise stated, the weight values are based on the total weight of the heat-curable flexible polyurethane foam stabilizer solution.
Unless otherwise indicated, each component may take the form of a single component or a mixture. In practice, polyether siloxanes preferably form a mixture. Likewise, it is preferred for the surfactant to take the form of a mixture of surfactants.
The polyether siloxanes, organic surfactants, water, organic solvents, and, if desired, further additives, the compounds which can be used according to the invention differ from one another in each case. For example, the surfactant does not comprise the polyether siloxane of formula I used in the present invention or the organic solvent does not comprise an organic surfactant, and vice versa.
It has been surprisingly found that the heat-curable flexible polyurethane foam stabilizer solutions of the present invention exhibit much lower viscosities than otherwise identical compositions lacking a surfactant.
The heat-curing flexible polyurethane foam stabilizer solution of the invention may comprise preferably from ≥ 10% to ≤ 60% by weight of water, in particular from ≥ 15% to ≤ 59.5% by weight of water, and from ≥ 0% to ≤ 20% by weight of organic solvent.
The heat-curable flexible polyurethane foam stabilizer solution of the present invention may have a viscosity that is at least 10%, preferably at least 20%, more preferably at least 30%, even more preferably at least 40%, even more preferably at least 50%, and most preferably at least 60% lower than the viscosity of an otherwise identical composition lacking the surfactant.
It is particularly preferred if the low-viscosity aqueous solutions of the heat-curing flexible polyurethane foam stabilizers of the invention have a viscosity of < 5000 mPas.
It is even more preferred if a low-viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer of the present invention comprising from ≥ 40% by weight to ≤ 50% by weight of the polyether siloxane, based on the total weight of the heat-curable flexible polyurethane foam stabilizer solution, has a viscosity in the range from ≥ 0.05 pas to ≤ 3 pas, preferably from ≥ 0.01 pas to ≤ 2 pas, and more preferably from ≥ 0.15 pas to ≤ 1 pas.
It is also preferable if a low-viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer of the present invention comprising from not less than 50% by weight to not more than 65% by weight of a polyether siloxane, based on the total weight of the heat-curable flexible polyurethane foam stabilizer solution, has a viscosity in the range of from not less than 0.1 pas to not more than 5 pas, preferably from not less than 0.3 pas to not more than 4.5 pas, and more preferably from not less than 0.4 pas to not more than 4 pas.
As organic solvents, solvents selected from dipropylene glycol, butylene glycol, ethylene glycol, diethylene glycol, propylene glycol, phthalates, polyesters, animal and vegetable oils, mineral oils and/or antifreeze liquid forms can be used.
It is particularly preferred that the organic solvent comprises an anti-freeze agent selected from dipropylene glycol and/or propylene glycol.
According to a further embodiment of the present invention, it is also possible that the organic solvent is not added to the low viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer.
It is obvious to the skilled person that the compounds used according to the invention are present in the form of a mixture whose distribution is essentially controlled by statistical rules. Thus, the values of x, y, z, t, u, v, w, m, a, b, c, d and/or g correspond to average values.
Preferably for R according to the invention1And R5Which may be identical to or different from one another in each case are methyl, ethyl or propyl. Particular preference is given to R1And R5Is methyl.
the value of t may preferably be 2 to 15 and more preferably 4 to 13, or 0.
The value of u may preferably be 0 to 4 and more preferably 1 to 2, or 0.
The value of v may preferably be 0 to 4 and more preferably 1 to 2, or 0.
The value of w may be 20 to 120, in particular 30 to 110, preferably 40 to 100, more preferably 50 to 95, particularly preferably 55 to 90, and very particularly preferably 60 to 85. Alternatively, the value of w may preferably be 40-130 if u + v ≦ 0, or 20-65 if u + v > 0 to ≦ 1, or 13-43 if u + v > 1.
The value of x may preferably be 2 to 15 and more preferably 4 to 13, or 0.
The value of y may preferably be 2 to 15 and more preferably 4 to 13, or 0.
The value of z may preferably be 2 to 15 and more preferably 4 to 13, or 0.
The value of a may preferably be 1 to 105, more preferably 5 to 100, and most preferably 10 to 90.
The value of b may preferably be 1 to 105, more preferably 5 to 100, and most preferably 10 to 90.
The value of c may preferably be 1 to 40, more preferably 2 to 30, and most preferably 2 to 20, or 0.
The value of d may preferably be 1 to 40, more preferably 2 to 30, and most preferably 2 to 20, or 0.
The value of g may preferably be 1 to 40, more preferably 2 to 30, and most preferably 2 to 20, or 0.
The value of m may preferably be 1 to 4 and more preferably 2 to 3.
According to a preferred embodiment, the polyether siloxane has the following general formula III:
wherein
n-50 to 120, preferably 60 to 100, and more preferably 65 to 90,
o-3-20, preferably 3.5-18, and more preferably 4-15, and
PE has the following general formula IV:
wherein
X ═ H, alkyl, acyl, acetyl, or aryl groups,
e.gtoreq.0 to 100, preferably 1 to 50, more preferably 3 to 40, and particularly preferably 5 to 30,
f.gtoreq.0 to 120, preferably 1 to 50, more preferably 5 to 40, and particularly preferably 10 to 30, wherein e + f.gtoreq.15.
PE here also represents a mixture of different polyethers, but they are all represented by the formula IV.
The use of water has further advantages over organic solvents: water is almost unlimited to obtain and is non-toxic and non-flammable. Furthermore, in the case of cleaning, the aqueous solution is easy to remove and can be discarded without technical complexity. A further advantage is that the safety measures for storage of the aqueous solution are generally less stringent. In summary, the use of water as a solvent can significantly reduce the complexity compared to non-aqueous systems, and thus can reduce the production cost of the heat-curable flexible polyurethane foam stabilizer solution of the present invention.
According to a preferred embodiment, the heat-curable flexible polyurethane foam stabilizer solution of the present invention comprises mainly water as a solvent.
The polyether siloxanes which can be used according to the invention are generally prepared by platinum-catalyzed addition reactions of siloxanes containing silane hydrogen atoms with linear polyalkylene oxide polyethers which are terminated at the reactive end by an alkenyloxy group, such as allyloxy or vinyloxy, and at the other end, for example, by an alkoxy, arylalkoxy or acyloxy group. The polyethers are prepared by alkoxylating allyl alcohols or higher molecular weight hydroxyl-functionalized allyl or vinyl compounds. Alternatively, the OH groups of the polyether may be capped after hydrosilylation. Only or mainly in this case, uncapped polyethers are used for hydrosilylation.
The preparation of polyether siloxanes is generally proposed and described in patents including EP-A10520392 and EP-A11350804, which are incorporated herein by reference.
The end groups of the polyether may start with alkoxylation, initially having free OH functionality. Such hydroxyl groups may also be present, at least in part, in the polyether siloxanes of the present invention. However, in the case of the preferred polyether siloxanes, the end groups are completely or at least predominantly blocked. This can be carried out by esterification, preferably acetylation, or etherification, preferably methylation, of the free OH functions.
The polyether siloxanes which can be used according to the invention can in particular be highly stable to hydrolysis, so that the polyether siloxanes of the invention can be designed to be stable to hydrolysis.
The polyether siloxanes which can be used according to the invention have high molecular weights, making their own viscosity too high for direct processing. The viscosity of the polyether siloxane can be more than or equal to 1000 mPas at 25 ℃; for most polyether siloxanes used to stabilize heat-cured flexible polyurethane foams, this value is greater than 3000mPa · s at 25 ℃; the specific representation of the viscosity for the polyether siloxanes according to the invention is that the viscosity is even just below 6000 mPas at 25 ℃. However, in the production of thermally cured flexible polyurethane foams, high viscosity constitutes a problem, one reason for which is the hindrance to pumping in the mixing head.
In the prior art, therefore, polyether siloxanes have been diluted with organic solvents, which dilution is associated with the disadvantages mentioned above. Typical polyether siloxanes in prior art heat-curable flexible polyurethane foam stabilizers are present in amounts of 50 to 70% by weight, the remainder being organic solvents.
Since a drastic increase in viscosity is observed in the mixtures when the polyether siloxanes according to the invention are prepared in a concentration of 40 to 80% by weight of polyether siloxanes with water, the use of water as solvent for the polyether siloxanes as stabilizers in heat-curing flexible polyurethane foams has hitherto not been considered. The viscosity significantly exceeds the level of the polyether siloxane itself. The reason for the increased viscosity is the appearance of the lyotropic liquid crystalline phase. These phases are based on a multidimensional ordered stack of amphoteric surfactant molecules. Such amphoteric surfactant molecules also include, for example, the polyether siloxanes used in accordance with the present invention. Such lyotropic (lyotropic) mesophases generally have an anisotropic distribution of physical properties in space. Depending on the particular mode of stacking, the viscosity has a value that completely inhibits the material from flowing and thus produces a gel-like character.
For example, aqueous solutions with a fraction of 40% by weight of polyether siloxane already have a viscosity of well above 5Pa · s, based on the aqueous solution, and so it is no longer possible to speak of low-viscosity aqueous solutions at this level. Aqueous solutions with a fraction of polyether siloxane of 50 to 70% by weight have even higher viscosities, usually much higher than 50Pa · s. The viscosity maximum is reached at about 60 wt.% polyether siloxane and 40 wt.% water.
Owing to their low concentration, aqueous solutions of polyether siloxanes having a fraction of < 40% by weight are not suitable, not least because, when preparing high-density thermally cured flexible polyurethane slabstock foams, an increase in the amount of water adversely affects the cell density distribution and in particular the foam density, because water acts as a chemical blowing agent for the preparation of thermally cured flexible polyurethane foams. Thus, with such large amounts of water in the stabilizer mixture, it is only possible to prepare foams having a lower density (larger amounts of water used in total). A further disadvantage of such highly diluted solutions is the transportation costs, which are higher than those of more concentrated solutions, and which deviate from the accepted activity levels of heat-curing flexible polyurethane foam stabilizers.
Aqueous solutions with a polyether siloxane content of > 80% by weight are likewise unsuitable due to the high viscosity. Water amounts of < 20% by weight are not suitable for reducing the viscosity, sufficient to give low-viscosity polyether siloxane solutions. Here, in fact, it is often the case that addition of < 20% by weight of water results in an increase in viscosity compared to the polyether siloxane itself. This is not changed at all without the addition of surfactant.
The preferred low-viscosity aqueous solutions of heat-curing flexible polyurethane foam stabilizers of the invention have a content of polyether siloxanes of from 40 to 70% by weight and a viscosity at 25 ℃ of < 5000 mPas (5Pa s).
It has now surprisingly been found that the occurrence of high viscosities in aqueous mixtures of 40 to 70% by weight of polyether siloxanes can be suppressed by the addition of organic surfactants. Anionic surfactants are particularly effective in this context.
