JP2004211094A - Method for improving physical properties of polyurethane foam by using tertiary amino alkyl amide catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preparing a polyurethane foam which comprises a reaction of an organic polyisocyanate and a polyol in the presence of water as a blowing agent, a cell stabilizer, a gelling catalyst, and a tertiary amino alkyl amide catalyst composition. <P>SOLUTION: The tertiary amino alkyl amide catalyst composition is represented by formula I: wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, A and n are each described in the specification, or the tertiary amino alkyl amide catalyst composition wherein the tertiary amino alkyl amide catalyst is acid-blocked. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to the use of tertiary aminoalkylamides as catalysts for producing polyurethane foam.

The present invention relates to tertiary aminoalkylamide catalysts for producing polyurethane foam. Polyurethane foam is widely known and used in the automotive, home construction and other industries. Such foams are made by reacting a polyisocyanate with a polyol in the presence of various additives. One such additive is chlorofluorocarbon (CFC), which evaporates as a result of a reaction exotherm to form a polymerizable material and form. The discovery that CFCs deplete ozone in the stratosphere has resulted in legislation that reduces the use of CFCs. Therefore, the production of water-foamed foams, in which foaming is carried out by carbon dioxide (CO ₂ ) generated by the reaction between water and polyisocyanate, has become increasingly important. Tertiary amine catalysts are typically used to accelerate foaming (reaction of water with polyisocyanate to generate CO ₂ ) and gelation (reaction of polyol with isocyanate).

The ability of a tertiary amine catalyst to selectively promote either foaming or gelling is an important consideration when selecting a catalyst for producing a particular polyurethane foam. When the catalyst is remarkably promotes the blowing reaction too, before the reaction of isocyanate and polyol occurs sufficiently, many CO ₂ is generated, and CO ₂ is went out as bubbles from the formulation, form Will be destroyed. Poor quality foam will be produced. If contrast catalyst to promote too strongly gelling reaction, after the polymerization has occurred to the extent significant, would substantial portion of the CO ₂ is generated. Again, poor quality foam will be produced, which is characterized by dense, broken or poorly contoured cells, and other undesirable shapes.

  Tertiary amine catalysts generally have a bad smell and discomfort, and are highly volatile due to their low molecular weight. The release of tertiary amines during foam processing poses significant safety and toxicity problems, and the release of residual amines from custom made products is generally undesirable.

Amine catalysts derived from carboxylic acids and fatty acids having a long chain alkyl group (C ₆ or higher) and having an amide function have lower molecular weight and hydrogen bonding capacity when compared to materials of related structure lacking this function. And the volatility and odor are reduced. In addition, catalysts containing amide functionality chemically bind to the polyurethane polymer during the reaction and are not released from the finished product. Catalyst structures embodying this concept are typically low to moderate in activity and promote both the foaming (water-isocyanate) and gelling (polyol-isocyanate) reactions to varying degrees.

  U.S. Pat. No. 4,242,467 discloses the use of morpholino-substituted and piperazino-substituted ureas as catalysts for making polyurethane foams.

  U.S. Pat. No. 4,644,017 discloses a diffusion-resistant compound having tertiary amino groups in the production of polyisocyanate adducts which do not discolor or alter the composition of the surrounding material. The use of such aminoalkyl ureas is disclosed. Particularly taught are catalysts A and D, the reaction products of dimethylamino-propylamine and urea.

  U.S. Pat. No. 4,007,140 discloses the use of low odor N, N'-bis (3-dimethylaminopropyl) urea for the production of polyurethane. The use of N- (3-dimethylaminopropyl) formamide has also been described as a catalyst for producing polyurethane foam.

  U.S. Pat. No. 4,012,445 discloses the use of beta-aminocarbonyl compounds as catalysts for the production of polyurethane foam. In this catalyst, the beta-amino moiety is present as a dialkylamino or N-morpholino or N, N'-piperazino heterocycle and the carbonyl moiety is present as an amide or ester group.

U.S. Patent No. 4,735,970, and special amines -CO ₂ adduct and a method of manufacturing a cellular polyurethane using a homogeneous mixture of the adduct is disclosed. The use of N- (3-dimethylaminopropyl) -formamide as a catalyst for producing polyurethane foams has also been described.

  U.S. Pat. No. 5,200,434 discloses the use of amide derivatives of alkylene oxide polyethers and their use in polyurethane foam formulations.

