CA2088091A1 - 3-quinuclidinol catalyst compositions for making polyurethane foams - Google Patents
3-quinuclidinol catalyst compositions for making polyurethane foamsInfo
- Publication number
- CA2088091A1 CA2088091A1 CA002088091A CA2088091A CA2088091A1 CA 2088091 A1 CA2088091 A1 CA 2088091A1 CA 002088091 A CA002088091 A CA 002088091A CA 2088091 A CA2088091 A CA 2088091A CA 2088091 A1 CA2088091 A1 CA 2088091A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- quinuclidinol
- composition
- hydrogen
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2054—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having one nitrogen atom in the condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/902—Cellular polymer containing an isocyanurate structure
Abstract
ABSTRACT
A method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst composition consisting essentially of at least one compound of the following formula:
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 0-3. The preferred catalyst consists essentially of of the compound when n is 0, namely 3-quinuclidinol.
MLO106A.APP
A method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst composition consisting essentially of at least one compound of the following formula:
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 0-3. The preferred catalyst consists essentially of of the compound when n is 0, namely 3-quinuclidinol.
MLO106A.APP
Description
2~8~91 FOR MAKING POLYURETHANE FOAMS
TECHNICAL FIELD
The present invention relates to tertiary amine catalysts for catalyzing the urethane reaction in making polyurethane foam.
BACKGROUND OF THE INVENTION
Polyurethane foams are widely known and used in automotive, housing and oth~r industries. Foam is generally referred to as rigid, microcellular, or flexible. Typically, in the~preparation of polyurethane foams, a tertiary amine catalyst is used to accelerate the reaction of the polyisocyanate with water to generate carbon dioxide as a blowing agent and to accelerate the reaction with polyols to promote gelling. Tertiary amines generally are malodorous and offensive, and many have high volatility due to low molecular weight. Release of tertiary amine during foam processing may present significant safety and toxicity problems, and release of residual amines from consumer products is generally undesirable.
Amine catalysts which contain primary and/or secondary hydroxyl functionality typically have limited volatility and low odor when compared to related structures which lack this functionality. Furthermore, catalysts which contain hydroxyl functionality chemically bond into the urethane during the reaction and are not released from the finished product.
Catalyst structures which embody this concept are typically of low to moderate activity and are designed to promote primarily the blowing (water-isocyanate) reaction.
2088~g~
U.S. 4,957,944 discloses certain dimethylamino alkyleneoxy isopropanols for use as a catalyst for preparing polyurethane foam.
U.S. 5,071,809 discloses tertiary amine catalysts containing secondary alcohol functionality for use in preparing polyurethane foams. The tertiary amines containing secondary alcohol functionality are prepared by reacting an olefinic nitrile with an aliphatic polyol having at least one secondary hydroxyl functionality, followed by reductive alkylation of the resulting cyanoalkylated polyol with a secondary aliphatic or cycloaliphatic amine, including those containing hetero atoms.
U.S. 4,590,223 discloses the preparation of tertiary aminea containing secondary alcohols by reacting N-alkyl-piperazines with an alkyleneoxidë~
Secondary alcohol functionality is preferred in these structures because the catalysts exhibit a desirable balance between their promotion o~ the water-isocyanate reaction and their own reactivity with isocyanates. In contrast, catalysts which contain primary alcohols react rapidly with isocyanates and thus high use levels are requir~d. Catalysts which contain tertiary alcohols react slowly with isocyanates, but the urethanes which are formed from the tertiary alcohols have poor thermal stability. See G. Oertel, ed. "Polyurethane Handbook,"
Hanser Publishers, Munich, 1985, pp. 82, 84 and H. J. Fabris, "Advances in Urethane Science and Technology," VO1D 5r Technomic Publishing Co., Westport, CT, 1978, pp. 173-179.
These urethanes may degrade and release the catalysts at temperatures substantially below the decomposition temperature of the foam itself. The free amine could then accelerate foam decomposition.
A catalyst which strongly promotes the polyol-isocyanate (gelling) reaction is necessary for the manufacture of many polyurethane foams. Triethylenediamine (1,4-diazabicyclo-2~8~91 [2.2.2.]octane) is widely used for this purpose. Quinuclidine(1-azabicyclo[2.2.2.]octane) can also be used as a gelling catalyst, particularly when the polyol contains a preponderance of secondary hydroxyl groups (U.S. 3,036,021). Quinuclidine is more reactive than triethylenediamine for the production of polyurethane foams. Both triethylenediamine and quinuclidine are volatile materials which will not remain trapped in the foam.
U.S. 3,036,021 also discloses that 1-azabicyclooctanes and their alkyl, amino, hydroxyl, nitro, alkoxy and halogen derivatives can also be used as gelling catalysts, although no distinctions were made with regard to the effect of catalyst structure on activity or suitability for incorporation into a foam.
U.S. 4,186,040 discloses a solid, pyrotechnic composition for dissemination of 3-quinuclidinyl benzylete, the composition consisting essentially of 3-quinuclidinyl benzylete and an oxidizer incorporated in a solid foamed polyurethane binder.
No information is provided on the utility of quinuclidinyl benzylete as a catalyst or as a TED~ replacement. Furthermore, quinuclidinyl benzylete does not remain trapped in the foam.
SUMMARY OF THE INVENTION
The present invention provides a catalyst composition for catalyzing the trimerization of an isocyanate and/or the reaction between an isocyanate and a compound containing a reactive hydrogen, e.g., the urethane reaction for making polyurethane. The catalyst composition is a family of hydroxy-functional amines which comprises 3-quinuclidinol, alterna-tively 3-hydroxy-1-azabicyclo[2.2.2.Joctane, as represented by the following formula I and the alkoxylated derivatives of 3-quinuclidinol as represented by the following formula II:
~,OH
N
:
~ ~ ~ 3n II
where R is hydrogen, a C1-C8 alkyl, C6 C10 ary , 7 10 aralkyl group; and n is 1-3.
Compositions comprising mixtures of 3-quinuclidinol and compounds o~ formula II in which "n" is within the specific range are particularly preferred as catalysts, e.g., in such mixtures "n" would be 0-3, and most desirably "n" is O and l.
~ As an advantage o~ the catalyst compositions, they ; strongly promote the polyol-isocyanate (gelling) reaction and are subsequently incorporated into th~ polyurethane product.