Preferred aqueous heat-curing flexible polyurethane foam stabilizer solutions have a low viscosity and therefore good rheological behaviour. The solutions of the heat-curing flexible polyurethane foam stabilizers according to the invention may have a viscosity of from ≥ 100 mPa.s to ≤ 5000 mPa.s, preferably from ≥ 500 mPa.s to ≤ 3000 mPa.s, more preferably from ≥ 700 mPa.s to ≤ 2000 mPa.s, and particularly preferably from ≥ 900 mPa.s to ≤ 1800 mPa.s, using a MCR301 rotational viscometer from Physica (Anton Paar, Ostfildern, Germany) at 1s-1The viscosity was measured in a spinning experiment at 25 ℃. Samples with a viscosity > 100mPa · s were measured using a cone/plate geometry (diameter 50.0mm, angle 0.981 °). Couette geometry (measuring element diameter ═ is used26.66mm, measuring beaker diameter 28.93mm, measuring slit width 1.135mm, measuring slit length 40.014mm) samples of viscosity < 100mPa · s were investigated. Since some samples exhibited structural viscosity characteristics, the initial conditions for creating control were first at 1000s-1The sample was sheared down for 60 seconds. The sample was then held without shear for 10 minutes. During which the structure may be produced again. Thereafter, at 1s-1The viscosity is measured at a shear rate of (a). For this measurement, shear was performed for up to 10 minutes until equilibrium was reached. Without pretreatment, at 1s-1Samples that do not exhibit structural viscosity behavior are measured directly until equilibrium is reached.
The advantage is that stable, storable heat-curable flexible polyurethane foam stabilizer solutions can be obtained which, despite the use of water as solvent within the scope of the claims, exhibit no tendency, or virtually no tendency, during storage of the heat-curable flexible polyurethane foam stabilizer solution, to form precipitates which settle on the base of the container or rise. This is advantageous because a heat-curable flexible polyurethane foam stabilizer having an effectively uniform distribution of components can thus be obtained.
A further advantage of these aqueous solutions of the heat-curable flexible polyurethane foam stabilizers of the present invention is that they remain clear and homogeneous even as the temperature increases. Thus, in some cases, no change was observed in aqueous solutions up to well above 50 ℃.
A further advantage of the aqueous, heat-curing, flexible polyurethane foam stabilizer solutions of the invention is that small amounts, for example from 5 to 10% by weight, of components which act as antifreeze agents can be added. Suitable substances are, for example, low molecular weight monoalcohols or diols, for example ethanol, isopropanol, dipropylene glycol, ethylene glycol or butanediol. Such freeze-stable aqueous solutions of the heat-curable flexible polyurethane foam stabilizers of the present invention do not freeze even at-20 ℃.
Freezing of heat-cured flexible polyurethane foam stabilizer solutions is potentially a big problem, as it can happen that only water freezes and polyether siloxanes cannot be incorporated into the ice structure, leading to phase separation upon melting. However, this problem strongly depends on the cooling rate during freezing and on the chemical structure of the polyether siloxanes, and is therefore not observed for all low-viscosity solutions of the heat-curing flexible polyurethane foam stabilizers according to the invention. However, if phase separation is observed, it should be eliminated by vigorous stirring.
However, the aqueous solutions of the freeze-stable, heat-curable flexible polyurethane foam stabilizers are very highly viscous at low temperatures. However, this process is not problematic because the raw materials for the preparation of the heat-cured flexible polyurethane foam are generally adjusted to room temperature (23 ℃). After cooling, the freeze-stable, heat-curing, flexible polyurethane foam stabilizer aqueous solution is heated to room temperature, and a low-viscosity solution of heat-curing, flexible polyurethane foam stabilizer is obtained again.
A further advantage of the heat-curing flexible polyurethane foam stabilizer solutions according to the invention is that it is now also possible to add without problems additional substances which are very hydrophilic and do not dissolve at all or at least only to a very incomplete extent in pure polyether siloxanes or in solutions of polyether siloxanes in organic solvents. These are, on the one hand, salt-like additives and, on the other hand, polyhydroxy-functional additives. As regards the first group concerned, for example, lithium, sodium or potassium salts may be added. These salts also act as antifreeze. The added salt may also play a catalytic role during the preparation of the heat-cured flexible polyurethane foam. The fraction of the additionally added salt-based compound may preferably be not less than 0% by weight and not more than 5% by weight based on the heat-curable flexible polyurethane foam stabilizer solution. As electrolytes selected from inorganic salts, a very large number of very different kinds of salts can be used. Preferred cations are from alkali metals and alkaline earth metals, and preferred anions are from halides, sulfates and carboxylates, for example from alkali metal benzoates or alkali metal acetates.
The heat-curable flexible polyurethane foam stabilizer solution of the present invention may preferably further comprise a polyhydroxyl functional additive having a hydroxyl functionality of 3 or more and serving as a cross-linking agent in the preparation of the heat-curable flexible polyurethane foam. The fraction of these polyhydroxy-functional compounds may be between 0% by weight and 10% by weight, based on the heat-curing flexible polyurethane foam stabilizer solution. The polyhydroxy-functional compound may preferably be selected from glycerol, trimethylolpropane, pentaerythritol, water-soluble low molecular weight carbohydrates, especially monomeric or dimeric glycosides, and water-soluble sugar alcohols, preferably sorbitol.
The use of polyhydroxy-functional compounds having a functionality of > 3 is possible to advantage, since these compounds, in addition to the physical stabilization by the polyether siloxanes, can also contribute to the chemical stabilization by increasing the crosslinking in the preparation of thermally cured flexible polyurethane foams. These crosslinking agents allow additional control of the foaming behavior when added to aqueous solutions of stabilizers of low concentration, which has hitherto only been possible by addition of the crosslinking agent alone.
In addition, the heat-curable flexible polyurethane foam stabilizer solution of the present invention may further contain typical additives such as catalysts, blowing agents, biocides and/or flame retardants. The insecticide may, where appropriate, reduce the risk of microbial contamination of the aqueous solution of the heat cured flexible polyurethane foam and thus increase the shelf life. Pesticides that can be used appropriately are in particular those listed in the substance list of European biological products Directive 98/8/EC.
Other additional additives that may be used include antioxidants. These antioxidants can extend the oxidizing power of aqueous solutions of heat-curable flexible polyurethane foam stabilizers. Suitable antioxidants are preferably sterically hindered phenols, such as Butylated Hydroxytoluene (BHT).
In addition, buffer substances may also be used as additional additives in order to set a neutral or weakly alkaline pH. Suitable buffer substances are preferably phosphate buffers, borate buffers, amino acids, carbonate buffers, or buffers based on salts of tertiary amines.
Polyether siloxanes having broad molecular weight distributions can be used to obtain stable, heat-cured, flexible polyurethane foam stabilizer solutions. According to the invention, polyethersiloxanes having a molar mass of from 10000g/mol to 50000g/mol, preferably from 13000g/mol to 40000g/mol and more preferably from 15000g/mol to 35000g/mol can be used.
It has also been shown that heat-curable flexible polyurethane foam stabilizer solutions comprising polyether siloxanes in which the polyether units have a molar mass of from 500g/mol to 7000g/mol, preferably from 1000g/mol to 6000g/mol, more preferably from 2000g/mol to 5000g/mol, have good product properties with regard to the stability of the solution and/or the concentration profile of the polyether siloxane component. It is therefore particularly preferred that at least one polyether unit has an average molar mass of Mn.gtoreq.2100 g/mol.
The fraction of ethylene oxide in the polyethers which can preferably be used according to the invention can be from 10 to 100% by weight, the amount of propylene oxide then being modified accordingly; in other words, at 10% by weight of ethylene oxide, the fraction of propylene oxide in the polyether units is 90% by weight, and if the content of ethylene oxide is 100% by weight, the fraction of propylene oxide in the polyether units is 0% by weight.
However, in a preferred embodiment of the invention, the fraction of propylene oxide in the polyether units may also be from 10 to 100% by weight, in which case the ethylene oxide content is then modified accordingly; in other words, at 10% by weight of propylene oxide, the fraction of ethylene oxide in the polyether units is 90% by weight, and if the content of propylene oxide is 100% by weight, the fraction of ethylene oxide in the polyether units is 0% by weight.
If the fraction of propylene oxide of the polyether siloxane, which exceeds on average all polyether units, is from 40 to 90% by weight, preferably > 50% by weight, more preferably > 55% by weight and particularly preferably > 60% by weight, a heat-curable flexible polyurethane foam stabilizer solution is obtained which has good properties with respect to the pore distribution and quality of the heat-curable flexible polyurethane foam.
However, it is additionally possible to incorporate other alkylene oxides in the polyether. They include in particular butylene oxide, dodecene oxide and styrene oxide.
For the uses relating to heat-curing flexible polyurethane foams, it is particularly suitable according to the invention to provide a heat-curing flexible polyurethane foam stabilizer solution, wherein the heat-curing flexible polyurethane foam stabilizer solution comprises:
a content of polyethersiloxane of from ≥ 42% by weight to ≤ 68% by weight, preferably from ≥ 45% by weight to ≤ 65% by weight, and more preferably from ≥ 47% by weight to ≤ 62% by weight, particularly preferably from 50% by weight to 60% by weight,
an organic surfactant in an amount of from ≥ 1% by weight to ≤ 10% by weight, preferably from ≥ 2% by weight to ≤ 8% by weight, and more preferably from ≥ 4% by weight to ≤ 6% by weight,
from ≥ 15% by weight to ≤ 55% by weight, preferably from ≥ 20% by weight to ≤ 50% by weight, and more preferably from ≥ 30% by weight to ≤ 40% by weight of water, and
an organic solvent, preferably an organic solvent used as an antifreeze, in an amount of from ≥ 0% by weight to ≤ 15% by weight, preferably from ≥ 1% by weight to ≤ 10% by weight, and more preferably from ≥ 2% by weight to ≤ 5% by weight.
The heat-curable flexible polyurethane foam stabilizer solution may contain other additives as supplementary components, if necessary. The fractions of the above components of the heat-curing flexible polyurethane foam stabilizer solution are selected in each case such that the total fraction of the components does not exceed 100% by weight.
A preferred heat-curable flexible polyurethane foam stabilizer solution of the present invention comprises:
from 45% by weight or more to 55% by weight or less, preferably 50% by weight, of a polyether siloxane,
from ≥ 1% by weight to ≤ 10% by weight, preferably from ≥ 2% by weight to ≤ 8% by weight and more preferably 5% by weight of an alkylbenzenesulfonate,
from ≥ 30% by weight to ≤ 50% by weight, preferably ≥ 35% by weight to ≤ 45% by weight, and more preferably 40% by weight of water, and
dipropylene glycol in an amount of from ≥ 1% by weight to ≤ 10% by weight, preferably from ≥ 3% by weight to ≤ 7% by weight, and more preferably 5% by weight.
The heat-curable flexible polyurethane foam stabilizer solution may contain other additives as supplementary components, if necessary. The fractions of the above components of the heat-curing flexible polyurethane foam stabilizer solution are selected in each case such that the total fraction of the components does not exceed 100% by weight.
It is obvious per se that the components are matched to one another in such a way that the viscosity is minimized. The viscosity ranges required for the present invention have been described above for heat-curing flexible polyurethane foam stabilizer solutions. The desired viscosity can be set by appropriately increasing or decreasing the fraction of organic surfactant and/or the ratio of water to polyether siloxane. The viscosity of the heat-curing flexible polyurethane foam stabilizer solution can be further influenced if desired by a corresponding addition of inorganic salts.