  U.S. Patent Nos. 5,302,303, 5,374,486, and 5,124,367 disclose the use of aliphatic amidoamines as a necessary component for the stabilization of isocyanate compositions containing flame retardants. Use is disclosed. The storage stability of isocyanate-reactive compositions is often adversely affected by the addition of flame retardants, especially those based on phosphorus, zinc, antimony, and aluminum. The use of aliphatic aminoamides improves the storage stability of this isocyanate mixture.

（式中、ＡはＣＨまたはＮを表し、
Ｒ¹は水素または

を表し、
ｎは１から３の整数を表し、
Ｒ²およびＲ³はそれぞれ水素またはＣ₁〜Ｃ₆の線状もしくは分枝状のアルキル基を表し、
ＡがＮを表すときＲ⁴およびＲ⁵はそれぞれＣ₁〜Ｃ₆の線状もしくは分枝状のアルキル基を表わすか、ＡがＮを表すときはＲ⁴およびＲ⁵は一緒にＣ₂〜Ｃ₅のアルキレン基を表わすか、またはＡがＣＨもしくはＮを表わすときは、Ｒ⁴およびＲ⁵は一緒にＮＲ⁷を含むＣ₂〜Ｃ₅のアルキレン基であってよく、ここでＲ⁷は水素、Ｃ₁〜Ｃ₄の線状もしくは分枝状のアルキル基および

からなる群から選択され、
そしてＲ⁶はＣ₅〜Ｃ₃₅の線状もしくは分枝状のアルキル、アルケニルまたはアリール基を表す）
によって表される。 The present invention relates to a method for producing a polyurethane foam comprising reacting an organic polyisocyanate with a polyol in the presence of water as a foaming agent, a cell stabilizer, a gelling catalyst, and a tertiary amine amide catalyst composition. The catalyst composition has the formula:

(Wherein A represents CH or N;
R ¹ is hydrogen or

Represents
n represents an integer of 1 to 3,
R ² and R ³ each represent hydrogen or a C ₁ -C ₆ linear or branched alkyl group;
When A represents N, R ⁴ and R ⁵ each represent a C ₁ -C ₆ linear or branched alkyl group, or when A represents N, R ⁴ and R ⁵ together represent C ₂ -C ₄ . When C ₅ represents an alkylene group or A represents CH or N, R ⁴ and R ⁵ may together be a C ₂ -C ₅ alkylene group including NR ⁷ , wherein R ⁷ is hydrogen, and linear or shaped branched alkyl group of C ₁ -C ₄

Selected from the group consisting of
And R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group)
Represented by

  SUMMARY OF THE INVENTION The present invention provides a reactive catalyst composition for making a water-blown flexible polyurethane foam. The reactive catalyst may have a reactive NH group derived from the amide function, which reacts the catalyst into the polyurethane substrate, avoiding its release from the finished product. To be able to

  The use of this catalyst with a gelling or foaming cocatalyst improves the physical properties of the foam and enhances processability. This amide catalyst with a foaming cocatalyst as a gelling catalyst improves the air flow of the foam. An improvement in air flow means an improvement in the porosity and openness of the foam, which is an indicator of an improvement in the dimensional stability of the foam. As a gelling catalyst, this amide catalyst with an effervescent co-catalyst improves the power to foam breakage. That is, this is reduced. Reduced force to failure means that the foam is more easily compressed, which is a significant advantage in minimizing foam shrinkage during processing. This amide catalyst with a gelling cocatalyst as an effervescent catalyst improves the load-bearing properties of the foam. Such high molecular weight compounds have been suggested in the prior art to react upon mixing and to be incorporated into the polymer matrix early in the polyurethane process, thus limiting the compound's mobility. Have a good catalytic activity in the production of polyurethanes.

  Another embodiment of the present invention provides a reactive catalyst of the present invention which is blocked with a different acid to produce a delayed action catalyst. Such acid-blocked catalysts are expected to provide a delayed action, which is an advantage in flexible cast and rigid polyurethane foams, in addition to the inherent advantages of the compositions of the present invention. Is done.

The present invention provides a method for producing a polyurethane foam using a reactive catalyst composition comprising a tertiary aminoalkylamide. The amide is derived from a carboxylic acid of the type R ⁶ —CO ₂ H where R ⁶ is a C ₅ -C ₃₅ linear or branched alkyl, alkenyl, or aryl group. Reactive catalyst compositions are typically used in the presence of a gelling catalyst that is a mono- and / or bis (tertiary aminoalkyl) urea. The catalyst may include a reactive NH group derived from an amide functionality, which allows the catalyst to react with and immobilize the polyurethane substrate into the polyurethane substrate. Produces polyurethane foams without amine odor or amine emissions.

