USRE38415E1 - Use of N-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process - Google Patents

Use of N-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process Download PDF

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USRE38415E1
USRE38415E1 US10/267,119 US26711902A USRE38415E US RE38415 E1 USRE38415 E1 US RE38415E1 US 26711902 A US26711902 A US 26711902A US RE38415 E USRE38415 E US RE38415E
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catalysts
pyrrolidine
isocyanate
aminoalkyl
compounds
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Richard Weider
Uwe Scholz
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Bayer AG
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Bayer AG
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    • 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
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2290/00—Compositions for creating anti-fogging

Definitions

  • This invention relates to the use of N-(aminoalkyl)pyrrolidines as catalysts for the preparation of products by the polyisocyanate addition process. These catalysts may be used as a replacement for or in combination with known urethane catalysts, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), for the preparation of rigid or flexible polyurethane foams and other polyurethane products.
  • urethane products is intended to encompass all reaction products of polyisocyanates with compounds containing at least two isocyanate-reactive hydrogen atoms. That is, the term “polyurethane” is understood to encompass, for example, pure polyurethanes, polyurethane polyureas, or pure polyureas.
  • the rate of the reaction between isocyanate groups and compounds containing NCO-reactive hydrogen atoms is determined not only by the temperature of the starting products and their structure but particularly by the use of suitable catalysts.
  • bases for example, tertiary amines such as triethylamine
  • organometallic compounds for example, tin carboxylates such as tin(II) octoate
  • electrophilic catalysts for example, electrophilic catalysts.
  • the prior art processes are based on the joint use of Lewis acids and Lewis bases, which is normally characterized by synergistic effects.
  • amines are exclusively used as catalysts in a number of applications.
  • R is a C 2-12 alkylene group (optionally containing O or N atoms but not isocyanate-reactive groups) and
  • R′ is hydrogen or a C 1-4 alkyl group
  • the polyisocyanate reaction products prepared according to the present invention are preferably cellular plastics.
  • the catalysts used according to the invention are known compounds.
  • the preferred catalysts are prepared, for example, by addition of pyrrolidine onto acrylonitrile, followed by reduction and, optionally, subsequent alkylation by known methods.
  • the catalysts according to the invention are colorless to pale yellowish compounds, the preferred types being liquid, and are soluble in organic solvents and soluble or dispersible in water.
  • the quantity of the catalysts is generally from about 0.01 to about 5% by weight, based on the isocyanate-reactive compound. Although more than the above-mentioned quantity may be used, no advantage is gained.
  • Preferred compounds are catalysts corresponding to general formula (I) in which R is a 1,3-propylene group and R′ is hydrogen or C 1-4 alkyl.
  • Suitable catalysts according to the invention include, for example, N-(2-aminoethyl)pyrrolidine, N-(2-(methylamino)ethyl)pyrrolidine, N-(3-aminopropyl)-pyrrolidine, N-(3-methylamino)propyl)pyrrolidine, N-(3-(ethylamino)propyl)pyrrolidine, N-(3-(propylamino)propyl)pyrrolidine, N-(4-aminobutyl)pyrrolidine, N-(3-amino-2-methylpropyl)-pyrrolidine, and N-(3-methylamino-2-methylpropyl)pyrrolidine.
  • Preferred catalysts include N-(3-aminopropyl)pyrrolidine, N-(3-methylamino)propyl)prrolidine, N-(3-(ethylamino)propyl)-pyrrolidine, and N-(3-(propylamino)propyl)pyrrolidine, with N-(3-aminopropyl)pyrrolidine and N-(3-(methylamino)propyl)-pyrrolidine being particularly preferred.