In order to ensure a good concentration distribution of the heat-curable flexible polyurethane foam stabilizer solution in the heat-curable flexible polyurethane foam reaction mixture, it is preferable to use a homogeneous and transparent solution of the heat-curable flexible polyurethane foam stabilizer solution. Such transparent, heat-curable, flexible polyurethane foam stabilizer solutions may take the form of, for example, clear or slightly cloudy solutions. Suitable transparent heat-curable flexible polyurethane foam stabilizer solutions may also have, for example, an opaque shimmer (shim).
If the viscosity is above 5000 mPas, a heat-curable flexible polyurethane foam stabilizer solution containing flocs or precipitates is unsuitable according to the invention.
By appropriately setting the proportions of water, surfactant and polyether siloxane, the formation of flocs and/or precipitates can be avoided, wherein increasing the concentration of surfactant and simultaneously decreasing the polyether siloxane concentration yields low-viscosity solutions of the preferred heat-curable flexible polyurethane foam stabilizers of the invention.
The heat-curable flexible polyurethane foam stabilizer solution of the present invention is storage stable at room temperature. It has been shown that the heat-curable flexible polyurethane foam stabilizer solutions of the present invention do not exhibit phase separation and/or precipitation over a period of at least 14 days. The components can be used: the proportions of organic surfactant, polyether siloxane, water and, if desired, inorganic salts set high storage stability and precipitation, such as flocs, can also be avoided.
The preferred heat-curable flexible polyurethane foam stabilizer solutions according to the invention are free of flocs and/or precipitates.
Despite their high water content, the heat-curable flexible polyurethane foam stabilizer solutions of the invention are also notable for an increased cloud point compared with polyether siloxanes in water without surfactants. The preferred heat-curable flexible polyurethane foam stabilizer solutions of the present invention have a cloud point of 40 ℃ or higher, preferably 50 ℃ or higher, more preferably 60 ℃ or higher.
The organic surfactant which may be used in the heat-curing flexible polyurethane foam stabilizer solution may be selected from anionic, cationic, nonionic and/or amphoteric surfactants, said organic surfactant preferably being an anionic surfactant. The heat-curable flexible polyurethane foam stabilizer solution according to the present invention preferably comprises one or more surfactants selected from anionic, cationic, amphoteric (amphiphilic, zwitterionic) surfactants and mixtures thereof.
A typical list of anionic, cationic, nonionic and amphoteric (zwitterionic) classes and types of these surfactants is given in U.S. patent No. 3,929,678 and U.S. patent No. 4,259,217, which are incorporated herein by reference in their entirety.
In general, it is preferred to use amphoteric, amphiphilic (amphoteric) and zwitterionic surfactants in combination with one or more anionic and/or nonionic surfactants.
Anionic surfactants
The compositions of the present invention preferably comprise an anionic surfactant. Essentially any anionic surfactant suitable for cleaning may be present in the heat-curable flexible polyurethane foam stabilizer solution. Such surfactants may include salts including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as the mono-, di-and tri-ethanolamine salt surfactants of anionic sulfuric, sulfonic, carboxylic and sarcosinates. Anionic sulfate and sulfonate surfactants are preferred.
Very much preferred are surfactant systems comprising sulfonate surfactants or sulfate surfactants, preferably linear or branched alkyl benzene sulfonates and alkyl ethoxy sulfates as described herein, optionally in combination with cationic surfactants as described herein.
Other anionic surfactants include isethionates, e.g. acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C)12-C18Monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C)6-C14Diesters), and N-acyl sarcosinates. Resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow, are also suitable.
Anionic sulfate surfactants
Anionic sulfate surfactants suitable for the application of interestContaining linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil alkenyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C17-acyl-N-(C1-C4-alkyl) -and-N- (C)1-C2Hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides, such as alkyl polyglycoside sulfates (non-ionic, non-sulfated compounds described herein).
The alkyl sulfate surfactant is preferably selected from linear and branched, primary and secondary C10-C18Alkyl sulfates, more preferably branched C11-C15Alkyl sulfates and straight chain C12-C14An alkyl sulfate.
The alkyl ethoxy sulfate surfactant is preferably selected from the group consisting of C ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule10-C18An alkyl sulfate. More preferably, the alkyl ethoxy sulfate surfactant is C ethoxylated with 0.5 to 7 moles, preferably 1 to 5 moles, of ethylene oxide per molecule11-C18More preferably C11-C15Alkyl sulfates of (2).
A particularly preferred aspect of the invention uses a mixture of preferred alkyl sulphate and/or sulphonate and alkyl ethoxy sulphate surfactants. Such mixtures have been disclosed in PCT patent application WO 93/18124, which is incorporated herein by reference in its entirety.
Anionic sulfonate surfactants
Anionic sulfate surfactants suitable for the application of interest comprise straight chain C5-C20Alkyl benzene sulphonate, alkyl ester sulphonate, primary or secondary C6-C22Alkane sulfonate, C6-C24Olefin sulfonates, aryl sulfonates (especially unsubstituted and alkyl-substituted benzene-and naphthalene-sulfonates), sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, monoesters of sulfosuccinates (especially saturated and unsaturated)Saturated C12-C18Monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C)6-C14Diesters), fatty oil alkenyl glycerol sulfonates, and any desired mixtures thereof.
Anionic carboxylate surfactants
Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps ("alkylcarboxylates"), particularly the specific secondary soaps (secondary soaps) described herein.
Suitable alkyl ethoxy carboxylates comprise those having the general formula RO (CH)2CH2O)xCH2COO-M⊕Wherein R is C6-C18X is in the range of 0-10, and the ethoxylation distribution is such that the amount of material with x being 0 is less than 20 wt%, and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants comprise those having the general formula RO (CHR)1-CHR2-O)-R3Wherein R is C6-C18X is 1-25, R1And R2Selected from the group consisting of hydrogen, formate, succinate, hydroxysuccinate, and mixtures thereof, and R3Selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbons having 1 to 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include secondary soap surfactants containing a carboxyl group attached to a secondary carbon. The preferred secondary soap surfactant for use in the heat-curable flexible polyurethane foam stabilizer solution of the present invention is a water-soluble component selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid, and 2-pentyl-1-heptanoic acid.
Sarcosinate surfactants
Other suitable anionic surfactants are those of the formula R-CON (R)1)CH2Sarcosinates of COOM, whereinR is straight or branched C5-C17Alkyl or alkenyl radicals, R1Is C1-C4Alkyl, and M is an alkali metal ion. Preferred examples are myristyl-and oleoylmethyl sarcosinates in the form of their sodium salts.
The anionic surfactant may particularly preferably be selected from the following: alkyl sulfates, aryl sulfonates, sulfates of fatty alcohols, secondary alkyl sulfates, paraffin sulfonates, alkyl ether sulfates, alkyl polyglycol ether sulfates, fatty alcohol ether sulfates, alkylbenzene sulfonates, alkylphenol ether sulfates, alkyl phosphates, phosphoric acid mono-, di-, tri-esters, alkyl ether phosphates, ethoxylated fatty alcohol phosphates, phosphonates, sulfosuccinic diesters, sulfosuccinic monoesters, ethoxylated sulfosuccinic monoesters, sulfosuccinic acid amides, alpha-olefin sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl polyethylene glycol carboxylates, fatty acid isethionates, fatty acid methyl taurates, fatty acid sarcosines, arylsulfonates, naphthalenesulfonates, alkylglyceryl ether sulfonates, polyacrylates, and/or alpha-sulfo fatty acid esters.
Cationic surfactant
Suitable cationic surfactants for use as the surfactant component of the solution for heat curing flexible polyurethane foam stabilizers include quaternary ammonium surfactants. The quaternary ammonium surfactant is preferably mono-C6-C16preferably-C6-C10-N-alkyl-or-alkenylammonium surfactants, the remaining N-positions being substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preference is likewise given to mono-and di-alkoxylated amine surfactants.
Another suitable group of cationic surfactants that can be used in the heat-curable flexible polyurethane foam stabilizer solution are cationic ester surfactants.
The cationic ester surfactant is preferably a water dispersible compound having surfactant properties comprising at least one ester linkage (i.e., -COO-) and at least one cationic-charged group.
Suitable cationic ester surfactants include choline ester compounds such as disclosed in U.S. patents 4,228,042, 4,239,660, and 4,260,529.
From a preferred perspective, the ester linkage and the cation-carrying group in the surfactant molecule are separated from each other by a spacer group consisting of a chain comprising at least 3 atoms (i.e., a chain length of 3 atoms), preferably 3 to 8 atoms, more preferably 3 to 5 atoms, and most preferably 3 atoms. The atoms forming the spacer chain are selected from carbon, nitrogen and oxygen atoms and any mixtures thereof, provided that each nitrogen or oxygen atom in the chain is attached only to carbon atoms in the chain. Thus, for example, spacer groups containing-O- (i.e.peroxides), -N-and-N-O-bonds are excluded, and for example containing-CH2-O-CH2-and-CH2-NH-CH2-a spacer group of bonds. From a preferred perspective, the spacer chain contains only carbon atoms, and most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Cationic mono-alkoxylated amine surfactants which may preferably be used have the general formula V:
R1R2R3N⊕ZnR4X- (V)
wherein R is1Is an alkyl or alkenyl unit having 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, most preferably 6 to 14 carbon atoms; r2And R3Each independently is an alkyl group having 1 to 3 carbon atoms, preferably methyl, and most preferably R2And R3Are both methyl; r4Selected from hydrogen (preferred), methyl and ethyl; x-Is an anion, such as chloride, bromide, methyl sulfate, and the like, thereby providing electrical neutrality; z is alkoxy, in particular ethoxy, propoxy or butoxy; and n is 0 to 30, preferably 2 to 15,most preferably 2 to 8.
Z in the formula VnR4The radical preferably has n ═ 1 and is a hydroxyalkyl radical having not more than 6 carbon atoms, the-OH group being separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Particularly preferred ZnR4The radical being-CH2CH2OH、-CH2CH2CH2OH、-CH2CH(CH3) OH and CH (CH)3)CH2OH，-CH2CH2OH is particularly preferred. Preferred R1The groups are straight chain alkyl groups. Straight-chain R having 8 to 14 carbon atoms1Groups are preferred.
Preferred cationic mono-alkoxylated amine surfactants which may also be preferably used have the general formula VI:
wherein R is1Is C10-C18Hydrocarbyl radicals and mixtures thereof, especially C10-C14Alkyl, preferably C10And C12Alkyl, X is any suitable anion to provide charge compensation, preferably chloride or bromide. Ethoxy (CH) of the formula II2CH2The O-) units (EO) may also be substituted by butoxy, isopropoxy [ CH (CH)3)CH2O]-、[CH2CH(CH3)O]Units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
Cationic bis-alkoxylated amine surfactants
The cationic bis-alkoxylated amine surfactant preferably has the general formula VII:
wherein R is1Is an alkyl or alkenyl unit having from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 10 to 14 carbon atoms; r2Is an alkyl group having 1 to 3 carbon atoms, preferably methyl; r4And R5Can be independently varied and is selected from hydrogen (preferred), methyl and ethyl; and X-Is an anion, such as chloride, bromide, methylsulfate, sulfate, and the like, sufficient to provide electrical neutrality. Z can be varied independently of one another and is in each case C1-C4Alkoxy, especially ethoxy (i.e. -CH)2CH2O-), propoxy, butoxy, and mixtures thereof; n is identical or different in each case and is from 1 to 30, preferably from 1 to 4 and most preferably 1.