Another embodiment oP the present inYention is a poly-urethane foam prepared by reacting a polyisocyanate, a polyol, water, cell sta~izer ~nd a cata~yst compositi~n wh~rh ~$~g~
comprises the hydroxyl functional amines of at least one o~ the above formulas I and II.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst compositions according to the invention can catalyze the reaction between an isocyanate functionality and an active hydrogen-containing compound, i.e. an alcohol, an amine or water, especially the urethane (gelling) reaction to make polyurethanes and the blowing reaction of water with isocyanate to release carbon dioxide for making foamed poly-urethanes, or the trimerization of the isocyanate functionality to form polyisocyanurates.
The polyurethane products are prepared usin~ suitable organic polyisocyanates well known in the art including, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4,4'-diphenylmethane diiso-cyanate ("MDI"). Especially suitable are the 2,4- and 2,6-TDIs individually or together as their commercially available mixtures. Other suitable isocyanates are mixtures of diisocyanates known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diiso-cyanate along with other isomeric and analogous higher polyisocyanates. Also suitable are "prepolymers" of these polyisocyanates comprising a partially prereacted mixture of polyisocyanates and polyether or polyester polyols.
Illustrative of suitable polyols as a component of the polyurethane composition are the polyalkylene ether and polyester polyols. The polyaIkylene ether polyols include th~
poly(alkylene oxide) polymers such as poly(ethylene oxide~ and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, among others, athylene glycol, propylene glycol, 1,3-butan2 diol, 1,4-butane diol, 1,6-hexane .
8~91 diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and like low molecular weight polyols.
In the pr~ctice of this invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols such as mixtures of di- and tri-functional materials and/or different molecular weight or different chemical composition materials may be used.
Useful polyester polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid with ethylene glycol or butanediol, or reacting a lactone with an excess of a diol such as reacting caprolactone with propylene glycol.
In addition to the polyether and polyester polyols, the masterbatches, or premix compositions, frequently contain a polymer polyol. Polymer polyols are used in polyurethane foam to increase the foam's resistance to deformation, i.e. to increase the load-bearing properties of the foam. Currently, two different types of polymer polyols are used to achieve load-bearing improvement. The first type, described as a graft polyol, consists of a triol on which vinyl monomers are graft copolymerized. Styrene and acrylonitrile are the usual monomers of choice. The second type, polyurea modified polyols, is a polyol containing a polyurea dispersion formed by the reaction of a diamine and TDI. Since TDI is used in excess, some of the TDI may react with both the polyol and polyurea. This second type of polymer polyol has a variant called PIPA polyol which is formed by the in-situ polymer-ization of TDI and alkanolamine in the polyol. Depending on the load-bearing requirements, polymer polyols may comprise 20-80% of the polyol portion of the masterbatch.
Other typical agents found in the polyurethane foam ~ormulations include crosslinkers such as ethylene glycol, _ 7 _ 2~
butanediol, diethanolamine, diisopropanolamine, triethanolamine and/or tripropanolamine; blowing agents such as water, methylene chloride, trichlorofluoromethane and the like; and cell stabilizers such as silicones.
A general polyurethane flexible foam formulation containing the catalyst composition according to the invention would comprise the following components in parts by weight (pbw) Flexible Foam Formulation Parts bv Weiqht ~ Polyol 20 - 80 Polymer Polyol 80 - 20 : Silicone Surfactant 1 - 2.5 - 20 Blowing Agent 2 - 4.5 Crosslinker 0.5 - 2 Catalyst 0.5 - 2 Isocyanate Index 92 - 115 The urethane catalyst composition consists essentially of 3-quinuclidinol or a 3-quinuclidinol deriva~ive compound of the following general formula II, or a mixture thereof:
~ ~ 0 N
2~8~91 where R is a hydrogen, C~-C8 alkyl, C~-C10 aryl or C7-C10 aralkyl group; and n is 1-3, preferably 1-2, and most preferably n is 1.
For mixtures of compounds suitable as catalyst compositions tbased on formula II), n is 0-3, preferably 0-2, and most preferably 0-1. For 3-quinuclidinol, n is 0 in formula II.
Preferred mixtures which are liquid products would comprise 0 to 85 wt%, preferably 50 to 85 wt%, 3~quinuclidinol and 15 to 100 wt%, preferably 15 to 50 wt~, derivatives of form~la II, provided that the derivative in which n is 3 and higher oligomers comprise no greater than 50 wt% of the mixture.
These mixtures can be prepared by simply blending the desired amounts of 3 quinuclidinol and appropriate derivatives or, in some cases by reacting 3-quinuclidinol with an appropriate amount of alkylene oxide.
Alkyl groups would include, for ~xample, methyl, ethyl, butyl, ethylhexyl and the like; aryl groups would include, for example, phenyl, p-tolyl and the like, and aralkyl groups would include, for example, benzyl, phenethyl and the likeO It is preferred that R be methyl.
The 3-quinuclidinol may be prepared by the procedure of U.S. 3,464,997. It is also commercially available, being marketed by Janssen Chemical and Aldrich Chemicals.
The alkoxylated derivatives of 3-quinuclidinol can be prepared by reacting 3-quinuclidinol with an alkylene oxide of the formula H2C-CHR
where R is hydrogen, C1-CB alkyl, C6-C10 aryl or C7-C~
aralkyl, in the presence of a base catalyst in a dipolar aprotic solvent at temperatures ranging from RT up to the boiling point of the solvent and at pressures up to autogenous pressure. It is preferred that R be H or methyl, especially methyl. The alkylene oxide and the 3-quinuclidinol can be 2~8~
_ 9 reacted in a 0.2:1 to 10:1 mole ratio range, preferably 1:1 to 3:1.
These derivatives of 3-quinuclidinol for the most part can be represented by formula II; however, lesser amounts of compounds involving ~1CH-CH20tn linkages could also be present R
in the reaction products.
A catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, suitable amounts of the catalyst composition may range from about 0.01 to 10 parts per 100 parts by weight polyol in the polyurethane formulation.
T~e catalyst compositions may be used in combination with other tertiary amine and organotin urethane catalysts well known in the urethane art.
Example 1 In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in parts by weight was:
COMPONENT PARTS
Multr~ol 9151 70 ~ultr~nol 91~ 30 ~ater 4.2 Diet~anolami~e 1.74 DC 5164 1.0 TDI 80 105 index ~ultranol 9151 polyol -- polyurea filled, ethylene oxide tipped polyether polyol marketed by Mobay Corp.