  • the isocyanate-reactive compounds which are used as component (b) in the process accordin9 to the invention are those used in previously known processes for the preparation of polyurethanes and are described, for example, in Kunststoffhandbuch, Vol. VII, Polyurethane, Hansen-Verlag, Kunststoff (1963) or in Houben-Weyl, Makromolekulare Stoffe Vol. E 20.
  • the isocyanate reactive compounds have a molecular weight M n of 3000-10000, preferably 3000-6000, e.g. polyether-polyols such as Bayfit®3973 or Bayfit®3963 (commercial product Bayer AG).
  • the compounds containing NCO groups used as component (a) in the process of the invention are the same compounds used in previously known processes and are described, for example, in Kunststoffhandbuch, Vol. VII, Polyurethane, Hansen-Verlag, Kunststoff (1983) or in Houben-Weyl, Makromolekulare Stoffe, Vol. E20.
  • the substituted pyrrolidines are used in the same way as the previously known catalysts.
  • the catalyst may be used in its liquid form or may be dissolved in a polyol or a suitable solvent.
  • the catalyst may be used at any temperature - or under other conditions - either alone or in combination with other known catalysts that are suitable for the preparation of polyurethanes.
  • Suitable other catalysts include organic or inorganic tin compounds or other organometallic compounds; tertiary amines, alkanolamines, cyclic amines, polyamines, and the like; alkali metal compounds; and other co-catalysts.
  • the catalysts according to the invention are preferably used in a quantity of at least 50% by weight, based on the total quantity of catalyst used.
  • the process according to the invention is suitable for conventional production methods, including, for example, one-shot or prepolymer processes for the preparation of polyurethane foams, polyurethane elastomers, polyurethane coatings, and the like, and for the crosslinking reaction which is often desirable after the direct polyaddition.
  • the above-mentioned catalysts of the invention accelerate the polyaddition reaction to a considerable extent so that the quantity of catalyst required is very small. Because the catalyst compounds according to the invention have only a faint odor and because they represent substantially nonvolatile liquids and incorporable compounds, the polyurethane products obtained are free from unwanted odors.
  • Catalyst 1 N-(3-aminopropyl)piperidine
  • Catalyst 2 N-(3-aminopropyl)-N′-methylpiperazine
  • Catalyst 5 N-(3-(methylamino)propyl)pyrrolidine
  • the catalysts have the following formulas:
  • Catalysts 4 and 5 correspond to the invention, with the other catalysts being comparison catalysts.
  • Component A 37.10 parts mixture of 80% 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (in a ratio of 80:20) and 20% 4,4′-diisocyanatodiphenylmethane with polymeric components (NCO content 44.5 ⁇ 0.5% by weight) (Desmodur ® VT 06, a commercial product of Bayer AG)
  • Component B 100.00 parts polyether polyol (OH value 28 ⁇ 2 mg KOH/g) prepared by reaction of trimethylolpropane (TMP) with propylene oxide (PO) and sub- sequent reaction with ethylene oxide (EO) in a PO:EO ratio of 82:18 3.00 parts water 0.05 part 70% solution of bis(2-dimethylaminoethyl) ether in dipropylene glycol (DPG) 0.25 part 33% solution of diazabicyclo[2.2.2]octane (DABCO) in DPG 0.20 part foam stabilizer B4617
  • Component A is combined with component B and the mixture is thoroughly mixed for 6 seconds using a high-speed stirrer. The reaction mixture is then foamed in an open mold at room temperature.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a process for preparing polyisocyanate polyaddition products by reacting
(a) polyisocyanates with
(b) relatively high molecular weight compounds containing at least two isocyanate-reactive hydrogen atoms and
(c) chain-extending agents, in the presence of
(d) N-(aminoalkyl)pyrrolidine catalysts corresponding to formula (I)
Figure USRE038415-20040203-C00001
in which
R is a C2-12 alkylene group (optionally containing O or N atoms but not isocyanate-reactive groups) and
R′ is hydrogen or a C1-4 alkyl group,
(e) optionally, other known catalysts, and
(f) other known additives.