Preferred cationic bis-alkoxylated amine surfactants have the general formula VIII:
wherein R is1Is C10-C18Hydrocarbyl radicals and mixtures thereof, preferably C10、C12、C14Alkyl groups and mixtures thereof, and X is any suitable anion to provide charge compensation, preferably chlorine. With reference to the general structure of the cationic bis-alkoxylated amines described above, in one preferred compound R1Derived from (coconut) C12-C14An alkyl fatty acid.
More suitable cationic bis-alkoxylated amine surfactants comprise compounds of formula IX:
wherein R is1Is C10-C18A hydrocarbon group, preferably C10-C14Alkyl, independently p is 1-3 and q is 1-3, R2Is C1-C3Alkyl, preferably methyl, and X is an anion, preferably chlorine or bromine.
Other compounds of the above type include those in which the ethoxy group (CH)2CH2The O-) units (EO) may also be substituted by butoxy (Bu), isopropoxy [ CH (CH)3)CH2O]And [ CH2CH(CH3)O]Units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The cationic surfactant may particularly preferably be selected from ester quaternary ammonium compounds, preferably di (tallow fatty acid amidoethyl) methyl polyethoxy ammonium methyl sulphate, diamido quaternary ammonium compounds, alkoxy alkyl quaternary ammonium compounds, preferably coco pentaethoxy methyl ammonium methyl sulphate (coco pentaethoxy methyl ammonium methosulfate), and/or trialkyl quaternary ammonium compounds, preferably cetyl trimethyl ammonium chloride.
Nonionic surfactant
Substantially all nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants may be selected from the following classes: nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated condensates with propylene glycol, and addition products of nonionic ethoxy condensation products with propylene oxide/ethylene diamine.
Nonionic surfactants for alkoxylated alcohols
Condensation products of fatty alcohols with from 1 to 25mol of alkylene oxides, in particular ethylene oxide, propylene oxide, butylene oxide, dodecene oxide or styrene oxide, are likewise suitable according to the invention. The alkyl chain of the aliphatic alcohol may optionally be straight or branched, primary or secondary, and typically contains from 6 to 22 carbon atoms. Particular preference is given to condensation products of alcohols having an alkyl group having from 8 to 20 carbon atoms with from 2 to 10mol of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactants
Suitable polyhydroxy fatty acid amides are those of the formula R2CONR1Z wherein R1Is H, C1-C4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably C1-C4Alkyl, more preferably C1Or C2Alkyl, most preferably C1Alkyl (i.e., methyl); and R is2Is C5-C31Hydrocarbyl, preferably straight chain C5-C19Alkyl or alkenyl, more preferably straight-chain C9-C17Alkyl or alkenyl, most preferably straight chain C11-C17Alkyl or alkenyl groups, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain in which at least 3 hydroxyls are directly linked to the chain, or an alkoxylated derivative (preferably an ethoxylated or propoxylated derivative) thereof. Z preferably results from reductive amination of a reducing sugar; more preferably Z is glycidyl.
Nonionic fatty acid amide surfactants
Suitable fatty acid amide surfactants include those having the general formula R6CON(R7)2Wherein R is6Is an alkyl group having 7 to 21, preferably 9 to 17 carbon atoms and each R7Selected from hydrogen, C1-C4Alkyl radical, C1-C4Hydroxyalkyl and- (C)2H4O)xH, wherein x is in the range of 1-3.
Nonionic alkyl polysaccharide surfactants
Suitable alkyl polysaccharide surfactants for use in the context of the present invention are disclosed in U.S. Pat. No. 4,565,647 having a hydrophobic group comprising 6 to 30 carbon atoms and a hydrophilic polysaccharide group comprising 1.3 to 10 saccharide units, such as a polyglucoside group.
Preferred alkyl polyglucosides have the formula R2O(CnH2nO)t(sugar base)xWherein R is2Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 10; and x is 1.3 to 8. The glycosyl is preferably derived from glucose.
The nonionic surfactant may particularly preferably be selected from the following: alcohol ethoxylates, fatty alcohol polyglycol ethers, fatty acid ethoxylates, fatty acid polyglycol esters, glycerol ester monoalkoxylates, alkanolamides, fatty acid alkanolamides, ethoxylated alkanolamides, fatty acid alkanolamide ethoxylates, imidazolines, ethylene oxide-propylene oxide block copolymers, alkylphenol ethoxylates, alkyl glucosides, ethoxylated sorbitan esters and/or amine alkoxylates.
Amphoteric surfactant
Amphoteric surfactants that may be suitably used include amine oxide surfactants and alkyl amphocarboxylic acids.
Suitable amine oxides include those having the formula R3(OR4)xNO(R5)2Wherein R is3Selected from alkyl, hydroxyalkyl, amidopropyl, and alkylphenyl having 8 to 26 carbon atoms or mixtures thereof; r4Is alkylene or hydroxyalkylene having 2 to 3 carbon atoms; or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R5Is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide having 1 to 3 ethylene oxide groups. It is preferably C10-C18Alkyl dimethyl amine oxide and C10-C18Amidoalkyldimethylamine oxides.
Furthermore, suitable amphoteric surfactants can be described essentially as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sulfobetaine surfactants are preferred amphoteric surfactants.
Suitable betaines are those having the formula R (R')2N+R2COO-compounds in which R is C6-C18A hydrocarbon radical, each R1Is generally C1-C3Alkyl, and R2Is C1-C5A hydrocarbyl group. The preferred betaine is C12-C18Dimethylaminohexanoic acid ester and C10-C18Amido-propane- (or ethane) dimethyl- (or diethyl-) betaine. Complex betaine surfactants are also suitable according to the invention.
The amphoteric surfactants are particularly preferably selected from amphoacetates, amphodiacetates, glycinates, amphopropionates, sulphobetaines, amine oxides and/or betaines.
A further object of the present invention relates to a heat-curable flexible polyurethane foam stabilizer mixture comprising an amine, a polyol and/or water, said heat-curable flexible polyurethane foam stabilizer mixture comprising at least 40% by weight, based on the total weight of the heat-curable flexible polyurethane foam stabilizer mixture, of the heat-curable flexible polyurethane foam stabilizer solution of the present invention.
The heat-curable flexible polyurethane foam stabilizer solution of the invention and/or the heat-curable flexible polyurethane foam stabilizer mixture of the invention can be used for producing a heat-curable flexible polyurethane foam.
For example, the heat-curable flexible polyurethane foam solution of the present invention can be used directly, i.e., without further addition, for the preparation of heat-curable flexible polyurethane foams.
In general, polyurethane foam means a foamed polymeric material formed when a polyfunctional isocyanate reacts with a polyol. The connecting structural element formed is in this case a urethane moiety. Water may be used as the blowing agent. In this case carbon dioxide and the corresponding amine are formed, which further reacts with isocyanate to give a urea group. Polyurethane foams can be composed in large part from urea groups as well as urethane groups.
The heat-cured flexible polyurethane material of the invention is preferably a flexible foam based on polyether polyols. The heat-cured flexible polyurethane material of the present invention may also take the form of slabstock or molded foam.
The deformation resistance of the thermally cured flexible polyurethane materials is low under compressive stress (DIN 7726).
The compressive stress at 40% compression of the thermally cured flexible polyurethane material typically has a value of between 1kPa and 10kPa (procedure according to DIN EN ISO 3386-1/2).
The pore (cell) structure of the heat cured soft polyurethane material is mainly open.
The density of the heat-curable flexible polyurethane foam of the present invention is preferably in the range of 5 to 80kg/m2In particular in the range of 7 to 50kg/m2Very particularly preferably in the range from 10 to 30kg/m2In the range of (measured according to DIN EN ISO 845, DIN EN ISO 823).
The heat-curable flexible polyurethane foam is obtained by the reaction of a polyol with an isocyanate using the heat-curable flexible polyurethane foam stabilizer solution of the present invention and/or other components.
By the heat-curable flexible polyurethane foam stabilizer solution of the present invention, for example, a heat-curable flexible polyurethane foam having a pore size distribution in the range of 5 to 25 pores/cm can be produced.
As blowing agents for the preparation of thermally cured flexible polyurethane foams, it is possible to use preferably water, which liberates carbon dioxide on reaction with isocyanate groups. Water is preferably used in amounts of from 0.2 to 6 parts by weight (all parts by weight based on 100 parts by weight of polyol), particularly preferably from 1.5 to 5.0 parts by weight. In addition to or instead of water, it is possible to use physically acting blowing agents, examples being carbon dioxide, acetone, hydrocarbons such as n-pentane, isopentane or cyclopentane, cyclohexane or halogenated hydrocarbons such as dichloromethane, tetrafluoroethane, pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane or difluoro-fluoroethane. The amount of physical blowing agent is in this case preferably in the range from 1 to 15 parts by weight, in particular from 1 to 10 parts by weight, and the amount of water is preferably in the range from 0.5 to 10 parts by weight, in particular from 1 to 5 parts by weight. Carbon dioxide is preferably used in the physical blowing agent and preferably in combination with water as the chemical blowing agent.
Suitable isocyanates include aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se. Particularly preferably, the amount of isocyanate used is in the range of 80 to 120 mol% relative to the sum of the isocyanate-consuming components.
Specific examples that may be mentioned include the following: alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1, 12-dodecylene diisocyanate, 2-ethyltetramethylene 1, 4-diisocyanate, 2-methylpentamethylene 1, 5-diisocyanate, tetramethylene 1, 4-diisocyanate and preferably hexamethylene 1, 6-diisocyanate, cycloaliphatic diisocyanates, for example cyclohexane 1, 3-and 1, 4-diisocyanate and also any desired mixtures of these isomers, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2, 4-and 2, 6-hexahydrotoluylene diisocyanate and corresponding isomeric mixtures, 4' -, 2, 2 '-and 2, 4' -dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic di-and polyisocyanates, for example 2, 4-and 2, 6-tolylene diisocyanate and the corresponding isomer mixtures, 4 '-, 2, 4' -and 2, 2 '-diphenylmethane diisocyanate and the corresponding isomer mixtures, mixtures of 4, 4' -and 2, 2 '-diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanates, mixtures of 4, 4' -, 2, 4 '-and 2, 2' -diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI), and mixtures of crude MDI and tolylene diisocyanates. The organic di-and polyisocyanates can be used individually or in the form of mixtures thereof. Particular preference is given to mixtures of polyphenyl polymethylene polyisocyanates with diphenylmethane diisocyanates, the fraction of 2, 4' -diphenylmethane diisocyanate preferably being > 30% by weight.
