DE102015014864A1 - Process for the preparation of cellular, elastic polycarbonate urethane materials and the polycarbonate urethane materials - Google Patents

Abstract

This invention relates to a process for the preparation of cellular polycarbonate urethane polycarbonate urethane based polycarbonate polyurethanes with blowing agent as the blowing agent. The object of the invention is to produce cellular, elastic polycarbonate urethane materials including foams of polycarbonate diols and polyisocyanates in the presence of catalysts and optionally further additives, with exclusively adsorptively bound carbon dioxide being used as blowing agent. According to the invention, the object is achieved with a process for the preparation of cellular, elastic polycarbonate urethane materials based on polycarbonate-polyurethanes with carbon dioxide as blowing agent from polycarbonate diols, chain extenders, catalysts, stabilizers and di- and / or polyisocyanates, which is characterized in that the reaction is carried out with polycarbonate diols containing 0.1 to 30 wt .-% adsorbed carbon dioxide.

Description

This invention relates to a process for the preparation of cellular polycarbonate urethane polycarbonate-based polyurethanes with carbon dioxide blowing agents from polycarbonate diols, chain extenders, catalysts, stabilizers and di- and / or polyisocyanates, and the polycarbonate urethane materials.

The materials are z. B. used as seals in housings.

The preparation of polyurethanes from polycarbonate diols or polycarbonate polyols is known. In particular, thermoplastic polyurethanes are prepared on the basis of Polypropylencarbonatdiolen, see, for. B. DE 10 2012 218 846 and DE 10 2012 218 848 . EP 1 288 241 or WO 2014/060348 , Polycarbonate diols are z. From alkylene oxides and alkyl carbonates, from alkylene oxides and carbon dioxide, from aliphatic diols having from 4 to 6 carbon atoms in the chain (see eg. EP 0 302 712 ) or from cycloaliphatic diols, see, for. B. US 2009/0030242 ,

Polyurethane flexible foams are made of polycarbonate diols in the WO 2008/058193 described. Here, the polycarbonate diols are reacted in place of conventional polyether alcohols with standard formulation ingredients including standard blowing agents. In the WO 2013/053665 Shoe soles, ie cellular elastomers, are described on the basis of polycarbonate diols. Again, blowing agents are added to achieve cellulosity.

In the WO 2012/069414 polyurethane resins are described with a carbonate group content of 1.5 to 25% and in the WO 2010/084872 , Polycarbonate polyurethanes are described with carboxyl groups for ionic polyurethanes, wherein the polycarbonate diols are started from a cycloaliphatic diol.

In the CA 2840738 (24.01.2014) describes two-component systems for the production of spray foams without the use of isocyanates: For the production of spray foams, a common technology with spray guns from two storage containers is used.

The object of the invention is to produce cellular, elastic polycarbonate urethane materials including foams of polycarbonate diols and polyisocyanates in the presence of catalysts and optionally further additives, with exclusively adsorptively bound carbon dioxide being used as blowing agent.

According to the invention, the object is achieved with a process for the preparation of cellular, elastic polycarbonate urethane materials based on polycarbonate-polyurethanes with carbon dioxide as blowing agent from polycarbonate diols, chain extenders, catalysts, stabilizers and di- and / or polyisocyanates, which is characterized in that the reaction is carried out with polycarbonate diols containing 0.1 to 30 wt .-% adsorbed carbon dioxide.

In addition, the object is achieved with cellular, elastic polycarbonate urethane materials, prepared according to a method according to claims 1 to 9.

Advantageous developments are specified in the subclaims.

Thereafter, the polycarbonate diols are prepared in an advantageous embodiment by reacting aliphatic diols and alkyl carbonates or of alkylene oxides and carbon dioxide.

In a further development, an increase in the required amount of adsorbed carbon dioxide by introducing CO ₂ at temperatures of 0 to 100 ° C, preferably 20 to 80 ° C, at an overpressure of 0.01 to 10 bar in the or the polycarbonate diols and a Lowering the amount by heating the loaded polycarbonate diol to temperatures above 50 ° C at reduced pressure, e.g. B. below 100 mbar, especially below 10 mbar.

Further embodiments are characterized in that the polycarbonate diols with diisocyanates in the presence of organotin catalysts and organosilicon compounds as stabilizers that the polycarbonate diols with diisocyanates in the presence of organotin catalysts or that the polycarbonate diols reacted with triisocyanates in the presence of organotin catalysts and organosilicon compounds as stabilizers become.