~ ultranol 91~3 polyol -- ethylene oxide tipped, conventional polyether polyol marketed by Mobay Corp.
2 ~
DABCO DC 516~ silicone surfactant marketed by Air Products and Chemicals, Inc.
TDI 80 -- a mixture of 80 wt% 2,4-TDI and 20 wt% 2,6-TDI.
The foam reactivity was measured using 33 wt% 3-quinucli-dinol (3-QND) in ethylene glycol or DABC0 33LV~ catalyst (33 wt% triethylenediamine in dipropylene glycol) as gelling catalysts and DABC0~ BL-11 catalyst [70 wt% bis(dimethylamino-ethyl)ether in dipropylene glycol] as the blowing catalyst.
The activity of 3-QND was also compared to that of DABC0 33LV~
catalyst in the absence of a cocatalyst. Table 1 sets forth conditions and results.
Tdbie 1 DABC0 33LV/ 3-~ND/
Catalvst DABC0 BL-11DABC0 BL-11DABC0 33LV 3-QND
Amount (parts) 0.42/0.150.42/0.15 1.26 1.26 Top o~ Cup 1 (sec)11.3 10.~ 11.6 10.6 20 Top of Cup 2 (sec)47.6 40.5 40.0 43.3 String ~el (sec) 65.6 61.8 63.6 69.0 Full Rise Time (sec) 132.1 141.3 112.1 142.0 Times cited were from mixing of the polyol masterbatch with isocyanate. Top Cup 1 represents the time required for the foam formulation to fill a 16 oz cup and is an indication of reaction initiation. ~op Cup ~ represents the time required for the foam formulation to fill a 1 gal cup in addition to the 16 oz cup mentioned above and is an indication of reaction progression. String Gel and Full Rise are further measures of reaction prsgression and provide some indication of extent of cure.
The advantage of 3-quinuclidinol is that it provides an excellent reactivity match for triethylenediamine during the critical early stages of the foaming reaction, and is then 2 ~
incorporated into the polymer, as seen in the increased full rise time measurement. Furthermore, the amount of 3-quinucli-dinol can be increased to shorten the full rise time, but volatile emissions from the final product will not increase.
Example 2 The example shows the propoxylation of 3-quinuclidinol.
To 25g (197.1 mmol) of 3-quinuclidinol suspended in 30 mL
of N,N-dimethylformamide (DMF) was added 0.0356g (0.89 mmol) of sodium hydroxide catalyst. The mixture was heated to 65C with stirring. Propylene oxide (103.22g, 592 mmols) was added dropwise while maintaining the temperature between 70 to 76C.
The 3-~uinuclidinol conversion was 98.5%. The DMF was removed by vacuum distillation, and the residue fractionated by Kugelrohr distillation. Selected fractions were designated Propoxylate 1-3 and were tested as described in Example 3 and Table 2.
Example 3 This example demonstrates the relative reactivity of the 3-quinuclidinol derivatives.
The rate of isocyanate consumption as a function of time was measured using a formulation similar to that of Example 1, but containing monofunctional reactants. Reaction samples drawn at the indicated times were quenched with dibutylamine and analyzed by liquid chromatography. The catalysts were compared on an equimolar basis corresponding to a loading of 0.35 parts per hundred parts of DABC0 33LV catalyst in the formulation in Example 1. Table 2 sets forth the results.
2 ~ 9 ~.
Table 2 ~ NC0 Conversion Time Catalv~t (minl 0 5 1.0 1.5 2.0 3.0 4.0 5 0 6.0 Trlethylenediamine 14.2 28.9 44.0 50.3 64.1 71.6 76.5 79.9 3-auinuclidinol 18.9 34.2 46.4 54.3 66.2 72.7 76.6 79.2 Propoxylat~ 1a l6.2 29.6 41.6 50.4 64.3 71.4 76.2 79.3 Propoxylat~ 2b 16.1 28.7 40.3 48.6 59.4 65.6 69.5 72.3 Propoxylate 3c 7.2 14.3 19.8 28.7 42.2 50.8 58.4 63.9 Hydroquinined 7.9 17.8 25.5 32.1 41.9 49.7 54.6 59.9 a Propoxylat~ 1 contains 2.7% 3-quinuclidinol, 70.0~ monopro ox late (Formula II, n=1) and 27.3~ dipropoxylate (Formula II, n=2) on a mo~e ~asis.
t5 b Propoxylate 2 contains 17.1~ monopropoxylate, 59.6% dipropoxylate, and 16.4%
tripopoxylate on a mole basis.
c Propoxylate 3 contains 6.6~ dipropoxylate, 79.8% tripropoxylate, and 9.2%
~tetrapropo~ylate on a mole basis.
d ~CH2CH~
~H
CH30 ~
Hyd~qu~ina The uniqueness of the propoxylated 3-quinuclidinol derivatives is that they retain the desirable hiyh activity of 3-quinuclidinol itself, as well as the necessary secondary alcohol functionality, but are liquids readily soluble in a variety of ommon catalyst carriers; e.g., dipropylene glycol.
3-Quinuclidinol, itself, is a high melting solid with limited solubility and thus is not convenient for all applications.
Hydroquinine, although it also contains a secondary alcohol, is poorly active. Desirable activity is obtained i~ substituents are placed on the 3-position, rather than the 2-position, of 1-azabicyclo[2.2.2.]octane. The size of the substituent on the 2 ~ 9 1 3-position may also influence the level of activity, as shown by the comparison of the results for propoxylate 3 to those for hydroquinine.
Example 4 This example demonstrates the partial propoxylation of 3-quinuclidinol.
3-Quinuclidinol (39.4 mmols, 5.01g~, sodium hydroxide (0.2 mmol, 0.008g), and DMF (lOmL) were charged to a 50mL 3-neck roundbottom flask equipped with a magnetic stir bar, thermometer, reflux condenser and a septum. Propylene oxide (19.7 mmols, 1.14g~ was added by syringe over 5 minutes while stirring and heating the solution ~o 60C. The temperature rose 5-10C following the propylene oxide addition, and gradually dropped back to 60C over the next 15 minutes. The DMF was removed by heating the reaction to 40C at 500 mTorr for several hours. The product was a liquid.
The experiment was repeated as above with 39.7 mmols (5.05g) of 3-r~uinuclidinol and 40.0 mmols (2.31g) of propylene oxide, the other reagents and conditions remaining unchanged.