The method of the present invention is described in "Tertiary Amino Alkyl Amide Catalysts Derived From Long Chain Alkyl And", filed by the present applicant at the same time as the present patent application and assigned to the present applicant.
It is more fully described in co-pending patent applications entitled "Fatty Carboxylic Acid" and "Tertiary Amino Alkyl Amide Catalysts For Improving The Physical Properties Of Polyurethane Foams," which are incorporated herein by reference.

The reactive catalyst composition of the present invention is represented by three moieties: a tertiary amine moiety, an amide moiety, and a long-chain alkyl moiety (R ⁶ ). The tertiary amine moiety catalyzes the formation of the polyurethane foam. The amide moiety provides a functional group that allows the catalyst to react into the polyurethane substrate such that the resulting polyurethane foam is free of amine odors or amine emissions. The long-chain alkyl moiety allows the catalyst to promote the reaction between the isocyanate and water, causing the polymer to foam to a sufficient extent to provide a polyurethane foam with optimal physical properties.

  Example 7 shows that conventional dialkylaminoamides in which the amide moiety is derived from a simple carboxylic acid such as formic or acetic acid do not function as well as their long alkyl chain or fatty acid counterparts. . Aminoamide catalysts, such as N- (3-dimethylaminopropyl) -formamide or N- (3-dimethylaminopropyl) acetamide, work by themselves according to current industry standards (DABCO® BLV catalyst) do not do. The performance limitations of these compounds are very well recognized in the art and similar limitations are expected for materials of related structure. Compounds such as N- (3-dimethylaminopropyl) -2-ethylhexamide or N- (3-dimethylaminopropyl) -lauramide have higher molecular weights and, as a result, higher levels of use. It would be expected to function similarly to N- (3-dimethylaminopropyl) -formamide and N- (3-dimethylaminopropyl) -acetamide with some limitations.

The examples disclosed herein clearly show that derivatives of long alkyl chains and of fatty acids perform surprisingly better than their lower molecular weight counterparts, This is because the rate of rise profiles can in most cases be superimposed on fugitive working industrial standards (DABCO® BLV catalysts). N- (3- dimethylaminopropyl) - and in formamide N- (3- dimethylaminopropyl) - Me ₂ N-moiety in acetamide, for example N- (3- dimethylaminopropyl) - Me ₂ in lauramide It seems that the activity as a catalyst is smaller than that of the N- moiety. Moreover, even though the molecular weight of the fatty acid catalyst is significantly larger than that of the standard, the catalyst usage remains moderate. Greater activity of the catalyst composition may explain its moderate usage level, but the reason for this increased activity is not clear or clearly understood. In addition, this benefit is not limited to dynamic speed balance, but also has the benefit of a systematic improvement in foam quality as noted by the airflow values. This suggests that there is an improvement in physical properties when using the DABCO® NE1060 catalyst in combination with DMAP-cocoamide, with similar levels of DABCO® NE1060 catalyst and TEXCAT®. ) Is clearly evident from Example 11 as compared to using a combination of ZF-10 catalysts.

  The catalyst composition of the present invention catalyzes the reaction between the isocyanate functionality and a compound containing active hydrogen, ie, an alcohol, polyol, amine or water. The catalyst composition also undergoes a urethane (gelling) reaction of the hydroxyl groups of the polyol with the isocyanate to form a polyurethane foam, and a blowing reaction with the isocyanate of water releasing carbon dioxide to form a foamed polyurethane. Catalyze.

  Flexible polyurethane foam products include those known in the art, including, for example, hexamethylene discarnate, phenylene discarnate, toluene discarnate (TDI) and 4,4'-diphenylmethane discarnate (MDI). Prepared using any organic polyisocyanate. Particularly preferred are 2,4- and 2,6-TDI combined together as individual or commercially available mixtures. Another suitable isocyanate is a mixture of diisocyanates commercially known as "crude MDI" marketed as PAPI by Dow Chemicals, which comprises about 60% of 4,4'-diphenylmethane discarnate by another. Included with higher polyisocyanates, isomers and analogs. Also suitable are "prepolymers" of these polyisocyanates which consist of a previously partially reacted mixture of polyisocyanate and polyether or polyester polyol.