In a further development, trimers of aliphatic or cycloaliphatic diisocyanates are reacted as triisocyanates.

As isocyanates, symmetrical trimers (hexahydrotriazintriones) of aliphatic diisocyanates are advantageously reacted.

A further embodiment provides that as isocyanates asymmetric trimers (iminooxadiazinediones having three terminal isocyanate groups) are reacted on the basis of aliphatic diisocyanates.

Surprisingly, it has been found that polycarbonate diols which contain one or more aliphatic diols and carbon dioxide and / or aliphatic cyclic carbonates and / or dicarbonates and also polycarbonate diols which are prepared from alkylene oxides and carbon dioxide have a greater or lesser amount of carbon dioxide adsorbed after the synthesis , Depending on the carbonate content of the polycarbonate diols and depending on the nature and the ratio of the diols used, the amount varies between 0.1 and 30% by weight, based on the polycarbonate diol. Since this amount varies, the preparation of cellular material requires a precise adjustment of carbon dioxide content and its control over GC-MS.

• (a) durch Einleiten von zusätzlichem CO₂ bei Temperaturen von 0 bis 100°C, vorzugsweise 20 bis 80°C in das Polycarbonatdiol unter einem Überdruck von 0,01 bis 10 bar oder
• (b) durch Erwärmen des beladenen Polycarbonatdiols auf Temperaturen oberhalb 50°C bei vermindertem Druck, z. B. unter 100 mbar, insbesondere unter 10 mbar

erfolgen.The adsorption of the carbon dioxide takes place on the one hand already in the context of the synthesis of the polycarbonate diols. The adsorbed carbon dioxide can be quantified by gas chromatography / mass spectrometry (GC-MS). The determination of commercial polycarbonate diols gave values in the range of 5 to 10 wt .-%. The maximum possible adsorbed amount of carbon dioxide to the polycarbonate diol appears to be one molecule of carbon dioxide per carbonate group. The adjustment of the adsorbed amount can

• (A) by introducing additional CO ₂ at temperatures of 0 to 100 ° C, preferably 20 to 80 ° C in the polycarbonate diol under an overpressure of 0.01 to 10 bar or
• (b) by heating the loaded polycarbonate diol to temperatures above 50 ° C at reduced pressure, e.g. B. below 100 mbar, especially below 10 mbar

respectively.

In particular, by increasing the temperature and optionally reduced pressure, the amount of adsorbed carbon dioxide can be adjusted. Suitable conditions for the elimination of carbon dioxide are, for. B. 80 ° C and 1 to 0.1 Torr pressure, if necessary with stirring.

• (a) Polyalkylencarbonatdiole aus Alkylenoxiden und Kohlendioxid oder cyclischen Carbonaten oder Biscarbonaten, die Gegenwart bestimmter Katalysatoren, z. B. Doppelmetallcyanid-Katalysatoren, hergestellt werden;
• (b) Polycarbonatdiole auf der Basis von Diolen wie Butan-1,4-diol, Pentan-1,5-diol, Hexan-1,6-diol, Octan-1,8-diol etc. und Kohlendioxid oder cyclischen Carbonaten oder Dicarbonaten;
• (c) Polycarbonatdiole auf der Basis cycloaliphatischer Diole wie Cyclohexan-1,4-dimethanol, Cyclohexan-1,4-diol etc. und Kohlendioxid oder cyclischen Carbonaten oder Dicarbonaten.

Suitable polycarbonate diols are:

• (A) Polyalkylencarbonatdiole from alkylene oxides and carbon dioxide or cyclic carbonates or biscarbonates, the presence of certain catalysts, eg. For example, double metal cyanide catalysts;
• (b) polycarbonate diols based on diols such as butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, etc., and carbon dioxide or cyclic carbonates or dicarbonates ;
• (c) Polycarbonate diols based on cycloaliphatic diols such as cyclohexane-1,4-dimethanol, cyclohexane-1,4-diol, etc., and carbon dioxide or cyclic carbonates or dicarbonates.

Preference is given to polycarbonate diols from mixtures of even and odd-numbered diols and carbonates, more preferably polycarbonate diols based on mixtures of pentane-1,5-diol and hexane-1,6-diol. Also preferred are polycarbonate diols of an aliphatic diol. Also preferred are polycarbonate diols based on low molecular weight ether diols such as diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol.