The samples were analyzed by gas chromatography to determine - the extent of propoxylation. The results are tabulated below.
3-Ouinuclidinol Propylene Oxide _ 9~i Area bV GC
Run (mmols) _ !mmols) DMF 3-Quinuclidinol mono-PO di-PO tri-PO4A 39.4 19.7 2 85 8 2 : 4B 39.7 40.0 0.6 54 22 9 11 Example 5 In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in weight parts was:
Component Parts PluraGol-816 40 Plur~col-973 60 W ter 3.5 Diethanolamine1.49 DC 50~3 1.5 TDI 80 105 index Pluraool-816 polyol -- ethylene oxide tipped, conventional polyether polyol marketed by BASF AG.
Pluracol-973 polyol -- styrene-acrylonitrile filled, ethylene oxide tipped polyether polyol marketed by BASF AG.
DABCO DC 5043 silicone surfactant marketed by Air Products and Chemicals, Inc.
The foam reactivity was measured using DABC0 33L~
: catalyst, Run 4A catalyst (50 wt% in water) or Run 4B catalyst (50 wt% in water) as gelling catalysts and DABC0 BL-11 catalyst as the blowing catalyst. Table 3 sets forth conditions and 20 results.
Table 3 DABC0 33LV/ Run 4A/ Run 4B/
Catalyst DABC0 BL-ll DABCO BL-11 DABCO BL-11 Level (parts) 0.50/0.150.41/0.15 0.54/0.15 Top of Cup 1 (sec) 10.2 10.7 11.3 Top of Cup 2 (sec) 32.3 35.2 34.9 String Gel (sec) 68.8 64.0 64.1 30 Full rise time (sec) 99.3 94.3 98.1 The results in Table 3 indicate that mixtures containing 3-quinuclidinol and propoxylated 3-quinuclidinol have activity o ~
comparable to that of triethylenediamine at equimolar use levels. Furthermore, the partially propoxylated mixtures are liquids which are more convenient to handle than 3-quinucli-dinol itself.
The prior art high activity amine gelling catalysts are fugitive in that they can escape from a foam during or after its manufacture. The present invention successfully incorporates secondary alcohol functionality into high activity gelling catalysts which display activity similar to that of TEDA, the industry standard. The secondary alcohol functionality lowers the volatility of the catalysts of the invention and prevents their escape from the finished foam prodùct through the chemical reaction with the foam itself.
Moreover, the catalyst compositions are liquids which are easïly processed and show negligible activity loss as compared to 3-quinuclidinol.
The prior art does not indicate that quinuclidine or its derivatives would be expected to have activity very similar to that of TEDA. An activity match is desirable so that the catalysts for the present invention can be easily employed as drop-in replacements for TEDA.
STATEMENT OF INDUSTRIAL APPLICATION
The present invention provides compositions for catalyzing the urethane reaction and preparing urethane products, especially polyur~thane foam products.
ML0106A.APP
TECHNICAL FIELD
The present invention relates to tertiary amine catalysts for catalyzing the urethane reaction in making polyurethane foam.
BACKGROUND OF THE INVENTION
Polyurethane foams are widely known and used in automotive, housing and oth~r industries. Foam is generally referred to as rigid, microcellular, or flexible. Typically, in the~preparation of polyurethane foams, a tertiary amine catalyst is used to accelerate the reaction of the polyisocyanate with water to generate carbon dioxide as a blowing agent and to accelerate the reaction with polyols to promote gelling. Tertiary amines generally are malodorous and offensive, and many have high volatility due to low molecular weight. Release of tertiary amine during foam processing may present significant safety and toxicity problems, and release of residual amines from consumer products is generally undesirable.
Amine catalysts which contain primary and/or secondary hydroxyl functionality typically have limited volatility and low odor when compared to related structures which lack this functionality. Furthermore, catalysts which contain hydroxyl functionality chemically bond into the urethane during the reaction and are not released from the finished product.
Catalyst structures which embody this concept are typically of low to moderate activity and are designed to promote primarily the blowing (water-isocyanate) reaction.
2088~g~
U.S. 4,957,944 discloses certain dimethylamino alkyleneoxy isopropanols for use as a catalyst for preparing polyurethane foam.
U.S. 5,071,809 discloses tertiary amine catalysts containing secondary alcohol functionality for use in preparing polyurethane foams. The tertiary amines containing secondary alcohol functionality are prepared by reacting an olefinic nitrile with an aliphatic polyol having at least one secondary hydroxyl functionality, followed by reductive alkylation of the resulting cyanoalkylated polyol with a secondary aliphatic or cycloaliphatic amine, including those containing hetero atoms.
U.S. 4,590,223 discloses the preparation of tertiary aminea containing secondary alcohols by reacting N-alkyl-piperazines with an alkyleneoxidë~
Secondary alcohol functionality is preferred in these structures because the catalysts exhibit a desirable balance between their promotion o~ the water-isocyanate reaction and their own reactivity with isocyanates. In contrast, catalysts which contain primary alcohols react rapidly with isocyanates and thus high use levels are requir~d. Catalysts which contain tertiary alcohols react slowly with isocyanates, but the urethanes which are formed from the tertiary alcohols have poor thermal stability. See G. Oertel, ed. "Polyurethane Handbook,"
Hanser Publishers, Munich, 1985, pp. 82, 84 and H. J. Fabris, "Advances in Urethane Science and Technology," VO1D 5r Technomic Publishing Co., Westport, CT, 1978, pp. 173-179.
These urethanes may degrade and release the catalysts at temperatures substantially below the decomposition temperature of the foam itself. The free amine could then accelerate foam decomposition.
A catalyst which strongly promotes the polyol-isocyanate (gelling) reaction is necessary for the manufacture of many polyurethane foams. Triethylenediamine (1,4-diazabicyclo-2~8~91 [2.2.2.]octane) is widely used for this purpose. Quinuclidine(1-azabicyclo[2.2.2.]octane) can also be used as a gelling catalyst, particularly when the polyol contains a preponderance of secondary hydroxyl groups (U.S. 3,036,021). Quinuclidine is more reactive than triethylenediamine for the production of polyurethane foams. Both triethylenediamine and quinuclidine are volatile materials which will not remain trapped in the foam.
U.S. 3,036,021 also discloses that 1-azabicyclooctanes and their alkyl, amino, hydroxyl, nitro, alkoxy and halogen derivatives can also be used as gelling catalysts, although no distinctions were made with regard to the effect of catalyst structure on activity or suitability for incorporation into a foam.