  Illustrative examples of polyols suitable as components of the polyurethane composition are polyalkylene ether polyols and polyester polyols. Polyalkylene ether polyols include poly (alkylene oxide) polymers such as poly (ethylene oxide) polymers and poly (propylene oxide) polymers, and polyhydric hydroxyl compounds including diols and triols, for example, ethylene glycol, propylene glycol, From 1,3-butane glycol, 1,4-butane glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane and similar low molecular weight polyols There are copolymers with terminal hydroxyl groups derived.

  In practicing the present invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols, for example, mixtures of bifunctional and trifunctional substances and / or mixtures of substances with different molecular weights or different chemical compositions may be used.

  Useful polyester polyols include reacting a dicarboxylic acid with an excess of diol, such as by reacting adipic acid with ethylene glycol or butanediol, or reacting a lactone with an excess of diol, such as reacting caprolactone with propylene glycol. Manufactured by the above-mentioned method.

  In addition to polyester polyols and polyether polyols, the main batch, or premix composition, often contains a polymer polyol. Polymer polyols are used in polyurethane foam to increase the resistance of the foam to deformation, ie, to improve the load-bearing properties of the foam. To improve load bearing, two different polymer polyols are currently used. The first type, designated as a graft polyol, consists of a triol in which a vinyl monomer is graft copolymerized. Styrene and acrylonitrile are commonly selected monomers. A second type of polyurea-modified polyol is a polyol containing a polyurea dispersion formed by the reaction of a diamine and TDI. Because TDI is used in excess, some of the TDI will react with both the polyol and the polyurea. This second type of polymer polyol has a variant called PIPA polyol, which is produced by the in-situ polymerization of TDI and alkanolamine in the polyol. Depending on the load support required, the polymer polyol may make up 20-80% of the polyol portion of the main batch.

  Typical other additives in polyurethane foam formulations include chain extenders such as ethylene glycol and butanediol; crosslinkers such as diethanolamine, diisopropanolamine, triethanolamine and tripropanolamine; , CFCs, HCFCs, HFCs, blowing agents such as pentane; and cell stabilizers such as silicone surfactants.

A typical formulation of a polyurethane flexible foam containing the gelling and foaming catalyst of the present invention will contain the following components in parts by weight (pbw).

Polyol 20-100
Polymer polyol 80-0
Silicone surfactant 1-2.5
Blowing agent 2 to 4.5
Crosslinking agent 0.5-2
Catalyst 0.25-2
Isocyanate index 70-115

（式中、ＡはＣＨまたはＮを表し、
Ｒ¹は水素または

を表し、
ｎは１から３の整数を表し、
Ｒ²およびＲ³はそれぞれ水素またはＣ₁〜Ｃ₆の線状もしくは分枝状のアルキル基を表し、
ＡがＮを表すときＲ⁴およびＲ⁵はそれぞれＣ₁〜Ｃ₆の線状もしくは分枝状のアルキル基を表わすか、ＡがＮを表すときはＲ⁴およびＲ⁵は一緒にＣ₂〜Ｃ₅のアルキレン基を表わすか、またはＡがＣＨもしくはＮを表わすときは、Ｒ⁴およびＲ⁵は一緒にＮＲ⁷を含むＣ₂〜Ｃ₅のアルキレン基であってよく、ここでＲ⁷は水素、Ｃ₁〜Ｃ₄の線状もしくは分枝状のアルキル基および

からなる群から選択され、
そしてＲ⁶はＣ₅〜Ｃ₃₅の線状もしくは分枝状のアルキル、アルケニルまたはアリール基を表す）
によって表される第３級アミノアルキルアミド組成物を含む。 The catalyst composition has the formula I:

(Wherein A represents CH or N;
R ¹ is hydrogen or

Represents
n represents an integer of 1 to 3,
R ² and R ³ each represent hydrogen or a C ₁ -C ₆ linear or branched alkyl group;
When A represents N, R ⁴ and R ⁵ each represent a C ₁ -C ₆ linear or branched alkyl group, or when A represents N, R ⁴ and R ⁵ together represent C ₂ -C ₄ . When C ₅ represents an alkylene group or A represents CH or N, R ⁴ and R ⁵ may together be a C ₂ -C ₅ alkylene group including NR ⁷ , wherein R ⁷ is hydrogen, and linear or shaped branched alkyl group of C ₁ -C ₄

Selected from the group consisting of
And R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group)
A tertiary aminoalkylamide composition represented by

Preferably, R ¹ , R ² and R ³ each represent hydrogen, and when A represents N, R ⁴ and R ⁵ each represent a methyl group. When A represents CH, R ⁴ and R ⁵ may together represent —CH ₂ CH ₂ N (CH ₃ ) CH ₂ —. n is preferably 2 or 3.