Such polycarbonate diols are known and described, for. In EP 1 288 241 . US 2011/0230580 . US 2011/0190471 . EP 2 213 696 . WO 2014/072336 . US 2009/0030242 . EP 2 390 277 . WO 2008/013731 . US 2013/0066044 etc. Such polyols are marketed by UBE Corp. available under the trade name ETHERNACOLL ^®, from the Novomer Inc. under the trade name CONVERGE ^® and from Bayer Materials Science.

The polycarbonate diols are reacted with di- and / or polyisocyanates. Suitable are all industrially relevant di- or polyisocyanates. It is possible to use both aromatic, aliphatic, cycloaliphatic, araliphatic diisocyanates, technical products such as crude 4,4'-diphenylmethane diisocyanate, modified diisocyanates such as diphenylmethane diisocyanate liquid at room temperature (either liquefied by means of carbodiimide or liquid at room temperature as isomer mixture), with diols and / or polyols and / or di- and / or polyamines reacted diisocyanates, so-called prepolymers, or triisocyanates, which are obtained by reaction with water in the form of biuretisocyanates or by trimerization of diisocyanates, wherein the trimerization may be symmetrical or asymmetric.

4,4'-diphenylmethane diisocyanate including its modified variants, toluene diisocyanate-2,4 or -2,6 or mixtures thereof, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tris-1,3,5- (6 -isocyanatohexyl) hexahydrotriazine, tris-1,3,5- (6-isocyanatocyclohexyl) hexahydrotriazinetrione, iminooxadiazinediones having three terminal isocyanate groups based on hexane-1,6-diisocyanate, methylpentane diisocyanate, trimethylhexane diisocyanate, bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate , as well as any mixtures thereof.

As catalysts, the known urethane-forming catalysts are used, d. H. teriary amines, organometallic catalysts, alkali metal carboxylates. Preference is given to organotin and bismuth organic compounds, if appropriate mixed with one another.

As a chain extender aliphatic or cycloaliphatic diols or ether diols are used, for. Butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or Tripropylene glycol or mixtures thereof.

As further additives, it is possible to use solids, in particular nanoscale metal oxides, semimetal oxides or metal oxide hydroxides, flame retardants, dyes, pigments, etc.

Elastic cellular materials are understood to mean those materials which have a density in the range from 80 to 900 g / dm ³ and a visible cell density. The cells may be distributed homogeneously or inhomogeneously in the material, be uniform or unevenly large, be open or closed. This also includes elastic foams with higher density and a cell size distribution, which can be different by +/- 70% from an average value.

The processing can be carried out by the one-step or two-step process by hand, with mixing machines, with bag technology or cartridge technology. The one-step process of two premixed components is preferred.

• (a) der Erzeugung von Kohlendioxid als Treibmittel durch Reaktion von Isocyanaten mit Wasser, wodurch ein Teil des (teuren) Isocyanats verbraucht wird oder
• (b) dem Einsatz von Flüssig-Kohlendioxid mit spezieller Maschinentechnik unter hohem Druck („frothing” Verfahren), was eine komplexe Maschinentechnik und besondere Formulierungen voraussetzt,

das Treibmittel mit der Hauptkomponente der Formulierung bereits mitgeliefert wird und kein spezielles chemisches oder physikalisches Treibmittel zugesetzt werden muss, wodurch einerseits die Menge an Isocyanaten gering gehalten und andererseits der Einsatz Fluor- oder Fluorchlor-organischer Verbindungen vermieden wird. Dadurch wird ein ökologisch besonders verträgliches Verfahren zur Herstellung von Materialien mit Dichten unter 1 g/cm³ zur Verfügung gestellt.The advantage of the invention is that over the known methods such as

• (A) the production of carbon dioxide as a blowing agent by reaction of isocyanates with water, whereby a part of the (expensive) isocyanate is consumed or
• (b) the use of liquid carbon dioxide with special machine technology under high pressure ("frothing" process), which requires a complex machine technology and special formulations,

the propellant with the main component of the formulation is already included and no special chemical or physical propellant must be added, whereby on the one hand the amount of isocyanates kept low and on the other hand the use of fluorine or fluorochloro-organic compounds is avoided. As a result, an ecologically particularly compatible process for the production of materials with densities below 1 g / cm ^{3 is} provided.

By using the adsorptively bound carbon dioxide advantageous properties of the material according to the invention are achieved. Reference should be made in particular to the combination of low hardness, high elasticity and very high restoring force as well as the cellular materials high compressive strength without the installation of the usual urea structures. The very high restoring forces at low hardness, z. In the range of Shore A hardness 25 to 35, these materials make candidates for particular polymers with shape memory properties.