U.S. 4,186,040 discloses a solid, pyrotechnic composition for dissemination of 3-quinuclidinyl benzylete, the composition consisting essentially of 3-quinuclidinyl benzylete and an oxidizer incorporated in a solid foamed polyurethane binder.
No information is provided on the utility of quinuclidinyl benzylete as a catalyst or as a TED~ replacement. Furthermore, quinuclidinyl benzylete does not remain trapped in the foam.
SUMMARY OF THE INVENTION
The present invention provides a catalyst composition for catalyzing the trimerization of an isocyanate and/or the reaction between an isocyanate and a compound containing a reactive hydrogen, e.g., the urethane reaction for making polyurethane. The catalyst composition is a family of hydroxy-functional amines which comprises 3-quinuclidinol, alterna-tively 3-hydroxy-1-azabicyclo[2.2.2.Joctane, as represented by the following formula I and the alkoxylated derivatives of 3-quinuclidinol as represented by the following formula II:
~,OH
N
:
~ ~ ~ 3n II
where R is hydrogen, a C1-C8 alkyl, C6 C10 ary , 7 10 aralkyl group; and n is 1-3.
Compositions comprising mixtures of 3-quinuclidinol and compounds o~ formula II in which "n" is within the specific range are particularly preferred as catalysts, e.g., in such mixtures "n" would be 0-3, and most desirably "n" is O and l.
~ As an advantage o~ the catalyst compositions, they ; strongly promote the polyol-isocyanate (gelling) reaction and are subsequently incorporated into th~ polyurethane product.
Another embodiment oP the present inYention is a poly-urethane foam prepared by reacting a polyisocyanate, a polyol, water, cell sta~izer ~nd a cata~yst compositi~n wh~rh ~$~g~
comprises the hydroxyl functional amines of at least one o~ the above formulas I and II.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst compositions according to the invention can catalyze the reaction between an isocyanate functionality and an active hydrogen-containing compound, i.e. an alcohol, an amine or water, especially the urethane (gelling) reaction to make polyurethanes and the blowing reaction of water with isocyanate to release carbon dioxide for making foamed poly-urethanes, or the trimerization of the isocyanate functionality to form polyisocyanurates.
The polyurethane products are prepared usin~ suitable organic polyisocyanates well known in the art including, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4,4'-diphenylmethane diiso-cyanate ("MDI"). Especially suitable are the 2,4- and 2,6-TDIs individually or together as their commercially available mixtures. Other suitable isocyanates are mixtures of diisocyanates known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diiso-cyanate along with other isomeric and analogous higher polyisocyanates. Also suitable are "prepolymers" of these polyisocyanates comprising a partially prereacted mixture of polyisocyanates and polyether or polyester polyols.
Illustrative of suitable polyols as a component of the polyurethane composition are the polyalkylene ether and polyester polyols. The polyaIkylene ether polyols include th~
poly(alkylene oxide) polymers such as poly(ethylene oxide~ and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, among others, athylene glycol, propylene glycol, 1,3-butan2 diol, 1,4-butane diol, 1,6-hexane .
8~91 diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and like low molecular weight polyols.
In the pr~ctice of this invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols such as mixtures of di- and tri-functional materials and/or different molecular weight or different chemical composition materials may be used.
Useful polyester polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid with ethylene glycol or butanediol, or reacting a lactone with an excess of a diol such as reacting caprolactone with propylene glycol.
In addition to the polyether and polyester polyols, the masterbatches, or premix compositions, frequently contain a polymer polyol. Polymer polyols are used in polyurethane foam to increase the foam's resistance to deformation, i.e. to increase the load-bearing properties of the foam. Currently, two different types of polymer polyols are used to achieve load-bearing improvement. The first type, described as a graft polyol, consists of a triol on which vinyl monomers are graft copolymerized. Styrene and acrylonitrile are the usual monomers of choice. The second type, polyurea modified polyols, is a polyol containing a polyurea dispersion formed by the reaction of a diamine and TDI. Since TDI is used in excess, some of the TDI may react with both the polyol and polyurea. This second type of polymer polyol has a variant called PIPA polyol which is formed by the in-situ polymer-ization of TDI and alkanolamine in the polyol. Depending on the load-bearing requirements, polymer polyols may comprise 20-80% of the polyol portion of the masterbatch.
Other typical agents found in the polyurethane foam ~ormulations include crosslinkers such as ethylene glycol, _ 7 _ 2~
butanediol, diethanolamine, diisopropanolamine, triethanolamine and/or tripropanolamine; blowing agents such as water, methylene chloride, trichlorofluoromethane and the like; and cell stabilizers such as silicones.
A general polyurethane flexible foam formulation containing the catalyst composition according to the invention would comprise the following components in parts by weight (pbw) Flexible Foam Formulation Parts bv Weiqht ~ Polyol 20 - 80 Polymer Polyol 80 - 20 : Silicone Surfactant 1 - 2.5 - 20 Blowing Agent 2 - 4.5 Crosslinker 0.5 - 2 Catalyst 0.5 - 2 Isocyanate Index 92 - 115 The urethane catalyst composition consists essentially of 3-quinuclidinol or a 3-quinuclidinol deriva~ive compound of the following general formula II, or a mixture thereof:
~ ~ 0 N
2~8~91 where R is a hydrogen, C~-C8 alkyl, C~-C10 aryl or C7-C10 aralkyl group; and n is 1-3, preferably 1-2, and most preferably n is 1.
For mixtures of compounds suitable as catalyst compositions tbased on formula II), n is 0-3, preferably 0-2, and most preferably 0-1. For 3-quinuclidinol, n is 0 in formula II.
Preferred mixtures which are liquid products would comprise 0 to 85 wt%, preferably 50 to 85 wt%, 3~quinuclidinol and 15 to 100 wt%, preferably 15 to 50 wt~, derivatives of form~la II, provided that the derivative in which n is 3 and higher oligomers comprise no greater than 50 wt% of the mixture.
These mixtures can be prepared by simply blending the desired amounts of 3 quinuclidinol and appropriate derivatives or, in some cases by reacting 3-quinuclidinol with an appropriate amount of alkylene oxide.
Alkyl groups would include, for ~xample, methyl, ethyl, butyl, ethylhexyl and the like; aryl groups would include, for example, phenyl, p-tolyl and the like, and aralkyl groups would include, for example, benzyl, phenethyl and the likeO It is preferred that R be methyl.