  Illustrative examples of dialkylaminoamides derived from higher alkyls and fatty acids are N- (3-dimethylaminopropyl) -amide, N- (2-dimethylaminoethyl) -amide, N-methyl-3-. Aminoethylpyrrolidineamide, 4,10-diaza-4,10,10-trimethyl-7-oxa-undecaamineamide and 2-ethylhexanoic acid, coconut oil fatty acid, tall oil fatty acid, caproic acid, heptyl acid, caprylic Acid, pelargonic acid, capric acid, hedecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, nonadecanoic acid, arachidic acid, Heneicosanoic acid, behenic acid, trichosanoic acid, lignoceric acid, pen Cosanoic acid, serotinic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, mericic acid, hentriacontanic acid, dotriacontanic acid, tritriacontanic acid, tetracontanic acid, hexatriacontanic acid, or aliphatic or aromatic thereof Is any dimethylamino-alkylamide or dialkylamino-alkylamide derived from materials of 9-phenylstearic acid and 10-phenylstearic acid and related structures, or alkyl-substituted amides.

  A preferred amide is N- (3-dimethylaminopropyl) -amide. Preferred acids are selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acids, and tall oil fatty acids.

  The amides are prepared by reacting the carboxylic acid with an appropriate molar ratio of the corresponding tertiary alkylamine at an elevated temperature of 80-300C, preferably 100-200C, and displacing the water. The amide can be further purified by distillation or chromatography as known in the art.

  The amides can be used with gelling catalysts such as tertiary amines or suitable transition metal catalysts, and / or blowing catalysts, depending on the desired benefits in processing.

  Examples of suitable tertiary amine gelling catalysts include Air Products and Chemicals Inc. Diazabicyclooctane (triethylenediamine), quinuclidine and substituted quinuclidine, substituted pyrrolidine and pyrrolididine, which are commercially available as DABCO 33LV (R) catalysts. Examples of suitable tertiary amine blowing catalysts include Air Products and Chemicals Inc. Bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine and related compositions, commercially available as DABCO® BL11 catalyst by DABCO® BL11, a higher permethylated polyamine, 2- [N- (dimethylaminoethoxyethyl)- N-methylamino] ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions and aminopropyl-bis (aminoethyl) ether compositions.

Another embodiment of the present invention is that the reactive catalyst of the present invention can be blocked with a different acid to produce a delayed action catalyst. Such acid-blocked catalysts are expected to provide a delayed action, which is an advantage in flexible cast and rigid polyurethane foams, in addition to the inherent advantages of the compositions of the present invention. Is done. The acid-blocked catalyst can be used to convert the catalyst composition to formic acid, acetic acid, 2-ethylhexanoic acid, gluconic acid, N- (2-hydroxyethyl) -iminodiacetic acid, and analogs well known in the art. It can be obtained simply by reacting with a carboxylic acid such as a product. The resulting salt is not catalytically active and therefore does not activate the polyurethane / foaming reaction until the temperature is sufficiently high that salt decomposition begins to occur. The acid-block catalysts of the present invention find their primary use in cast, flexible, rigid polyurethane foams where delayed initiation of the reaction is desired. This delay slows the increase in viscosity so that proper filling of the mold is achieved, allowing maximum productivity to be maintained while keeping the overall casting time as short as possible.

  Catalyst compositions comprising amine and tertiary amine gelling or foaming catalysts may be used in the polyurethane formulation in catalytically effective amounts. More particularly suitable amounts of the catalyst composition range from about 0.01 to 10 parts per hundred parts by weight polyol (pphp), preferably 0.05 to 2 pphp, in the polyurethane formulation.

  The catalyst composition may be used with other tertiary amine, organotin or carboxylate urethane catalysts well known in the urethane art.

  Although the invention has been described as being useful for making flexible polyurethane foams, the invention may also be used to make semi-flexible and rigid foams. Rigid polyurethane foams can be distinguished from flexible polyurethane foams by the presence of higher levels of isocyanurate in the rigid foam. For flexible foams, as part of the total polymer polyol content in the foam composition, the conventional polymer polyols have a weight average molecular weight (Mw) of 4000-5000 and a hydroxyl number (OH #) of 28-35. Typically used with triols. In contrast, rigid polyurethane foam compositions use polyols having from 3 to 9 hydroxyl functional groups, OH # s of 160-700 and Mw of 500-1000. Rigid foams can also be distinguished from flexible foams by the isocyanate (NCO) index of the foam composition. For rigid foam compositions, an NCO index of 100 to 300 is employed, whereas for flexible foam compositions, an NCO index of 70 to 115 is typically required.