Description

BACKGROUND OF THE INVENTION
This invention relates to the use of N-(aminoalkyl)pyrrolidines as catalysts for the preparation of products by the polyisocyanate addition process. These catalysts may be used as a replacement for or in combination with known urethane catalysts, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), for the preparation of rigid or flexible polyurethane foams and other polyurethane products. In the context of the present invention, the term “polyurethane products” is intended to encompass all reaction products of polyisocyanates with compounds containing at least two isocyanate-reactive hydrogen atoms. That is, the term “polyurethane” is understood to encompass, for example, pure polyurethanes, polyurethane polyureas, or pure polyureas.
The rate of the reaction between isocyanate groups and compounds containing NCO-reactive hydrogen atoms is determined not only by the temperature of the starting products and their structure but particularly by the use of suitable catalysts. In practice, bases (for example, tertiary amines such as triethylamine) are used mainly as nucleophilic catalysts, whereas organometallic compounds (for example, tin carboxylates such as tin(II) octoate) are used mainly as electrophilic catalysts. The prior art processes are based on the joint use of Lewis acids and Lewis bases, which is normally characterized by synergistic effects. However, it is also known that amines are exclusively used as catalysts in a number of applications. However, only a few of the large number of known amine catalysts (cf. Ullmann, 4th Edition, and Kunststoffhandbuch, Vol. VII, Polyurethane, Hanser-Verlag, Munich (1983)) have hitherto been adopted for use on a wide scale, with 1,4-diazabicyclo[2.2.2]octane (DABCO), bis(2-dimethylaminoethyl) ether, triethylamine, dimethyl cyclohexylamine, dimethylethanolamine, dimethylbenzylamine, methylmorpholine, and ethylmorpholine being the most important. More particularly, of course, catalysts distinguished by high activity, economic production, and a broad range of applications are used. Another increasingly important consideration is the toxicological evaluation of the catalysts with regard to processing safety and odor emission. Many of the amine catalysts in use today, such as DABCO or triethylamine, may be regarded as unsatisfactory in this respect because of their high volatility and the relatively intensive amine odor that is carried over into the end product produced with such catalysts.
Amine catalysts containing an additional, isocyanate reactive group corresponding to the general formula
Figure USRE038415-20040203-C00002
are described in German Offenlegungsschrift 2,116,535, which also mentions, inter alia, compounds in which the two substituents R are attached to each other to form 3- to 6-membered rings. The use of one representative member of this special class of compounds, namely N-(2-aminoethyl)aziridine, is illustrated by Examples 10 and 16-18 of the German patent. In the Examples mentioned, this compound proved to be distinctly poorer than the corresponding acyclic compounds with regard to the density, strength, and elasticity of the foams prepared (Example 10) and particularly with regard to activity (Examples 16 to 18).
It has now surprisingly been found that certain pyrrolidine derivatives may be used advantageously as catalysts for the preparation of polyurethanes. Compared with the above-mentioned N-(2-aminoethyl)aziridine and cyclic compounds other than those having 5-membered rings, the compounds used in accordance with the invention have considerably greater activity that even surpasses that of the acyclic members disclosed in the above-cited German patent specification. Another advantage is the faint odor and low volatility of compounds in which the isocyanate-reactive groups are bound in the polymer, which leads to distinctly reduced odor emission in the preparation of polyurethane products. In addition, other advantages have been observed, including, for example, ease of handling (because the pyrrolidines preferably used are liquid), good curing behavior, and, not least, the very simple preparation of the compounds.
SUMMARY OF THE INVENTION
According to the present invention relates to a process for preparing polyisocyanate polyaddition products comprising reacting
(a) polyisocyanates with
(b) relatively high molecular weight compounds containing at least two isocyanate-reactive hydrogen atoms and
(c) chain-extending agents, in the presence of
(d) N-(aminoalkyl)pyrrolidine catalysts corresponding to formula (1)
Figure USRE038415-20040203-C00003
in which
R is a C2-12 alkylene group (optionally containing O or N atoms but not isocyanate-reactive groups) and
R′ is hydrogen or a C1-4 alkyl group,
(e) optionally, other known catalysts, and
(f) other known additives.
DETAILED DESCRIPTION OF THE INVENTION
The polyisocyanate reaction products prepared according to the present invention are preferably cellular plastics.
The catalysts used according to the invention are known compounds. The preferred catalysts are prepared, for example, by addition of pyrrolidine onto acrylonitrile, followed by reduction and, optionally, subsequent alkylation by known methods. The catalysts according to the invention are colorless to pale yellowish compounds, the preferred types being liquid, and are soluble in organic solvents and soluble or dispersible in water. The quantity of the catalysts is generally from about 0.01 to about 5% by weight, based on the isocyanate-reactive compound. Although more than the above-mentioned quantity may be used, no advantage is gained.