It is also advantageous to use what are known as modified polyfunctional isocyanates, i.e. products obtained by chemical reaction of organic di-and/or polyisocyanates. By way of example, mention may be made of di-and/or polyisocyanates comprising ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione and/or urethane groups. Suitable specific examples include the following: modified 4, 4 ' -diphenylmethane diisocyanate, modified mixtures of 4, 4 ' -and 2, 4 ' -diphenylmethane diisocyanates, modified crude MDI or 2, 4-and/or 2, 6-toluene diisocyanate, organic, preferably aromatic polyisocyanates containing urethane groups, having an NCO content of from 15 to 43% by weight, preferably from 21 to 31% by weight, based on the total weight, examples being diols, triols, dialkylene glycols, trialkylene glycols or polyoxyalkylene glycols having a molecular weight of up to 6000, in particular having a molecular weight of up to 1500, which may be used individually or as mixtures as di-and/or polyoxyalkylene glycols. Examples that may be mentioned include the following: diethylene glycol, dipropylene glycol, polyethylene oxide, polypropylene oxide and polypropylene oxide-polyethylene oxide diols, triols and/or tetrols. Also suitable are NCO-containing prepolymers prepared from polyester polyols and/or preferably polyether polyols described below and mixtures of 4, 4 ' -diphenylmethane diisocyanate, mixtures of 2, 4 ' -and 4, 4 ' -diphenylmethane diisocyanate, 2, 4-and/or 2, 6-tolylene diisocyanate or crude MDI, the NCO content of said NCO-containing prepolymers being from 3.5 to 25% by weight, preferably from 14 to 21% by weight, based on the total weight. Other substances which have proven suitable are liquid polyisocyanates containing carbodiimide groups and/or isocyanurate rings, the NCO content of which is from 15 to 43% by weight, preferably from 21 to 31% by weight, based on the total weight, for example based on 4, 4 ' -, 2 ' -and/or 2, 4 ' -diphenylmethane diisocyanate and/or 2, 4-and/or 2, 6-tolylene diisocyanate.
The modified polyisocyanates can be mixed with one another or with unmodified organic polyisocyanates, such as, for example, 2, 4 '-and 4, 4' -diphenylmethane diisocyanate, crude MDI, 2, 4-and/or 2, 6-tolylene diisocyanate.
The following substances have proven particularly suitable as organic polyisocyanates and are therefore preferably used: toluene diisocyanate, mixtures of diphenylmethane diisocyanate isomers, diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanates or mixtures of toluene diisocyanate and diphenylmethane diisocyanate and/or polyphenyl polymethylene polyisocyanates, or so-called prepolymers. It is particularly preferred to use toluene diisocyanate in the process of the present invention.
In a particularly preferred embodiment, the organic and/or modified organic polyisocyanate used is a mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, the fraction of 2, 4-tolylene diisocyanate being 80% by weight.
Suitable polyols are those having at least two H atoms which are reactive with isocyanate groups; polyether polyols are preferably used. Such polyether polyols can be prepared by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides or nonmetallic alkoxylates as catalysts and with addition of at least one starter molecule containing 2 to 3 linked reactive hydrogen atoms, or by cationic polymerization of alkylene oxides in the presence of Lewis acids, such as antimony pentachloride or boron fluoride etherate, or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene group. Examples are tetrahydrofuran, 1, 3-propylene oxide, 1, 2-and 2, 3-butylene oxide, ethylene oxide and/or 1, 2-propylene oxide preferably being used. The alkylene oxides may be used individually, alternately in succession, or as mixtures. Suitable starter molecules include water and 2-and 3-hydroxy alcohols such as ethylene glycol, propane-1, 2-and-1, 3-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, and the like. Polyfunctional polyols such as sugars may also be used as initiators (starters).
The polyether polyols, preferably polyoxypropylene-polyoxyethylene polyols, have a functionality of 2-5 and a number average molecular weight in the range of 500-.
If desired, flame retardants may also be added to the starting materials, preferably those that are liquid and/or soluble in one or more of the components used in the preparation of the foam. Commercially available phosphorus-containing flame retardants are preferably used, examples being tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, tris (1, 3-dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, tributoxyethyl phosphate, dimethyl methanephosphonate, diethyl ethanephosphonate and diethyl diethanolaminomethylphosphonate. Also suitable are halogen-and/or phosphorus-containing flame-retardant polyols and/or melamines. In addition, melamine may also be used. The flame retardant is preferably used in an amount of not more than 35% by weight, preferably not more than 20% by weight, based on the polyol component. Further examples of surface-active additives which may also be used if desired are foam stabilizers and cell regulators, reaction retarders, stabilizers, flame retardants, dyes, and also substances having a fungistatic and bacteriostatic action. Details of the use and the mode of behavior of these auxiliaries are found in g.oertel (eds): "Kunststoff-Handbuch", volume VII, Carl Hanser Verlag, 3 rd edition, Munich 1993, page 110-.
In addition, in the process of the present invention, preferably from 0.05 to 0.5 parts by weight, in particular from 0.1 to 0.2 parts by weight, of the catalyst for the blowing reaction can be used. These catalysts for the blowing reaction are selected from the following: tertiary amines [ triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, bis (3-dimethylaminopropyl) amine, N, N, N '-trimethylaminoethylethanolamine, 1, 2-dimethylimidazole, N- (3-aminopropyl) imidazole, 1-methylimidazole, N, N, N', N '-tetramethyl-4, 4' -diaminodicyclohexylmethane, N, N-dimethylethanolamine, N, N-diethylethanolamine, 1, 8-diazabicyclo-5, 4, 0-undecene, N, N, N ', N' -tetramethyl-1, 3-propanediamine, N, N-dimethylcyclohexylamine, dimethylaminoethoxyethanol, bis (3-aminopropyl) imidazole, 1-methylimidazole, N, N, N ', N' -diaminodicyclohexylmethane, N, N, N-dimethylethanolamine, n, N ', N ", N'" -pentamethyl-diethylenetriamine, N ', N ", N'" -pentamethyldipropylenetriamine, N '-dimethylpiperazine, N-methylmorpholine, N-ethylmorpholine, 2' -dimorpholinodiethylether, N-dimethylbenzylamine, N ', N "-tris (dimethylaminopropyl) hexahydrotriazine, N' -tetramethyl-1, 6-hexanediamine, tris (3-dimethylaminopropyl) amine and/or tetramethylpropylamine ]. Also suitable are acid-blocked derivatives of tertiary amines. In a particular embodiment, the amine used is dimethylethanolamine or bis (2-dimethylaminoethyl) ether. In another embodiment, the amine used is triethylenediamine.
In the process of the invention, it is also possible to use preferably from 0.05 to 0.5 part by weight, in particular from 0.1 to 0.3 part by weight, of catalyst for the gel reaction. The catalyst for the gel reaction is selected from organometallic compounds and metal salts of the following metals: tin, zinc, tungsten, iron, bismuth and titanium. One particular embodiment uses a catalyst selected from tin carboxylates. Very particular preference is given here to tin (2-ethylhexanoate) and tin ricinoleate. Tin 2-ethylhexanoate is important for the inventive preparation of heat-cured flexible polyurethane foams. Furthermore, tin compounds having completely or partially covalently bonded organic groups are also preferred. Particular preference is given here to using dibutyltin dilaurate.
Overview is g.oertel (eds): "Kunststoff-Handbuch", volume VII, CarlHanser Verlag, 3 rd edition, Munich 1993, page 139-192 and in D.Randall and S.Lee (eds): "The Polyurethanes Book" J.Wiley, 1 st edition, 2002.
In a further application, the low viscosity aqueous solutions of the heat-curable flexible polyurethane foam stabilizers of the invention can be used in low pressure machines. In this case, a low-viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer of the invention can be introduced separately into the mixing chamber. In a further version of the process, it is also possible to mix the aqueous solution of the low-viscosity, thermally curing, flexible polyurethane foam stabilizer of the invention into one of the components which subsequently enters the mixing chamber upstream of the mixing chamber. This mixing can also be carried out in a raw material tank.
In a further application, it is also possible to use low-viscosity aqueous solutions of the heat-curing flexible polyurethane foam stabilizers of the invention on high-pressure machines. In this case, a low-viscosity aqueous solution of a heat-curable flexible polyurethane foam stabilizer may be directly added to the mixing head.
In a further version of the process of the present invention, it is also possible to mix a low-viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer of the present invention into one of the components which subsequently enters the mixing chamber, upstream of the mixing chamber. This mixing can also be carried out in a raw material tank.
The apparatus for the preparation of thermally cured flexible polyurethane foam can be operated continuously or batchwise. The low-viscosity aqueous solutions of the heat-curing flexible polyurethane foam stabilizers of the invention are particularly advantageous for continuous foaming. In which case the foaming operation can be carried out in either the horizontal or vertical direction. In yet another embodiment, the low viscosity aqueous solution of the heat-curable flexible polyurethane foam stabilizer of the present invention may be used for CO2Provided is a technique.
In yet another embodiment, foaming may also be performed in a mold.
The gas permeability of the heat-cured flexible polyurethane foam of the present invention is preferably in the range of 1-300mm ethanol column, in particular in the range of 7-25mm ethanol column (ethanol column) (measured by measuring pressure while flowing through the foamed sample). For this purpose, a 5cm thick foam tray was placed on a smooth surface. A plate (10 cm. times.10 cm) weighing 800g and having a central hole (diameter 2cm) and a hose connection was placed on the foamed sample. A constant air flow of 8l/min was passed into the foamed sample via the central hole. The pressure difference that occurred (relative unimpeded effluent) was determined by the ethanol column in the graduated manometer. The more closed foam, the greater the pressure build up and the greater the degree of pushing down on the surface of the ethanol column, and the greater the value measured).
The present invention also provides a product comprising a heat-curable flexible polyurethane foam prepared using the heat-curable flexible polyurethane foam stabilizer solution and/or the heat-curable flexible polyurethane foam stabilizer mixture of the present invention.
Detailed Description
The subject matter of the invention is illustrated in more detail with reference to the examples and the following tables. For these examples, the polyether siloxanes typical for stabilizing heat-cured flexible polyurethane foams were prepared and characterized by various mixtures thereof.
Polyether siloxane A
Polyether siloxane a is a polyether siloxane of the present invention of the general formula:
where o is 4, n is 70, PE is a mixture of two polyethers: 37.5 eq% of methylated polyether having a Mn of 3800g/mol prepared from 58% by weight of propylene oxide and 42% by weight of ethylene oxide, and 62.5 eq% of methylated polyether having a Mn of 600g/mol prepared from 100% by weight of ethylene oxide.
Preparation of polyether siloxane A
The polyether siloxanes were prepared from the corresponding pendant Si-H-functional polydimethylsiloxanes and the corresponding allyl polyethers. The siloxanes are prepared by equilibration according to known methods, for example the method described in EP 0499200. Allyl polyethers are obtained by alkoxylating alkylene oxides, such as ethylene oxide, propylene oxide, dodecene oxide or styrene oxide, in anionic polymerization using allyl alcohol as initiator. Examples of synthesis options for such allyl polyethers are disclosed in EP 0822218. For hydrosilylation, 30% by weight excess of allyl polyether relative to the stoichiometrically required amount was added. A typical platinum catalyst for the hydrosilylation reaction, such as cis-platinum or hexachloroplatinic acid, is added in an amount of 10 ppm. The reaction mixture was heated at 90 ℃ for 6 hours for the reaction, the residual SiH functionality content was determined from time to time by volume reaction (volumetric reaction) with potassium butoxide solution and determination of the hydrogen formed. The reaction is ended when > 98% of the Si-H functions used have undergone a reaction. Excess polyether present in the reaction product remains in the reaction mixture. The product thus obtained was used directly as polyether siloxane a for further testing. The preparation of such Si-C linked polyether siloxanes has often been described in the literature, for example in US 4,147,847, EP 0493836 and US 4,855,379, all of which are incorporated herein by reference in their entirety.