The 3-quinuclidinol may be prepared by the procedure of U.S. 3,464,997. It is also commercially available, being marketed by Janssen Chemical and Aldrich Chemicals.
The alkoxylated derivatives of 3-quinuclidinol can be prepared by reacting 3-quinuclidinol with an alkylene oxide of the formula H2C-CHR
where R is hydrogen, C1-CB alkyl, C6-C10 aryl or C7-C~
aralkyl, in the presence of a base catalyst in a dipolar aprotic solvent at temperatures ranging from RT up to the boiling point of the solvent and at pressures up to autogenous pressure. It is preferred that R be H or methyl, especially methyl. The alkylene oxide and the 3-quinuclidinol can be 2~8~
_ 9 reacted in a 0.2:1 to 10:1 mole ratio range, preferably 1:1 to 3:1.
These derivatives of 3-quinuclidinol for the most part can be represented by formula II; however, lesser amounts of compounds involving ~1CH-CH20tn linkages could also be present R
in the reaction products.
A catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, suitable amounts of the catalyst composition may range from about 0.01 to 10 parts per 100 parts by weight polyol in the polyurethane formulation.
T~e catalyst compositions may be used in combination with other tertiary amine and organotin urethane catalysts well known in the urethane art.
Example 1 In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in parts by weight was:
COMPONENT PARTS
Multr~ol 9151 70 ~ultr~nol 91~ 30 ~ater 4.2 Diet~anolami~e 1.74 DC 5164 1.0 TDI 80 105 index ~ultranol 9151 polyol -- polyurea filled, ethylene oxide tipped polyether polyol marketed by Mobay Corp.
~ ultranol 91~3 polyol -- ethylene oxide tipped, conventional polyether polyol marketed by Mobay Corp.
2 ~
DABCO DC 516~ silicone surfactant marketed by Air Products and Chemicals, Inc.
TDI 80 -- a mixture of 80 wt% 2,4-TDI and 20 wt% 2,6-TDI.
The foam reactivity was measured using 33 wt% 3-quinucli-dinol (3-QND) in ethylene glycol or DABC0 33LV~ catalyst (33 wt% triethylenediamine in dipropylene glycol) as gelling catalysts and DABC0~ BL-11 catalyst [70 wt% bis(dimethylamino-ethyl)ether in dipropylene glycol] as the blowing catalyst.
The activity of 3-QND was also compared to that of DABC0 33LV~
catalyst in the absence of a cocatalyst. Table 1 sets forth conditions and results.
Tdbie 1 DABC0 33LV/ 3-~ND/
Catalvst DABC0 BL-11DABC0 BL-11DABC0 33LV 3-QND
Amount (parts) 0.42/0.150.42/0.15 1.26 1.26 Top o~ Cup 1 (sec)11.3 10.~ 11.6 10.6 20 Top of Cup 2 (sec)47.6 40.5 40.0 43.3 String ~el (sec) 65.6 61.8 63.6 69.0 Full Rise Time (sec) 132.1 141.3 112.1 142.0 Times cited were from mixing of the polyol masterbatch with isocyanate. Top Cup 1 represents the time required for the foam formulation to fill a 16 oz cup and is an indication of reaction initiation. ~op Cup ~ represents the time required for the foam formulation to fill a 1 gal cup in addition to the 16 oz cup mentioned above and is an indication of reaction progression. String Gel and Full Rise are further measures of reaction prsgression and provide some indication of extent of cure.
The advantage of 3-quinuclidinol is that it provides an excellent reactivity match for triethylenediamine during the critical early stages of the foaming reaction, and is then 2 ~
incorporated into the polymer, as seen in the increased full rise time measurement. Furthermore, the amount of 3-quinucli-dinol can be increased to shorten the full rise time, but volatile emissions from the final product will not increase.
Example 2 The example shows the propoxylation of 3-quinuclidinol.
To 25g (197.1 mmol) of 3-quinuclidinol suspended in 30 mL
of N,N-dimethylformamide (DMF) was added 0.0356g (0.89 mmol) of sodium hydroxide catalyst. The mixture was heated to 65C with stirring. Propylene oxide (103.22g, 592 mmols) was added dropwise while maintaining the temperature between 70 to 76C.
The 3-~uinuclidinol conversion was 98.5%. The DMF was removed by vacuum distillation, and the residue fractionated by Kugelrohr distillation. Selected fractions were designated Propoxylate 1-3 and were tested as described in Example 3 and Table 2.
Example 3 This example demonstrates the relative reactivity of the 3-quinuclidinol derivatives.
The rate of isocyanate consumption as a function of time was measured using a formulation similar to that of Example 1, but containing monofunctional reactants. Reaction samples drawn at the indicated times were quenched with dibutylamine and analyzed by liquid chromatography. The catalysts were compared on an equimolar basis corresponding to a loading of 0.35 parts per hundred parts of DABC0 33LV catalyst in the formulation in Example 1. Table 2 sets forth the results.
2 ~ 9 ~.
Table 2 ~ NC0 Conversion Time Catalv~t (minl 0 5 1.0 1.5 2.0 3.0 4.0 5 0 6.0 Trlethylenediamine 14.2 28.9 44.0 50.3 64.1 71.6 76.5 79.9 3-auinuclidinol 18.9 34.2 46.4 54.3 66.2 72.7 76.6 79.2 Propoxylat~ 1a l6.2 29.6 41.6 50.4 64.3 71.4 76.2 79.3 Propoxylat~ 2b 16.1 28.7 40.3 48.6 59.4 65.6 69.5 72.3 Propoxylate 3c 7.2 14.3 19.8 28.7 42.2 50.8 58.4 63.9 Hydroquinined 7.9 17.8 25.5 32.1 41.9 49.7 54.6 59.9 a Propoxylat~ 1 contains 2.7% 3-quinuclidinol, 70.0~ monopro ox late (Formula II, n=1) and 27.3~ dipropoxylate (Formula II, n=2) on a mo~e ~asis.
t5 b Propoxylate 2 contains 17.1~ monopropoxylate, 59.6% dipropoxylate, and 16.4%
tripopoxylate on a mole basis.
c Propoxylate 3 contains 6.6~ dipropoxylate, 79.8% tripropoxylate, and 9.2%
~tetrapropo~ylate on a mole basis.
d ~CH2CH~
~H
CH30 ~
Hyd~qu~ina The uniqueness of the propoxylated 3-quinuclidinol derivatives is that they retain the desirable hiyh activity of 3-quinuclidinol itself, as well as the necessary secondary alcohol functionality, but are liquids readily soluble in a variety of ommon catalyst carriers; e.g., dipropylene glycol.