Preferred compounds are catalysts corresponding to general formula (I) in which R is a 1,3-propylene group and R′ is hydrogen or C1-4 alkyl. Suitable catalysts according to the invention include, for example, N-(2-aminoethyl)pyrrolidine, N-(2-(methylamino)ethyl)pyrrolidine, N-(3-aminopropyl)-pyrrolidine, N-(3-methylamino)propyl)pyrrolidine, N-(3-(ethylamino)propyl)pyrrolidine, N-(3-(propylamino)propyl)pyrrolidine, N-(4-aminobutyl)pyrrolidine, N-(3-amino-2-methylpropyl)-pyrrolidine, and N-(3-methylamino-2-methylpropyl)pyrrolidine. Preferred catalysts include N-(3-aminopropyl)pyrrolidine, N-(3-methylamino)propyl)prrolidine, N-(3-(ethylamino)propyl)-pyrrolidine, and N-(3-(propylamino)propyl)pyrrolidine, with N-(3-aminopropyl)pyrrolidine and N-(3-(methylamino)propyl)-pyrrolidine being particularly preferred.
The isocyanate-reactive compounds which are used as component (b) in the process accordin9 to the invention are those used in previously known processes for the preparation of polyurethanes and are described, for example, in Kunststoffhandbuch, Vol. VII, Polyurethane, Hansen-Verlag, Munich (1963) or in Houben-Weyl, Makromolekulare Stoffe Vol. E 20. The isocyanate reactive compounds have a molecular weight Mn of 3000-10000, preferably 3000-6000, e.g. polyether-polyols such as Bayfit®3973 or Bayfit®3963 (commercial product Bayer AG).
The compounds containing NCO groups used as component (a) in the process of the invention are the same compounds used in previously known processes and are described, for example, in Kunststoffhandbuch, Vol. VII, Polyurethane, Hansen-Verlag, Munich (1983) or in Houben-Weyl, Makromolekulare Stoffe, Vol. E20.
When carrying out the process according to the invention, the substituted pyrrolidines are used in the same way as the previously known catalysts. For example, the catalyst may be used in its liquid form or may be dissolved in a polyol or a suitable solvent. The catalyst may be used at any temperature - or under other conditions - either alone or in combination with other known catalysts that are suitable for the preparation of polyurethanes. Suitable other catalysts include organic or inorganic tin compounds or other organometallic compounds; tertiary amines, alkanolamines, cyclic amines, polyamines, and the like; alkali metal compounds; and other co-catalysts.
The catalysts according to the invention are preferably used in a quantity of at least 50% by weight, based on the total quantity of catalyst used.
The process according to the invention is suitable for conventional production methods, including, for example, one-shot or prepolymer processes for the preparation of polyurethane foams, polyurethane elastomers, polyurethane coatings, and the like, and for the crosslinking reaction which is often desirable after the direct polyaddition.
All other conditions are the same as those used in conventional urethane polyaddition processes. In each case, other known additives may be used, including chain-extending agents, blowing agents, foam stabilizers, emulsifiers, dyes, pigments, and fillers.
The above-mentioned catalysts of the invention accelerate the polyaddition reaction to a considerable extent so that the quantity of catalyst required is very small. Because the catalyst compounds according to the invention have only a faint odor and because they represent substantially nonvolatile liquids and incorporable compounds, the polyurethane products obtained are free from unwanted odors.
The following examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.
EXAMPLES Examples 1 to 6
These Examples demonstrate the high catalytic activity of N-(3-aminopropyl)pyrrolidine and N-(3-methylamino)propyl)pyrrolidine in comparison with analogous catalysts which do not contain a pyrrolidine ring in a polyurethane cold-cure flexible foam system.
The following catalysts were used:
Catalyst 1: N-(3-aminopropyl)piperidine
Catalyst 2: N-(3-aminopropyl)-N′-methylpiperazine
Catalyst 3: 3-dimethylaminopropylamine
Catalyst 4: N-(3-aminopropyl)pyrrolidine
Catalyst 5: N-(3-(methylamino)propyl)pyrrolidine
The catalysts have the following formulas:
Figure USRE038415-20040203-C00004
Catalysts 4 and 5 correspond to the invention, with the other catalysts being comparison catalysts.
Component A:
 37.10 parts mixture of 80% 2,4-toluene diisocyanate and
2,6-toluene diisocyanate (in a ratio of 80:20) and
20% 4,4′-diisocyanatodiphenylmethane with
polymeric components (NCO content
44.5 ± 0.5% by weight)
(Desmodur ® VT 06, a commercial product of
Bayer AG)
Component B:
100.00 parts polyether polyol (OH value 28 ± 2 mg KOH/g)
prepared by reaction of trimethylolpropane
(TMP) with propylene oxide (PO) and sub-
sequent reaction with ethylene oxide
(EO) in a PO:EO ratio of 82:18
 3.00 parts water
 0.05 part 70% solution of bis(2-dimethylaminoethyl) ether
in dipropylene glycol (DPG)
 0.25 part 33% solution of diazabicyclo[2.2.2]octane
(DABCO) in DPG
 0.20 part foam stabilizer B4617 (Goldschmidt AG)
 0.80 part polyether polysiloxane as stabilizer
(Stabilisator IS 50, a product of Bayer AG)
  0.6 part catalyst 1 to 5
Component A is combined with component B and the mixture is thoroughly mixed for 6 seconds using a high-speed stirrer. The reaction mixture is then foamed in an open mold at room temperature.
The results obtained with the various catalysts are set out in Table 1.
TABLE I
Cream time Gel time Rise time
Example Catalyst (sec) (sec) (sec)
1 None 9 108 213
2 1 9 105 210
3 2 8  75 150
4 3 7  52 115
 5* 4 6-7  48 100
 6* 5 4-5  46  93
*Examples according to the invention
Foams having a satisfactory foam structure were obtained.