Mixing of polyether siloxanes A
For the purpose of illustrating the present invention, the above polyether siloxanes are mixed with various organic solvents, with water, and with water containing a surfactant, for example. The viscosity of each sample was measured.
Mixing of polyether siloxane A with Water
In the mixing series, polyether siloxane a was mixed with water at 10 wt% intervals and the viscosity was determined.
TABLE I
Mixture of polyether siloxane A and water
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 11.5 |
| 80 | 20 | 10.0 |
| 70 | 30 | 46.4 |
| 60 | 40 | 113 |
| 50 | 50 | 34.5 |
| 40 | 60 | 6.1 |
| 30 | 70 | 2.0 |
| 20 | 80 | 0.6 |
| 10 | 90 | 0.08 |
The trend of viscosity, clearly between pure water and pure polyether siloxane, is by no means linear. In contrast, there was a very significant increase in viscosity starting from a 30 wt.% polyether siloxane in water mixture. About 60% by weight of the polyether siloxane to water mixture is maximized. Values greater than 100Pa · s may occur. Such high viscosity leads to gel-like behavior. If the fraction of polyether siloxane is increased further, the viscosity decreases again. At about 80 wt%, the region of intense viscosity increase ends. The viscosity then decreases towards the pure polyether siloxane. The viscosity number plot is connected in figure 1. It is clearly impossible to prepare readily usable, low-viscosity solutions (viscosity. ltoreq.5000 mPas) of heat-curing flexible polyurethane foam stabilizers with water as solvent without additives in mixtures in which the polyether siloxanes are in the range from 40% to 80% by weight.
To the mixture prepared from polyether siloxane and water, various auxiliaries were added:
then, various auxiliaries were added to the previously prepared mixture of polyether siloxane and water. The weight content of auxiliaries in percent by weight, based on the polyether siloxane/water mixture (100% by weight), is weighed out and added to the mixture. The absolute content of polyether siloxane and water in the surfactant-containing mixture is reduced by the corresponding factor, but the ratio of polyether siloxane to water is maintained (which is very important for the phase behavior). First, it was attempted to achieve a solution of the two polyether siloxanes in water of the desired viscosity by adding typical organic solvents for polyether siloxanes. The solvent used was dipropylene glycol (DPG). DPG is a standard solvent for heat-cured flexible polyurethane foams. In this case, DPG was added to the mixture of polyether siloxane and water in an amount of 5% by weight.
TABLE II
Mixture of polyether siloxane A and water with addition of 5% by weight of DPG
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 7.4 |
| 80 | 20 | 5.9 |
| 70 | 30 | 48.5 |
| 60 | 40 | 63.5 |
| 50 | 50 | 19.1 |
| 45 | 55 | 10.7 |
| 30 | 70 | 0.8 |
| 20 | 80 | 0.1 |
| 10 | 90 | 0.02 |
It is clear that the addition of 5 wt.% DPG does reduce the viscosity to some extent, but a sharp increase in viscosity is still observed. The addition of higher amounts of DPG did not change this situation anymore, as can be inferred from the comparative examples in table III. As with DPG, here liquid polyether (IPE) is used as a solvent. This IPE is a liquid polyether prepared starting from n-butanol, which combines ethylene oxide and propylene oxide in a random distribution, having an average molar mass of about 1000 g/mol. 42% by weight is propylene oxide and 58% by weight is ethylene oxide. This polyether is prepared by alkoxylation in analogy to the allyl-functional polyether described above.
TABLE III
Mixtures of polyether siloxanes A and various solvents at higher concentrations
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Type of auxiliary agent | The dosage of the auxiliary agent is (by weight)] | Viscosity (1 s)-1[ Pa · s ] below] |
| 60 | 40 | - | - | 113 |
| 60 | 40 | DPG | 20 | 11.1 |
| 60 | 40 | Liquid polyether (IPE) | 20 | 10.5 |
Although the viscosity increase is more moderate, there are still cases where viscosities above 5Pa · s are observed, precluding the use of such mixtures for industrial use as polyurethane stabilizers.
In contrast to the above solvents, a surfactant or surfactant mixture was added to the mixture of the lower polyether siloxane a and water. As far as surfactants are concerned, mixtures with water are in some cases customary in the art. In these cases, the aim in the preparation of the samples was to add 5% by weight of pure surfactant, in other words in the case of dilute surfactants, a correspondingly larger amount of surfactant mixture was used. With respect to the total water content of the polyether siloxane/water/surfactant mixture, the water present in the surfactant mixture is considered in some cases.
First, the trade name Rewopol obtained from Degussa is used2-ethylhexyl sulfonic acid-Na salt of D510. RewopolD510 is itself a 40 wt.% mixture with 60 wt.% water.
TABLE IV
Polyether siloxane A and water and 5% by weight of a mixture of 2-ethylhexyl sulfonic acid-Na salt
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 4.8 |
| 80 | 20 | 7.9 |
| 70 | 30 | 4.9 |
| 60 | 40 | 4.8 |
| 50 | 50 | 1.1 |
| 40 | 60 | 0.14 |
| 30 | 70 | 0.04 |
| 20 | 80 | 0.04 |
| 10 | 90 | 0.004 |
It is clear that in the case of polyether siloxanes A within the scope according to the invention, an acceptably low viscosity can be achieved at all by adding 5% by weight of the surfactant 2-ethylhexylsulfonic acid-Na salt.
In addition to the use of pure surfactants, other possibilities are considered to be suitable mixtures of surfactants. 50% by weight of Tegotens826-an oligomeric alkyl glycoside available from Degussa-and 50% by weight of sodium lauryl sulfate are of particular interest in this regard.
TABLE V
Polyether siloxane a and water and 5 wt.% of surfactant mixture (surfactant mixture 50 wt.% of Tegotens) was added826, 50% by weight sodium lauryl sulphate)
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 7.9 |
| 80 | 20 | 20.8 |
| 70 | 30 | 5.0 |
| 60 | 40 | 1.9 |
| 50 | 50 | 1.0 |
| 40 | 60 | 0.12 |
| 30 | 70 | 0.03 |
| 20 | 80 | 0.01 |
| 10 | 90 | 0.001 |
With the polyether siloxanes A, viscosities of ≦ 5 pas can be obtained for all mixtures according to the invention.
Used below is a compound having C obtained from Degussa10-C13Sodium salt of linear alkyl benzene sulphonic acid of alkyl chain length, trade name RewiylNKS 50. It is a 50% by weight mixture in water.
TABLE VI
Mixture of polyether siloxane A and water with addition of 5% by weight of sodium alkylbenzenesulfonate
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 6.3 |
| 80 | 20 | 11.3 |
| 70 | 30 | 3.1 |
| 60 | 40 | 1.6 |
| 50 | 50 | 0.49 |
| 40 | 60 | 0.17 |
| 30 | 70 | 0.053 |
| 20 | 80 | 0.016 |
| 10 | 90 | 0.006 |
It is clear that within the scope according to the invention the alkylbenzene sulfonates reduce the viscosity to below 5Pa · s.
In addition to the use of the surfactant, a surfactant and an organic solvent may be used in combination. This may be particularly desirable from the standpoint of improved freeze protection. Below, 5 wt.% DPG was also added to the samples of table VI for this purpose.
TABLE VII
Polyether siloxane A and water and 5% by weight of sodium alkylbenzenesulfonate and
5% by weight mixture of DPG
| Amount of polyether siloxane A [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| 90 | 10 | 8.7 |
| 80 | 20 | 10.1 |
| 70 | 30 | 5.0 |
| 60 | 40 | 1.5 |
| 50 | 50 | 0.42 |
| 40 | 60 | 0.15 |
| 30 | 70 | 0.048 |
| 20 | 80 | 0.016 |
| 10 | 90 | 0.006 |
Comparing table VI and table VII, no significant change in viscosity profile was observed. The addition of DPG does not initially alter much the viscosity reducing properties of the addition of organic surfactants to the mixture of polyether siloxane and water, but may still have further advantages such as greater freeze protection safety.
Furthermore, when preparing heat-cured flexible polyurethane foams in the laboratory, the polyether siloxanes described are used in mixtures with DPG (not according to the invention) and with water and organic surfactants (examples according to the invention). The mixtures used in this case were as follows:
60% by weight of a polyether siloxane
40% by weight of DPG
Or
60% by weight of a polyether siloxane
35% by weight of water
5% by weight of sodium alkylbenzenesulfonate
The mixture thus prepared was then investigated with a typical heat-cured flexible polyurethane foam formulation.
General formulation for preparing experimental heat-cured flexible polyurethane foams:
100 parts by weight of a polyol (Desmophen from Bayer)PU20WB01，OHnumber 56)
5.0 parts by weight of water (chemical blowing agent) (in the case of aqueous polyether siloxane mixtures, correspondingly lower)
1.0 parts by weight of a polyether siloxane mixture
0.15 parts by weight of amine catalyst (triethylenediamine)
0.23 parts by weight of tin catalyst (tin 2-ethylhexanoate)
5.0 parts by weight of methylene chloride (supplementary physical blowing agent)
63.04 parts by weight of isocyanate (tolylene diisocyanate, TDI-80) (ratio of isocyanate groups to isocyanate-consuming reactive groups ═ 1.15)
The procedure is as follows:
the polyol, water, catalyst and stabilizer were placed in a paper cup and mixed using a stir plate (45 s at 1000 rpm). Then, dichloromethane was added and mixed again at 1000rpm for 10 s. Thereafter, isocyanate (TDI-80) was added and stirring was again carried out at 2500rpm for 7 s. The mixture was then added to a box measuring 30cmx30cmx30 cm. During foaming, the rising height is measured by an ultrasonic height measurement system. The rise time is the time elapsed when the foam has reached its maximum rise height. Sedimentation refers to the sinking of the foam surface after the heat-cured flexible polyurethane foam has been foamed. Sedimentation was measured relative to the maximum rise height 3 minutes after foaming. The density was measured according to DIN EN ISO 845 and DIN EN ISO 823. The hole number was obtained at three points using a graduated magnifier.
TABLE VIII
Test results of foaming of Heat-cured Flexible polyurethane foam
| Polyether siloxane | The mixture has | Rise time [ s ]] | Sedimentation [ cm ]] | Density [ kg/m ]3] | Number of holes [ l/cm ]] |
| A | DPG | 86 | -0.1 | 18.0 | 7 |
| A | Water + sodium alkyl benzene sulfonate | 87 | -0.1 | 18.1 | 6 |
During the test foaming, it appeared that both mixtures of polyether siloxanes showed the same properties. Thus, no solvent effect was observed under the test foaming. However, in other heat-cured flexible polyurethane foam formulations, the difference in foaming behavior of polyether siloxanes with mixtures of organic solvents and water cannot be eliminated. Specifically, the absence of dipropylene glycol may also result in a more open foam structure. In the context of related purposes, mixtures of polyether siloxanes with water/surfactant mixtures can be classified as useful as heat-curable flexible polyurethane foam stabilizers.