3-Quinuclidinol, itself, is a high melting solid with limited solubility and thus is not convenient for all applications.
Hydroquinine, although it also contains a secondary alcohol, is poorly active. Desirable activity is obtained i~ substituents are placed on the 3-position, rather than the 2-position, of 1-azabicyclo[2.2.2.]octane. The size of the substituent on the 2 ~ 9 1 3-position may also influence the level of activity, as shown by the comparison of the results for propoxylate 3 to those for hydroquinine.
Example 4 This example demonstrates the partial propoxylation of 3-quinuclidinol.
3-Quinuclidinol (39.4 mmols, 5.01g~, sodium hydroxide (0.2 mmol, 0.008g), and DMF (lOmL) were charged to a 50mL 3-neck roundbottom flask equipped with a magnetic stir bar, thermometer, reflux condenser and a septum. Propylene oxide (19.7 mmols, 1.14g~ was added by syringe over 5 minutes while stirring and heating the solution ~o 60C. The temperature rose 5-10C following the propylene oxide addition, and gradually dropped back to 60C over the next 15 minutes. The DMF was removed by heating the reaction to 40C at 500 mTorr for several hours. The product was a liquid.
The experiment was repeated as above with 39.7 mmols (5.05g) of 3-r~uinuclidinol and 40.0 mmols (2.31g) of propylene oxide, the other reagents and conditions remaining unchanged.
The samples were analyzed by gas chromatography to determine - the extent of propoxylation. The results are tabulated below.
3-Ouinuclidinol Propylene Oxide _ 9~i Area bV GC
Run (mmols) _ !mmols) DMF 3-Quinuclidinol mono-PO di-PO tri-PO4A 39.4 19.7 2 85 8 2 : 4B 39.7 40.0 0.6 54 22 9 11 Example 5 In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in weight parts was:
Component Parts PluraGol-816 40 Plur~col-973 60 W ter 3.5 Diethanolamine1.49 DC 50~3 1.5 TDI 80 105 index Pluraool-816 polyol -- ethylene oxide tipped, conventional polyether polyol marketed by BASF AG.
Pluracol-973 polyol -- styrene-acrylonitrile filled, ethylene oxide tipped polyether polyol marketed by BASF AG.
DABCO DC 5043 silicone surfactant marketed by Air Products and Chemicals, Inc.
The foam reactivity was measured using DABC0 33L~
: catalyst, Run 4A catalyst (50 wt% in water) or Run 4B catalyst (50 wt% in water) as gelling catalysts and DABC0 BL-11 catalyst as the blowing catalyst. Table 3 sets forth conditions and 20 results.
Table 3 DABC0 33LV/ Run 4A/ Run 4B/
Catalyst DABC0 BL-ll DABCO BL-11 DABCO BL-11 Level (parts) 0.50/0.150.41/0.15 0.54/0.15 Top of Cup 1 (sec) 10.2 10.7 11.3 Top of Cup 2 (sec) 32.3 35.2 34.9 String Gel (sec) 68.8 64.0 64.1 30 Full rise time (sec) 99.3 94.3 98.1 The results in Table 3 indicate that mixtures containing 3-quinuclidinol and propoxylated 3-quinuclidinol have activity o ~
comparable to that of triethylenediamine at equimolar use levels. Furthermore, the partially propoxylated mixtures are liquids which are more convenient to handle than 3-quinucli-dinol itself.
The prior art high activity amine gelling catalysts are fugitive in that they can escape from a foam during or after its manufacture. The present invention successfully incorporates secondary alcohol functionality into high activity gelling catalysts which display activity similar to that of TEDA, the industry standard. The secondary alcohol functionality lowers the volatility of the catalysts of the invention and prevents their escape from the finished foam prodùct through the chemical reaction with the foam itself.
Moreover, the catalyst compositions are liquids which are easïly processed and show negligible activity loss as compared to 3-quinuclidinol.
The prior art does not indicate that quinuclidine or its derivatives would be expected to have activity very similar to that of TEDA. An activity match is desirable so that the catalysts for the present invention can be easily employed as drop-in replacements for TEDA.
STATEMENT OF INDUSTRIAL APPLICATION
The present invention provides compositions for catalyzing the urethane reaction and preparing urethane products, especially polyur~thane foam products.
ML0106A.APP
Claims (27)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a method for catalyzing the trimerization of an isocyanate and/or its reaction with an active hydrogen-containing compound, the improvement which comprises using a catalyst composition prepared by reacting 3-quinuclidinol with an alkylene oxide of the formula where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl.
2. The method of Claim 1 in which the alkylene oxide is ethylene oxide or propylene oxide.
3. The method of Claim 1 in which the alkylene oxide is propylene oxide.
4. In a method for catalyzing the trimerization of an isocyanate and/or its reaction with an active hydrogen-containing compound, the improvement which comprises using as a catalyst at least one compound of the following formula :
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 1-3.
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 1-3.
5. The method of Claim 4 in which R is hydrogen or methyl.
6. The method of Claim 4 in which R is methyl.
7. The method of Claim 4 in which n is 1-2.
8. The method of Claim 4 in which n is 1.
9. The method of Claim 4 in which 3-quinuclidinol is also used as a catalyst.
10. In a method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst, the improvement which comprises employing as the catalyst a composition consisting essentially of at least one compound of the following formula:
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 1-3.
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aralkyl, and n is 1-3.
11. The method of Claim 10 in which R is hydrogen or methyl.
12. The method of Claim 10 in which R is methyl.
13. The method of Claim 10 in which n is 1-2.
14. The method of Claim 10 in which n is 1.
15. The method of Claim 10 in which 3-quinuclidinol is also used as a catalyst.
16. A catalyst composition comprising at least one compound of the following formula:
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aryalkyl, and n is 1-3.
where R is hydrogen, C1-C8 alkyl, C6-C10 aryl or C7-C10 aryalkyl, and n is 1-3.
17. The composition of Claim 16 in which R is hydrogen or methyl.
18. The composition of Claim 16 in which R is methyl.
19. The composition of Claim 16 in which n is 1-2.
20. The composition of Claim 16 in which n is 1.
21. The composition of Claim 16 in which 3-quinuclidinol is also used as a catalyst.
22. A catalyst composition comprising at least two different compounds of the following formula:
where R is methyl and n is 0-3.