  A typical rigid insulating foam formulation of polyurethane containing the catalyst composition of the present invention will contain the following components in parts by weight (pbw).

Polyol 100
Silicone surfactant 1-3
Foaming agent 0-50
Water 0-8
Catalyst 0.5 to 15
Isocyanate index 80-300

  For producing foams for laminates (insulating boards) and appliances, the NCO index is typically 100-300, and for producing open-cell foams, the NCO index is typically 100-120. Yes, and usually all foams are foamed with water.

  Semi-flexible molded foams have been utilized for many applications in the automotive domain. The main applications are instrument panels and interiors. A typical semi-flexible foam formulation containing the catalyst composition of the present invention contains the following components in parts by weight (pbw).

SPECFLEX NC630 polyol 80.0
SPECFLEX NC710 copolymer 20.0
Crosslinking agent 1.5
Water 2.2
Catalyst 0.5 to 10
Black colorant 0.3
Adhesion promoter 2.0
Cell opener 1.0
Polymer MDI, index 105

  The two main components are the base polyol and the copolymer polyol (CPP). The base polyol is utilized at a level of 70-100%. The molecular weight of the base polyol ranges from 4500 to 6000 for triols and from 2000 to 4000 for diols. Ethylene-oxide capped polyether polyols as base polyols replace most polyester polyols. The main hydroxyl content is usually above 75% and the capping range is typically 10-20%. The other major component is CPP, which is used at a level of 0-20%. To increase hardness and make demolding faster, the base polyol and CPP are combined with a low molecular weight crosslinker. The level of crosslinker will vary depending on the hardness requirements of the part being finished. The water level is chosen to give a free expansion density of 3 to 6 pounds. For semi-flexible foams, cell openers are also utilized to reduce the internal pressure of the foam during the cure cycle, thus reducing pressure relief porosity and "parting lines". An adhesion promoter may be added to improve the adhesion between the polyurethane foam and the vinyl coating, depending on the nature of the vinyl coating. The use of the catalyst composition of the present invention results in the vinyl film discoloration typically observed with conventional amine catalysts, since the NH group of the amine function can react with the isocyanate to form a covalent bond with the polyurethane polymer. Reduce.

  The present invention is further illustrated by the following examples, which are provided to illustrate, but not limit, the preparation of the compounds and compositions of the present invention.

Synthesis of N- (3-dimethylaminopropyl) -acetamide (DMAPA-acetamide) In a 500 ml three-necked round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel, 3-dimethylaminopropyl 83.3 g of amine (DMAPA) were charged. Excess acetic acid (210 g) was slowly added to the reaction mixture while monitoring the temperature with a thermocouple. At the end of the addition, the liquid was heated to reflux for 5 hours and the progress of the reaction was monitored by GC. Excess acetic acid was removed by distillation to obtain 118 g of N, N-dimethylaminopropylamino-acetamide as a pale yellow liquid.

Synthesis of N- (3-dimethylaminopropyl) -formamide (DMAPA-formamide) 80 g of DMAPA was placed in a 500 ml three neck round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel. Excess formic acid (160 g) was slowly added to the reaction mixture while monitoring the temperature with a thermocouple. At the end of the addition, the liquid was heated to reflux for 2 hours and the progress of the reaction was monitored by GC. The product was distilled off under reduced pressure to obtain 93.4 g of N, N-dimethylaminopropylamino-formamide as a transparent and colorless liquid.

Synthesis of N- (3-dimethylaminopropyl) -2-ethyl-hexamide (DMAPA-2-ethyl-hexamide) 500 ml three-necked round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel Inside, 100 g of DMAPA was put. The addition of 2-ethyl-hexanoic acid (120 g) was monitored with a thermocouple. At the end of the addition, the liquid was heated to reflux and the progress of the reaction was monitored by GC. At the end of the reaction, DMAPA was removed under reduced pressure to obtain 190 g of 3- (N, N-dimethylamino) -1- (2-ethylhexanoyl) propironamide as a transparent yellow liquid.

Synthesis of N- (3-dimethylaminopropyl) -lauramide (DMAPA-lauramide) 88 g of DMAPA was placed in a 500 ml three-necked round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel. Lauric acid (100 g) was slowly added to the reaction mixture while monitoring the temperature with a thermocouple. At the end of the addition, the liquid was heated to reflux and water was removed as the reaction progressed. Once the reaction was completed, excess DMAPA was removed under reduced pressure to give 141 g of 3- (N, N-dimethylamino) -1- (lauroyl) propionamide as a yellow solid. 52% of DPG (dipropylene glycol) was used as a catalyst.