The ultimate objective of interest relates to the types of surfactants that can be proposed in the present invention that result in a reduction in viscosity. To clarify this, polyether siloxanes were mixed with a large amount of surfactant. The amount of pure surfactant used in each case was 5% by weight in the entire mixture. The proportions set forth in Table IX were found based on a mixture of polyether siloxane and water in the absence of surfactant. The resulting viscosities are listed in tables IX and X.
TABLE IX
Mixture of two polyether siloxanes and Water in the subsequent surfactant series experiments
| Polyether siloxanes | Amount of polyether siloxane [ wt.%] | Amount of Water [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| A | 52.6 | 47.4 | 45.6 |
Table X
50% by weight of polyethersiloxane A, 45% by weight of water and
5% by weight of a mixture of various surfactants
Cationic surfactant
Nonionic surfactant
Amphoteric surfactant
Characteristics of the surfactant:
-RewopolNLS 28 (28% by weight sodium lauryl sulfate) from Degussa
-HostapurSAS30 (30% by weight sodium C14/17 alkyl sulfate) available from Clariant
-ReworylNKS 50 (50% by weight sodium C10/C13 alkylbenzenesulfonate, 50% by weight water) from Degussa
-Berol522 (45% by weight potassium decyl phosphate), from Akzo Nobel
-HostaphatOPS (100% by weight octan phosphonic acid) from Clariant
-RewopolSB DO 75 (75% by weight sodium diethylhexyl sulfosuccinate) available from Degussa
-RewopolSB FA 30 (40% by weight sodium lauryl ethoxy sulfosuccinate) from Degussa
-HostapurOS (42% by weight sodium C14/16. alpha. -olefin sulfonate) available from Clariant
-HostaponSCI 85C (85% by weight sodium coconut fatty acid isethionate) from Clariant
-HostaponCT (30% by weight sodium coconut fatty acid methyl taurate), available from Clariant
-RewoquatCPEM (Cococopentaethoxymethylammonium methylsulfate 100% by weight), available from Degussa
-Adogen444-29 (29% by weight of cetyltrimethylammonium chloride), available from Degussa
-RewopalLA10-80(75 wt.% lauryl alcohol ethoxylate, n ═ 10) available from Degussa
-RewodermLI63 (100% by weight coconut oil fatty acid monoglyceride ethoxylate, n ═ 30) was purchased from Degussa
-RewopalHV25(100 wt% nonylphenol ethoxylate, n ═ 25) available from Degussa
-TEGOSML20 (100% by weight PEG20 sorbitan monolaurate) from Degussa
-RewotericAM C (25% by weight sodium cocoamphoacetate), available from Degussa
-RewotericAM 2C NM (40% by weight sodium cocoamphodiacetate) from Degussa
-RewotericAM TEG (40% by weight of tallow Glycine), available from Degussa
-RewotericAM KSF 40 (40% by weight sodium cocoamphopropionate), available from Degussa
-RewotericAM CAS (40-45 wt.% Cocamidopropyl hydroxysultaine) available from Degussa
-RewominoxL408 (30% by weight of lauryl dimethylamine oxide) from Degussa
-TEGOBetain F50 (38% by weight of cocamidopropyl betaine), available from Degussa.
For comparison, the viscosities obtained with the addition of 5% by weight of DPG at the proportions of polyether siloxane A and water as in Table X are as follows.
TABLE XI
Ratios of surfactant series experiments in Table X
And water and mixtures when 5% by weight of DPG are added
| Polyether siloxanes | Amount of polyether siloxane [ wt.%] | Amount of Water [ wt.%] | Amount of DPG [ wt.%] | Viscosity (1 s)-1[ Pa · s ] below] |
| A | 50 | 45 | 5 | 18.3 |
Obviously for each of the surfactants listed (anionic, cationic, nonionic, amphoteric), one can find examples of viscosities lower than 5Pa · s in a mixture with water and surfactant. In principle, this is not possible except for any organic surfactant groups. Comparison with DPG (Table XI) again shows a far lower viscosity due to the use of organic solvents.
Determination of viscosity
All viscosities reported in the present invention are determined as follows, unless otherwise indicated.
MCR301 rotational viscometer from Physica (Anton Paar, Ostfildern, Germany) was used at 1s-1The viscosity was measured in a spinning experiment at 25 ℃. Samples with a viscosity > 100mPa · s were measured using a cone/plate geometry (diameter 50.0mm, angle 0.981 °). Samples with a viscosity < 100mPa · s were investigated using a Couette geometry (measuring element diameter 26.66mm, measuring beaker diameter 28.93mm, measuring slit width 1.135mm, measuring slit length 40.014 mm). Since some samples exhibited structural viscosity characteristics, the initial conditions for creating control were first at 1000s-1The sample was sheared down for 60 seconds. The sample was then held without shear for 10 minutes. During which the structure may be produced again. Thereafter, at 1s-1The viscosity is measured at a shear rate of (a). For this measurement, shear was performed for up to 10 minutes until equilibrium was reached. Without pretreatment, at 1s-1Samples that do not exhibit structural viscosity behavior are measured directly until equilibrium is reached.
Claims (58)
1. A low viscosity aqueous solution of a heat-cured flexible polyurethane foam stabilizer having a viscosity of 5000mPa · s or less at 25 ℃, useful for the preparation of a heat-cured flexible polyurethane foam, wherein the low viscosity aqueous solution of the heat-cured flexible polyurethane foam stabilizer comprises the following components:
polyether siloxane of more than or equal to 40 weight percent and less than or equal to 70 weight percent,
more than or equal to 0.5 weight percent and less than or equal to 20 weight percent of organic surfactant,
not less than 10% by weight of water,
not less than 0% by weight of an organic solvent,
wherein the polyether siloxane has the following general formula (I)
R1-Si(CH3)2O-[Si(CH3)(OSi(CH3)2R0)O-]u-[Si(OSi(CH3)2R0)2O-]v
-[Si(CH3)2O-]w-[SiCH3R2O-]x-[SiCH3R3O-]y-[SiCH3R4O]z
-[SiR3R4O]t-Si(CH3)2-R5 (I)
Wherein
R0＝-O-[Si(CH3)2O-]w-[SiCH3R2O-]x-[SiCH3R3O-]y-[SiCH3R4O]z-Si(CH3)2-R5，
R1、R2、R3、R4And R5Are in each case identical to or different from one another, are alkyl or aryl radicals of 1 to 12 carbon atoms or are-CH2-R6or-CH2-CH2-R6Or polyalkylene oxide polyethers of the general formula (II)
-CmH2mO(C2H4O)a(C3H6O)b(C4H8O)c(C6H5-C2H3O)d(C12H24O)gR7 (II)，
R6＝H、-C6H5-CN having C1-C10Alkyl, epoxy ring-CH of2O, -alkyl-OH, -aryl-OH, -Cl, -OH, -R8-O-R9、-R8-O-CO-R9Or a divalent bridging group linked to other siloxane groups, selected from alkylene groups, -R8-O-R9-、-R8-COO-R9-、-R8-O-R9-O-R8-、-R8-COO-R9-OOC-R8-、-R8-OOC-R9-COO-R8-，
R7H, alkyl, acyl or aryl groups, alkyl-or aryl-urethane groups or divalent bridging groups linked to other siloxane groups, selected from alkylene groups, -R8-O-R9-、-R8-COO-R9-、-R8-O-R9-O-R8-、-R8-COO-R9-OOC-R8-、-R8-OOC-R9-COO-R8-，
R8Either an alkylene group or an arylene group,
R9alkyl-, aryl-, alkylene or arylene,
u＝0-5，
v＝0-5，
t＝0-15，
w＝15-130，
x＝0-15，
y＝0-15，
z＝0-15，
m＝0-4，
a is more than or equal to 0 and less than or equal to 160,
b is more than or equal to 0 and less than or equal to 140,
c is more than or equal to 0 and less than or equal to 50,
g is more than or equal to 0 and less than or equal to 50,
d is more than or equal to 0 and less than or equal to 50, in the case that a + b + c + d + g is more than or equal to 10,
with the proviso that x + y + z + t.gtoreq.3 and at least one substituent R1、R2、R3、R4And R5Is a polyether of the general formula II, the weight fractions of the above-mentioned components being selected such that the total weight fraction of the components does not exceed 100% by weight, based on the heat-cured flexible polyurethane foam stabilizer solution,
wherein the polyether units in the polyether siloxane have a molar mass of from 500g/mol to 7000g/mol and at least one polyether unit has an average molar mass of Mn ≥ 2100g/mol,
the viscosity was measured at 1s using a Physiea MCR301 rotational viscometer-1Measured in a spinning experiment at 25 ℃.
2. The heat-curable flexible polyurethane foam stabilizer solution of claim 1 wherein said acyl group is acetyl.
3. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 1 wherein for said polyether siloxane
t is 2-15 or 0, and/or
u is 0-4, and/or
v is 0 to 4, and/or
w is 50-100, and/or
x is 2-15 or 0, and/or
y is 2-15 or 0, and/or
z is 2-15 or 0, and/or
a 1-105, and/or
b is 1-105, and/or
c is 1-40 or 0, and/or
d is 1-40 or 0, and/or
g 1-40 or 0, and/or
m＝1-4。
4. The heat-curable flexible polyurethane foam stabilizer solution as claimed in claim 3, wherein,
t＝4-13，
u is 1, 2 or 0, and/or
v is 1, 2 or 0, and/or
w is 55-90, and/or
x is 4-13, and/or
y is 4-13, and/or
z is 4-13, and/or
a is 5-100, and/or
b is 5-100, and/or
c is 2-30, and/or
d is 2-30, and/or
g is 2-30, and/or
m＝2-3。
5. The heat-curable flexible polyurethane foam stabilizer solution as claimed in claim 4, wherein,
w＝60-85，
a is 10-90, and/or
b is 10-90, and/or
c is 2-20, and/or
d is 2-20, and/or
g＝2-20。
6. A heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 1 or 3 wherein said polyether siloxane has the following general formula (III):
wherein
n＝50-120，
o is 3-20, and
PE has the following general formula IV:
wherein
X ═ H, alkyl, acyl, or aryl groups,
e is more than or equal to 0 to 100,
f is more than or equal to 0 to 120, wherein e + f is more than or equal to 15.
7. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 6 wherein
n＝60-100，
o＝3.5-18，
e is the number of the groups 1 to 50,
f is 1 to 50.
8. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 7 wherein
n＝65-90，
o＝4-15，
e is the number of the amino acid residues in the range of 3-40,
f is 5 to 40.
9. The heat-curable flexible polyurethane foam stabilizer solution of claim 8 wherein
e is the number of 5 to 30,
f is 10 to 30.
10. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 1 wherein R1And R5Identical or different from one another in each case, is methyl, ethyl or propyl; and/or m is 2 or 3.
11. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 10 wherein R1And R5Is methyl.
12. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 1 wherein said polyether units have a molar mass of from 1000g/mol to 6000 g/mol.
13. The heat-curable flexible polyurethane foam stabilizer solution of claim 12 wherein said polyether units have a molar mass of from 2000g/mol to 5000 g/mol.
14. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 1, wherein the fraction of ethylene oxide in said polyether units is from 10 to 100% by weight or the fraction of propylene oxide in said polyether units is from 10 to 100% by weight.