MLO106.APP
where R is methyl and n is 0-3.
MLO106.APP
23. In a method for catalyzing the trimerization of an isocyanate and/or its reaction with an active hydrogen-containing compound, the improvement which comprises using as a catalyst 3-quinuclidinol.
24. In a method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst, the improvement which comprises employing a catalyst composition consisting essentially of 3-quinuclidinol.
25. The method of Claim 24 which employs 0.1 to 10 parts 3-quinuclidinol per 100 parts by weight polyol.
26. In a polyurethane foam composition which comprises an organic polyisocyanate, a polyol, a blowing agent, a cell stabilizer and a catalyst, the improvement which comprises a catalytically effective amount of a catalyst composition consisting essentially of 3-quinuclidinol.
27. The composition of Claim 26 which contains 0.1 to 10 parts 3-quinuclidinol per 100 parts by weight polyol.
ML0106A.APP
ML0106A.APP
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/828433 | 1992-01-30 | ||
| US07/828,433 US5143944A (en) | 1992-01-30 | 1992-01-30 | 3-quinuclidinol catalyst compositions for making polyurethane foams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2088091A1 true CA2088091A1 (en) | 1993-07-31 |
Family
ID=25251792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002088091A Abandoned CA2088091A1 (en) | 1992-01-30 | 1993-01-26 | 3-quinuclidinol catalyst compositions for making polyurethane foams |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5143944A (en) |
| JP (1) | JPH0670118B2 (en) |
| KR (1) | KR970001537B1 (en) |
| BR (1) | BR9300272A (en) |
| CA (1) | CA2088091A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194609A (en) * | 1992-01-30 | 1993-03-16 | Air Products And Chemicals, Inc. | 3-quinuclidinol catalyst compositions for making polyurethane foams |
| US5512603A (en) * | 1994-02-22 | 1996-04-30 | Air Products And Chemicals, Inc. | Hydroxy and amino functional pyrrolizidine catalyst compositions for the production of polyurethanes |
| US5710191A (en) * | 1995-06-05 | 1998-01-20 | Air Products And Chemicals, Inc. | Hydroxymethyl quinuclidine catalyst compositions for making polyurethane foams |
| DE69601328T2 (en) * | 1995-06-05 | 1999-05-27 | Air Prod & Chem | Hydroxymethylquinuclidine catalyst compositions for the production of polyurethane foams |
| US6534555B1 (en) | 2001-09-10 | 2003-03-18 | Huntsman Petrochemical Corporation | Catalyst systems for polyurethane polyester foams |
| US6998508B2 (en) * | 2003-03-10 | 2006-02-14 | Air Products And Chemicals, Inc. | Tertiary alkanolamines containing surface active alkyl groups |
| US6747069B1 (en) | 2003-03-10 | 2004-06-08 | Air Products And Chemicals, Inc. | Tertiary alkanolamine polyurethane catalysts derived from long chain alkyl and fatty carboxylic acids |
| US7169823B2 (en) * | 2003-03-10 | 2007-01-30 | Air Products And Chemicals, Inc. | Tertiary alkanolamine polyurethane catalysts derived from long chain alkyl and fatty carboxylic acids |
| US20050059749A1 (en) * | 2003-09-16 | 2005-03-17 | Huntsman Petrochemical Corporation | Catalysts useful in polyurethane foam |
| US20050267227A1 (en) * | 2004-05-28 | 2005-12-01 | Andrew Gary D | Fast demold/extended cream time polyurethane formulations |
| US8258198B2 (en) * | 2004-05-28 | 2012-09-04 | Air Products And Chemicals, Inc. | Fast demold/extended cream time polyurethane formulations |
| US10023683B2 (en) | 2006-06-12 | 2018-07-17 | Evonik Degussa Gmbh | Catalyst compositions for improving polyurethane foam performance |
| US20080269365A1 (en) | 2007-04-25 | 2008-10-30 | Gary Dale Andrew | Additives for Improving Surface Cure and Dimensional Stability of Polyurethane Foams |
| US8637584B2 (en) | 2007-05-25 | 2014-01-28 | Air Products And Chemicals, Inc. | Polyester polyol-containing polyurethane systems having improved hydrolytic stability |
| EP2295438B1 (en) | 2008-05-30 | 2015-03-18 | Tosoh Corporation | Process for producing hydroxyalkyltriethylenediamine compound, and catalyst composition for the production of polyurethane resin using the hydroxyalkyltriethylenediamine compound |
| US9133377B2 (en) * | 2010-05-20 | 2015-09-15 | A. Raymond Et Cie | Adhesive polyurethane powder capable of being activated by heat |
| EP2657237B1 (en) | 2010-12-22 | 2015-05-20 | Tosoh Corporation | Cyclic amine compound, and process for producing polyurethane resin using same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE584604A (en) * | 1958-11-14 | |||
| US4186040A (en) * | 1964-12-02 | 1980-01-29 | The United States Of America As Represented By The Secretary Of The Army | "BZ" containing pyrotechnic compositions |
| JPS58162625A (en) * | 1982-03-23 | 1983-09-27 | Toyo Soda Mfg Co Ltd | Catalyst for polyurethane production |
| US4957944A (en) * | 1989-06-16 | 1990-09-18 | Union Carbide Chemicals And Plastics Company Inc. | Urethane catalysts |
| US5071809A (en) * | 1990-05-07 | 1991-12-10 | Air Products And Chemicals, Inc. | Tertiary amine catalysts for polyurethanes |
-
1992
- 1992-01-30 US US07/828,433 patent/US5143944A/en not_active Expired - Lifetime
-
1993
- 1993-01-25 BR BR9300272A patent/BR9300272A/en not_active Application Discontinuation
- 1993-01-26 CA CA002088091A patent/CA2088091A1/en not_active Abandoned
- 1993-01-27 KR KR1019930000965A patent/KR970001537B1/en active IP Right Grant
- 1993-01-28 JP JP5032809A patent/JPH0670118B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| BR9300272A (en) | 1993-08-24 |
| KR930016458A (en) | 1993-08-26 |
| JPH0670118B2 (en) | 1994-09-07 |
| JPH0680750A (en) | 1994-03-22 |
| US5143944A (en) | 1992-09-01 |
| KR970001537B1 (en) | 1997-02-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19960727 |