Synthesis of N- (3-dimethylaminopropyl) -cocoamide (DMAPA-cocoamide) 88 g of DMAPA was placed in a 500 ml three neck round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel. Coconut oil fatty acid (100 g) was slowly added to the reaction mixture while monitoring the temperature with a thermocouple and, at the end of the addition, the liquid was heated to reflux. Water was removed periodically as the reaction proceeded. Once finished, excess DMAPA was removed under reduced pressure to give 147 g of the amide product as a pale yellow liquid which solidified slowly on a table.

Synthesis of N- (3-dimethylaminopropyl) -tall oil (DMAPA-TOFA) 26 g of DMAPA was placed in a 500 ml three-necked round bottom flask equipped with a Teflon-coated magnetic stir bar and pressure equalizing dropping funnel. . Tall oil fatty acid (61 g) was slowly added to the reaction mixture while monitoring the temperature with a thermocouple, and at the end of the addition, the liquid was heated to reflux. Water was removed periodically as the reaction proceeded. Once finished, excess DMAPA was removed under reduced pressure to give 74 g of the amide product as an amber liquid.

Foam rate of rise: DMAPA-formamide and DMAPA-acetamide versus industrial standards
In this example, a polyurethane foam was produced by a conventional method. The polyurethane formulations in parts by weight were as follows.

  For each foam made, add catalyst to 158 g of the above premix in a 32 oz (951 ml) paper cup, and overhead stirrer with a 2 inch (5.1 cm) diameter paddle for stirring. The formulation was mixed using a mixer at 6,000 RPM for 10 seconds. Sufficient TDI 180 was added to make an index 100 form [index = (mol NCO / mol active hydrogen) x 100] and the formulation was mixed well for 6 seconds at 6,000 RPM using the same stirrer. . A 32 oz (951 ml) cup was dropped through the hole in the bottom of a 128 oz (3804 ml) paper cup on the table. The hole is dimensioned to capture the edge of a 32 oz (951 ml) cup. The total volume of the foam container was 160 oz (4755 ml). The foam approached this volume at the end of the molding process. The maximum foam height was recorded.

  The following data shows the combination of DMAPA-acetamide and TEXACAT® ZF-10 catalyst with industry standards (DABCO 33-LV® and DABCO® BL-11 catalyst). And a comparison with commercially available non-fugitive standard catalysts (both NE1060 and TEXACAT® ZF-10 catalysts).

  From the above, the use of DMAPA-acetamide as the gelling catalyst in place of DABCO® 33-LV or DABCO® NE1060 catalyst causes premature collapse of the foam. This disintegration is probably due to the poor gelling ability of DMAPA-acetamide when tested against this formulation. In another attempt, DMAPA-formamide was tested using a similar procedure and the data could be summarized in the table below.

  The results showed that the quality of the foam obtained was very poor and in one case the foam collapsed. An extremely slow foam rise was manifested by a complete rise time exceeding 180 seconds in some cases. Even when using large amounts of catalyst, the poor behavior of the catalyst could not be corrected.

Rate of foam rise: DMAPA-2-ethyl-hexamide and DMAPA-lauramide versus industrial standards In this example, DMAPA-2-ethyl-hexamide and DMAPA-lauramide were used as industrial standards as described in the previous examples. And compared. The data obtained can be summarized in the table below.

  The results obtained clearly show that, in contrast to DMAPA-acetamide and DMAPA-formamide, DMAPA-2-ethyl-hexamide gives a stable foam with a rate of rise that is on par with industry standards. It is also clear that increasing the amount of catalyst used in the formulation affects the complete rise time, in sharp contrast to formamide and acetamide.

The results show that DMAPA-lauramide also gives a stable foam with almost the same rise rate curve as the technical standard. The data show that DMAPA-lauramide cannot function by itself as a sole amine catalyst, but TEXACAT® ZF-10
It also shows that the presence of a blowing catalyst such as a catalyst is required.

Rate of foam rise: DMAPA-amide and alkyl-substituted urea without TEXACAT® ZF-10 blowing catalyst In this example, DMAPA-2-ethyl without the presence of TEXACAT® ZF-10 blowing catalyst Hexamide and DMAPA-cocoamide were used with DABCO® NE1060 catalyst. The rate of rise of these foams was compared to the technical standards described in the previous examples. The data obtained is summarized below.