Claims (4)

What is claimed is:
1. A process for preparing a polyisocyanate polyaddition product comprising reacting
(a) a polyisocyanate with
(b) a relatively high molecular weight compound containing at least two isocyanate-reactive hydrogen atoms and
(c) a chain-extending agent, in the presence of
(d) an N-(aminoalkyl)pyrrolidine catalyst corresponding to the formula
Figure USRE038415-20040203-C00005
in which
R is a C2-12 alkylene group (optionally containing O or N atoms but not isocyanate-reactive groups) and
R′ is hydrogen or a C1-4 alkyl group,
(e) optionally, other known catalysts, and
(f) other known additives.
2. A process according to claim 1 wherein R is a 1,3-propylene group and R′ is hydrogen or C1-4 alkyl group.
3. A process according to claim 1 wherein the N-(aminoalkyl)pyrrolidine catalyst is N-(3-aminopropyl)pyrrolidine and N-(3-(methylamino)propyl)pyrrolidine.
4. A process according to claim 1 wherein the polyisocyanate polyaddition product is a cellular plastic.
US10/267,119 1991-01-12 2002-10-07 Use of N-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process Expired - Lifetime USRE38415E1 (en)

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Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4100811A DE4100811A1 (en) 1991-01-12 1991-01-12 USE OF N- (AMINOALKYL) PYRROLIDINES AS A CATALYST FOR THE POLYISOCYANATE POLYADDITIONAL METHOD AND METHOD FOR THE PRODUCTION OF POLYURETHANE (UREA)
DE4100811 1991-01-12
US07/817,240 US5134217A (en) 1991-01-12 1992-01-06 Use of n-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process
US10/267,119 USRE38415E1 (en) 1991-01-12 2002-10-07 Use of N-(aminoalkyl) pyrrolidines as catalysts for the polyisocyanate polyaddition process

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170101501A1 (en) * 2014-06-27 2017-04-13 Huntsman Petrochemical Llc Pyrrolidine-based catalysts for use in polyurethane materials
US10457769B2 (en) 2014-08-05 2019-10-29 Evonik Degussa Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes
US10703851B2 (en) 2014-08-05 2020-07-07 Evonik Operations Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes
US10793662B2 (en) 2014-08-05 2020-10-06 Evonik Operations Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1338275A (en) * 1970-04-09 1973-11-21 Dow Chemical Co Process for making a polyurethane foam
US3888831A (en) * 1973-10-01 1975-06-10 Du Pont Curing with complexes of selected diamines and alkali metal salts
US3963680A (en) * 1975-03-17 1976-06-15 Minnesota Mining And Manufacturing Company One-part, room-temperature latent, curable isocyanate compositions
US4251637A (en) * 1979-09-13 1981-02-17 Texaco Development Corporation Tertiary amino substituted oxazolidines as polyisocyanurate catalysts
US4292411A (en) * 1979-03-09 1981-09-29 S.A. Prb Process for preparing integral skin polyurethane and polyurethane so obtained
US4379861A (en) * 1980-12-12 1983-04-12 Bayer Aktiengesellschaft Process for the production of polyurethanes using morpholine compounds as catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1338275A (en) * 1970-04-09 1973-11-21 Dow Chemical Co Process for making a polyurethane foam
US3888831A (en) * 1973-10-01 1975-06-10 Du Pont Curing with complexes of selected diamines and alkali metal salts
US3963680A (en) * 1975-03-17 1976-06-15 Minnesota Mining And Manufacturing Company One-part, room-temperature latent, curable isocyanate compositions
US4292411A (en) * 1979-03-09 1981-09-29 S.A. Prb Process for preparing integral skin polyurethane and polyurethane so obtained
US4251637A (en) * 1979-09-13 1981-02-17 Texaco Development Corporation Tertiary amino substituted oxazolidines as polyisocyanurate catalysts
US4379861A (en) * 1980-12-12 1983-04-12 Bayer Aktiengesellschaft Process for the production of polyurethanes using morpholine compounds as catalysts

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170101501A1 (en) * 2014-06-27 2017-04-13 Huntsman Petrochemical Llc Pyrrolidine-based catalysts for use in polyurethane materials
US9988483B2 (en) * 2014-06-27 2018-06-05 Huntsman Petrochemical Llc Pyrrolidine-based catalysts for use in polyurethane materials
US10457769B2 (en) 2014-08-05 2019-10-29 Evonik Degussa Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes
US10703851B2 (en) 2014-08-05 2020-07-07 Evonik Operations Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes
US10793662B2 (en) 2014-08-05 2020-10-06 Evonik Operations Gmbh Nitrogen-containing compounds suitable for use in the production of polyurethanes

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