Examples

example 1

From 19.8 g of a polycarbonate diol based on hexane-1,6-diol of molecular weight 2200 and 4.76% adsorbed carbon dioxide, 0.9 g of butane-1,4-diol, 0.06 g of dibutyltin bis (2 -ethylhexylthioglykolat) and 0.0235 g TEGOSTAB ^® B 8433 is prepared a a-component by intensive stirring at room temperature (2 hours). S stirring are added 5.9 g of liquid 4,4'-diphenylmethane diisocyanate (Lupranat ^® MP 105 of BASF SE) under 30 to this A component. The mixture foams, the cellular elastomeric material is tack-free after 90 s. It has a density of 422 g / dm ³ .

Example 2

Example 1 is repeated except that 6.7 g of the isocyanate are added. It is after 85 s a after 120 s non-stick cellular elastomeric material (foam) density of 246 g / dm ³ with an average cell size of 1.7 mm (open cells) obtained, which has a Shore A hardness of 38 and while a compression hardness of 12 N / mm ² .

Example 3

The procedure is as in Example 1, but 0.0373 g of DC 193 Dow Corning Corp. are used as the stabilizer. added in place of TEGOSTAB ^® 68,433th The reaction starts after 28 s, the cellular elastomeric material is tack-free after 76 s, has a density of 367 g / dm ³ and a Shore A hardness of 45.

Example 4

The procedure is as in Example 3, but the following amounts are used:
59.4 g of polycarbonate diol as above with 5.33% carbon dioxide
2.025 g of butane-1,4-diol,
0.15 g of tin dioctoate
0.05 g DC 193
13.5 g Lupranat® ^® MP 105

The reaction begins after 26 s, after 90 s is a white, fine-pored cellular elastomeric material (foam) of density 416 g / dm ^{3 formed} with a maximum cell size distribution at 0.9 mm, which is tack-free after 80 s and a Shore A hardness of 31 has.

Example 5

The procedure is as in Example 4, but with the following composition:
59.4 g of polycarbonate diol from a mixture of pentane-1,5-diol and hexane-1,6-diol with 7.18% carbon dioxide by loading at 50 ° C under 1 bar pressure in 30 min
2.025 g of butane-1,4-diol,
0.15 g of tin dioctoate
0.05 g DC 193
13.5 g Lupranat® ^® MP 105

The reaction begins after 22 s, after 70 s is a white, fine-pored cellular elastomeric material (foam) of density 275 g / dm ^{3 formed} with a maximum cell size distribution at 0.6 mm, which is tack-free after 90 s and a Shore A hardness of 35 has.

Example 6

Example 5 is repeated but 14.1 g MP105 Desmodur ^® N 3300 (trimerized hexane-1,6-diisocyanate), Bayer Materials Science be used in place of Lupranat ^®.

The reaction begins after 45 s, 140 s after a white, fine-pored cellular elastomeric material (foam) of density 356 g / dm ^{3 is} formed, which is tack-free after 180 s and a Shore A hardness of 30 and a compression hardness of 9 N / mm ² .

Example 7

As in Example 1, an A component is prepared from
198 g of polypropylene carbonate diol (molar mass 2000) whose CO ₂ content was adjusted to 8.2% by weight by introducing CO ₂ at 45 ° C. in one hour with stirring,
20.1 g of dipropylene glycol
0.08 g TEGOSTAB ^® 8433
0.3 g of catalyst mixture of tin bis (neodecanoate) and dibutyltin bis (2-ethylhexyl thioglycolate) in the ratio 1: 1

By first premixing the chain extender dipropylene glycol with the catalysts for one hour at 200 rpm and then adding with stirring into the polycarbonate diol, this mixture is mixed for a further three hours.

The mixture is reacted with stirring
72.5 g asymmetrically trimerized hexane-1,6-diisocyanate (Desmodur ^® N 3900)

The reaction begins after 45 s, after 190 s, a white cellular elastomeric material of density 366 g / dm ^{3 is} formed, which is tack-free after 270 s and has a Shore A hardness of 39 and a compression hardness of 12 N / mm ² ,

Example 8

As in Example 7, an A component is made up
99 g polycarbonate diol based on hexane-1,6-diol with 4.96 wt .-% adsorbed CO ₂
13.4 g of dipropylene glycol
0.3 g of catalyst mixture of tin bis (neodecanoate) and dibutyltin bis (2-ethylhexylthioglycolate) in the ratio 2: 1

The mixture is reacted with stirring
54.4 g asymmetrically trimerized hexane-1,6-diisocyanate (Desmodur ^® N 3900)

The reaction begins after 40 seconds, after 200 seconds a white cellular elastomeric material of density 522 g / dm ^{3 is} formed which is tack-free after 240 seconds and has a Shore A hardness of 43.