15. The heat-curable flexible polyurethane foam stabilizer solution of claim 14 wherein said polyether siloxane has a fraction of said propylene oxide that exceeds all polyether units on average, said fraction of propylene oxide being from 40 to 90 weight percent.
16. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 15, wherein said propylene oxide fraction is not less than 50% by weight.
17. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 16, wherein said propylene oxide fraction is not less than 55% by weight.
18. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 17, wherein said propylene oxide fraction is 60% by weight or more.
19. The heat-curable flexible polyurethane foam stabilizer solution of claim 1 wherein said polyether siloxane has a molecular weight of from 10000g/mol to 50000 g/mol.
20. The heat-curable flexible polyurethane foam stabilizer solution of claim 19 wherein said polyether siloxane has a molecular weight of 13000g/mol to 40000 g/mol.
21. The heat-curable flexible polyurethane foam stabilizer solution of claim 20 wherein said polyether siloxane has a molecular weight of from 15000g/mol to 35000 g/mol.
22. The heat-cured flexible polyurethane foam stabilizer solution of claim 1 wherein said heat-cured flexible polyurethane foam stabilizer solution comprises:
42 to 68 wt.% of a polyether siloxane,
-from not less than 1% by weight to not more than 10% by weight of an organic surfactant,
from not less than 15% by weight to not more than 55% by weight of water, and
-from 0% by weight to 15% by weight of an organic solvent.
23. The heat-curable flexible polyurethane foam stabilizer solution of claim 22 wherein
-the content of the polyether siloxane is more than or equal to 45 wt% and less than or equal to 65 wt%,
-the content of the organic surfactant is from more than or equal to 2% by weight to less than or equal to 8% by weight,
a water content of from not less than 20% by weight to not more than 50% by weight, and
-the content of the organic solvent is from more than or equal to 1 wt% to less than or equal to 10 wt%.
24. The heat-curable flexible polyurethane foam stabilizer solution of claim 23 wherein
-the polyether siloxane content is from not less than 47% by weight to not more than 62% by weight,
-the content of the organic surfactant is from not less than 4% by weight to not more than 6% by weight,
a water content of from not less than 30% by weight to not more than 40% by weight, and
-the content of the organic solvent is more than or equal to 2 wt% and less than or equal to 5 wt%.
25. The heat-curable flexible polyurethane foam stabilizer solution of claim 24 wherein
-the content of polyether siloxane is 50-60% by weight.
26. The heat-cured flexible polyurethane foam stabilizer solution of claim 22 wherein said organic solvent is an antifreeze.
27. The heat-cured flexible polyurethane foam stabilizer solution of claim 1 wherein said heat-cured flexible polyurethane foam stabilizer solution comprises:
-from 45% by weight or more to 55% by weight or less of a polyether siloxane,
an alkylbenzene sulfonate in an amount of from not less than 1% by weight to not more than 10% by weight,
from ≥ 30% by weight to ≤ 50% by weight of water, and
dipropylene glycol in an amount of from not less than 1% by weight to not more than 10% by weight.
28. The heat-curable flexible polyurethane foam stabilizer solution of claim 27 wherein
-the content of the polyether siloxane is 50% by weight,
-the alkylbenzene sulfonate content is from ≥ 2% to ≤ 8% by weight,
a water content of from not less than 35% by weight to not more than 45% by weight, and
-the content of dipropylene glycol is not less than 3 wt% to not more than 7 wt%.
29. The heat-curable flexible polyurethane foam stabilizer solution of claim 28 wherein
-the alkylbenzene sulfonate is present in an amount of 5% by weight,
a water content of 40% by weight, and
-the content of dipropylene glycol is 5 wt%.
30. The heat-cured flexible polyurethane foam stabilizer solution as set forth in claim 1, wherein said heat-cured flexible polyurethane foam stabilizer solution has a viscosity of from ≥ 100mPa · s to ≤ 5000mPa · s.
31. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 30 wherein said viscosity is from ≥ 500 to ≤ 3000 mPa-s.
32. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 31, wherein said viscosity is from ≥ 700 mPa-s to ≤ 2000 mPa-s.
33. The heat-curable flexible polyurethane foam stabilizer solution as set forth in claim 32, wherein said viscosity is from ≥ 900 Pa-s to ≤ 1800 mPa-s.
34. The heat-cured flexible polyurethane foam stabilizer solution of claim 1 wherein said heat-cured flexible polyurethane foam stabilizer solution is a clear solution.
35. The heat-cured flexible polyurethane foam stabilizer solution of claim 34 wherein said heat-cured flexible polyurethane foam stabilizer solution is a clear solution.
36. The heat-cured flexible polyurethane foam stabilizer solution of claim 1 wherein the heat-cured flexible polyurethane foam stabilizer solution is storage stable at room temperature and does not phase separate and/or precipitate over a period of at least 14 days.
37. The heat-cured flexible polyurethane foam stabilizer solution of claim 1 wherein said heat-cured flexible polyurethane foam stabilizer solution has a cloud point of greater than or equal to 40 ℃.
38. The heat-cured flexible polyurethane foam stabilizer solution of claim 37 wherein said cloud point is greater than or equal to 50 ℃.
39. The heat-cured flexible polyurethane foam stabilizer solution of claim 38 wherein said cloud point is greater than or equal to 60 ℃.
40. The heat-cured flexible polyurethane foam stabilizer solution as set forth in claim 1 wherein said organic surfactant is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, and/or amphoteric surfactants.
41. The heat-cured flexible polyurethane foam stabilizer solution of claim 40 wherein said organic surfactant is an anionic surfactant.
42. The heat-cured flexible polyurethane foam stabilizer solution of claim 41 wherein said organic surfactant is an organic sulfate or sulfonate surfactant.
43. The heat-cured flexible polyurethane foam stabilizer solution of claim 42 wherein said organic surfactant is an alkyl benzene sulfonate.
44. The heat-cured flexible polyurethane foam stabilizer solution of claim 40 wherein said anionic surfactant is selected from the group consisting of: alkyl sulfates, sulfates of fatty alcohols, secondary alkyl sulfates, paraffin sulfonates, alkyl ether sulfates, alkyl polyethylene glycol ether sulfates, aryl sulfonates, fatty alcohol ether sulfates, alkylbenzene sulfonates, alkylphenol ether sulfates, alkyl phosphates, phosphoric acid mono-, di-, tri-esters, alkyl ether phosphates, ethoxylated fatty alcohol phosphate esters, phosphonates, sulfosuccinic diesters, sulfosuccinic monoesters, ethoxylated sulfosuccinic monoesters, sulfosuccinic amides, alpha-olefin sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl polyethylene glycol carboxylates, fatty acid isethionates, fatty acid methyl taurates, fatty acid sarcosines, alkyl glyceryl ether sulfonates, polyacrylates, and/or alpha-sulfo fatty acid esters.
45. The heat-cured flexible polyurethane foam stabilizer solution of claim 40 wherein said cationic surfactant is selected from the group consisting of ester quats, alkoxyalkyl quats, and/or trialkyl quats.
46. The heat-curable flexible polyurethane foam stabilizer solution of claim 45 wherein said ester quaternary ammonium compound is bis (tallow fatty acid amidoethyl) methyl polyethoxy ammonium methosulfate, a diamide amine quaternary ammonium compound, said alkoxyalkyl quaternary ammonium compound is coco pentaethoxy methylammonium methylsulfate, and said trialkyl quaternary ammonium compound is cetyl trimethylammonium chloride.
47. The heat-cured flexible polyurethane foam stabilizer solution of claim 40 wherein said nonionic surfactant is selected from the group consisting of: alcohol ethoxylates, fatty alcohol polyglycol ethers, fatty acid ethoxylates, fatty acid polyglycol esters, glycerol ester monoalkoxylates, alkanolamides, fatty acid alkanolamides, ethoxylated alkanolamides, fatty acid alkanolamide ethoxylates, imidazolines, ethylene oxide-propylene oxide block copolymers, alkylphenol ethoxylates, alkyl glucosides, ethoxylated sorbitan esters and/or amine alkoxylates.
48. The heat-curable flexible polyurethane foam stabilizer solution of claim 40 wherein said amphoteric surfactant is selected from the group consisting of amphoacetates, amphodiacetates, glycinates, amphopropionates, sulfobetaines, amine oxides and/or betaines.
49. The heat-cured flexible polyurethane foam stabilizer solution as claimed in claim 1, wherein the heat-cured flexible polyurethane foam stabilizer solution comprises a fraction of at least one salt compound selected from organic and inorganic salts as a supplementary additive in an amount of 0% or more and 5% or less by weight; the cations are from alkali metal and alkaline earth metal salts and the anions are from sulfates, halides and carboxylates.
50. The heat-cured flexible polyurethane foam stabilizer solution of claim 49 wherein said cations are derived from lithium, sodium, potassium, ammonium and substituted ammonium salts and said anions are derived from benzoate and lactate salts.
51. The heat-cured flexible polyurethane foam stabilizer solution of claim 50 wherein said ammonium salt is a mono-, di-, and tri-ethanolamine salt.
52. The heat-curable flexible polyurethane foam stabilizer solution as claimed in claim 1, wherein the heat-curable flexible polyurethane foam stabilizer solution comprises as a supplementary additive at least one polyhydroxy-functional compound having a functionality of > 3, selected from glycerol, trimethylolpropane, pentaerythritol, monomeric or dimeric glycosides, or water-soluble sugar alcohols, and the fraction of the polyhydroxy-functional additive is > 0% by weight to < 10% by weight, based on the heat-curable flexible polyurethane foam stabilizer solution.
53. The heat-cured flexible polyurethane foam stabilizer solution as set forth in claim 1 wherein said solution comprises at least one additive selected from the group consisting of catalysts, blowing agents, biocides, antioxidants, buffering substances, and/or flame retardants.
54. A heat-cured flexible polyurethane foam stabilizer mixture comprising an amine, a polyol, and/or water, said heat-cured flexible polyurethane foam stabilizer mixture having at least 40 weight percent of the heat-cured flexible polyurethane foam stabilizer solution of any one of claims 1-53, based on the total weight of said heat-cured flexible polyurethane foam stabilizer mixture.
55. Use of a heat-cured flexible polyurethane foam stabilizer solution as claimed in any one of claims 1 to 53 or of a heat-cured flexible polyurethane foam stabilizer mixture as claimed in claim 54 for the preparation of a flexible polyurethane foam.
56. A heat-cured flexible polyurethane foam obtained from the reaction of a polyol and an isocyanate using the heat-cured flexible polyurethane foam stabilizer solution of any one of claims 1 to 53 and/or the heat-cured flexible polyurethane foam stabilizer mixture of claim 54.
57. The heat-cured flexible polyurethane foam of claim 56, wherein the heat-cured flexible polyurethane foam has a pore size distribution in a range from 3 pores/cm to 25 pores/cm.
58. A product comprising the heat-cured flexible polyurethane foam of claim 56 or 57.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006038661A DE102006038661A1 (en) | 2006-08-18 | 2006-08-18 | Use of low-viscosity aqueous polyurethane hot flexible foam stabilizer solutions comprising polyethersiloxanes in the production of hot-cure polyurethane foams |
| DE102006038661.2 | 2006-08-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1127075A1 HK1127075A1 (en) | 2009-09-18 |
| HK1127075B true HK1127075B (en) | 2012-10-12 |
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