Example 9

A polycarbonate diol is prepared from hexane-1,6-diol and diethyl carbonate in the presence of double metal catalysts. After the preparation and removal of the ethanol, the polycarbonate diol has a molecular weight M _n (maximum of the GPC peak) of 2265 and a hydroxyl value of 51.3 mg KOH / g. According to GC-MS, the content of CO _{2 is} 1.26% by weight. 2500 g of this polycarbonate diol are heated in a stainless steel miniplant to 58 ° C. with stirring and carbon dioxide is introduced until the pressure in the reactor is 7.66 bar. After cooling, the content of CO _{2 is} 9.55 wt .-% by GC-MS.

Example 10

In a pressure reactor at 32 bar propylene oxide and carbon dioxide are reacted in two streams at a temperature rising from 30 to 120 ° C in the presence of double metal catalysts in five hours. A polypropylene carbonate diol containing 32.2% by weight of CO ₂ in the chain and 12.3% by weight is adsorbed.

250 g of this polypropylene carbonate diol are processed on a rotary evaporator at 75 ° C. and 0.1 torr for 2 hours. After cooling, an adsorbed carbon dioxide content of 2.12 wt.% Is determined by GC-MS.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102012218846 [0003]
• DE 102012218848 [0003]
• EP 1288241 [0003, 0022]
• WO 2014/060348 [0003]
• EP 0302712 [0003]
• US 2009/0030242 [0003, 0022]
• WO 2008/058193 [0004]
• WO 2013/053665 [0004]
• WO 2012/069414 [0005]
• WO 2010/084872 [0005]
• CA 2840738 [0006]
• US 2011/0230580 [0022]
• US 2011/0190471 [0022]
• EP 2213696 [0022]
• WO 2014/072336 [0022]
• EP 2390277 [0022]
• WO 2008/013731 [0022]
• US 2013/0066044 [0022]

Claims (10)

A process for the preparation of cellular, elastic Polycarbonateaturethan materials based on polycarbonate-polyurethanes with carbon dioxide blowing agent from Polycarbonatdiolen, chain extenders, catalysts, stabilizers and di- and / or polyisocyanates characterized in that the reaction is carried out with polycarbonate diols, the 0.1 to 30 wt .-% adsorbed carbon dioxide. A method according to claim 1, characterized in that the polycarbonate diols are prepared by reacting aliphatic diols and alkyl carbonates or of alkylene oxides and carbon dioxide, A method according to claim 1 or 2, characterized in that an increase in the required amount of adsorbed carbon dioxide by introducing CO ₂ at temperatures of 0 to 100 ° C, preferably 20 to 80 ° C, at an overpressure of 0.01 to 10 bar in the or the polycarbonate diols and a reduction in the amount by heating the loaded polycarbonate diol to temperatures above 50 ° C at reduced pressure, for. B. below 100 mbar, especially below 10 mbar. Method according to one of claims 1 to 3, characterized in that the polycarbonate diols are reacted with diisocyanates in the presence of organotin catalysts and organosilicon compounds as stabilizers. Method according to one of claims 1 to 4, characterized in that the polycarbonate diols are reacted with diisocyanates in the presence of organotin catalysts. Method according to one of claims 1 to 5, characterized in that the polycarbonate diols are reacted with triisocyanates in the presence of organotin catalysts and organosilicon compounds as stabilizers. Method according to one of claims 1 to 6, characterized in that are reacted as triisocyanates trimers of aliphatic or cycloaliphatic diisocyanates. Method according to one of claims 1 to 7, characterized in that as isocyanates symmetrical trimers (Hexahydrotriazintrione) of aliphatic diisocyanates are reacted. Method according to one of claims 1 to 8, characterized in that as isocyanates asymmetric trimers (iminooxadiazinediones with three terminal isocyanate groups) are reacted on the basis of aliphatic diisocyanates. Cellular, elastic polycarbonate urethane materials producible according to a process according to claims 1 to 9.