  This result shows that the blowing catalyst TEXACAT® ZF-10 catalyst was replaced by a combination of DABCO® NE1060 and DMAPA-amide catalysts to give rise rate profiles comparable to the standard. Indicate that In other words, DMAPA-cocoamide and DMAPA-2-ethyl-hexamide can act as blowing catalysts and replace ZF-10.

Physical Properties of Automotive Cushions Made with DMAPA-Cocoamide Foaming Catalyst In this example, car cushions are made by using DMAPA-cocoamide as the main blowing catalyst and DABCO® NE1060 gelling catalyst. did. The foam was made at 160 ° F. (71 ° C.) in a heated test block mold. In all cases, the reactivity of the foam was matched to the extrusion time, which measures the progress of the reaction and gives some indication of the degree of cure.

The results for force to failure are mechanical means with a 1000 pound (453.6 kg) pressure transducer mounted between a 50 square inch (322.6 cm ² ) disk and the drive shaft. Obtained using The Dayton motor specification, Model 4Z528, has 1/6 horsepower (124.3 J / sec), F / L rpm of 1800 and F / L torque of 5.63 in-lb (6.36 x 104 Nm). there were. The actual pressure was shown on a digital display. The foam pad was compressed to 50% of its original thickness and the force required to effect the compression was recorded in total pounds (Newtons). One cycle took 24 seconds to complete, and the actual destruction of the foam occurred within 7-8 seconds. This mechanical means followed ASTM D-3574, Indentation Force Deflection Test, and gave a value for the initial hardness or softness one minute after demolding.

  When DMAPA-cocoamide was used as the blowing catalyst instead of the TEXACAT® ZF-10 catalyst, the force to failure values measured were significantly smaller than those obtained with ZF-10. Thus, DMAPA-amides derived from higher alkyl or fatty acids act as blowing catalysts and can not only replace conventional catalysts such as ZF-10, but also have some Physical properties can also be improved.

Physical Properties of Automotive Cushions Made with DMAPA-Cocoamide Blowing Catalyst In this example, other physical properties were measured to see the additional benefits of this reactive catalyst composition. Automotive cushions were manufactured as described above. The physical properties are shown below.

  The above table shows that as going from C to E, the DABCO® NE1060 catalyst was sequentially and partially replaced by some DMAPA-cocoamide, and the effect of such changes caused the physical properties of the foam to change. Indicates that consistent proximity to industrial standard A has occurred. This demonstrates that the physical properties of the foam have been improved and can be intentionally modified to approach foams made with fugitive catalysts, today's industry standard.

  Other physical properties showed similar trends. These are briefly summarized in the table below.

Claims (22)

Water as blowing agent, cell stabilizer, gelling catalyst, and formula I:

(Wherein A represents CH or N;
R ¹ is hydrogen or

Represents
n represents an integer of 1 to 3,
R ² and R ³ each represent hydrogen or a C ₁ -C ₆ linear or branched alkyl group;
When A represents N, R ⁴ and R ⁵ each represent a C ₁ -C ₆ linear or branched alkyl group, or when A represents N, R ⁴ and R ⁵ together represent C ₂ or represents an alkylene group having -C _5, or when a represents CH or N, R ⁴ and R ⁵ may be an alkylene group of C ₂ -C ₅ containing NR ⁷ together, wherein R ⁷ hydrogen, an alkyl group of C ₁ -C ₄ linear or branched and are

Selected from the group consisting of
And R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group)
Or a method for producing a polyurethane foam comprising reacting an organic polyisocyanate with a polyol in the presence of a tertiary amine amide catalyst composition represented by the formula: or a catalyst composition in which the tertiary amine amide catalyst is blocked with an acid. The method of claim 1, R ^1, R ² and R ³ represent each hydrogen. When A represents N, A method according to claim 1 wherein R ⁴ and R ⁵ each represent a methyl group. When A represents CH, R ⁴ and _{^{R 5 -CH 2 CH 2 N (}} CH 3) together CH ₂ - The method of claim 1 which represents a.   2. The method according to claim 1, wherein n represents 2 or 3.   The tertiary amine amide catalyst composition comprises 2-ethylhexanoic acid, coconut oil fatty acid, tall oil fatty acid, caproic acid, heptyl acid, caprylic acid, pelargonic acid, capric acid, hedecanoic acid, lauric acid, tridecanoic acid, myristic acid, Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, serotinic acid, heptacosanoic acid , Montanic acid, nonacosanoic acid, mericic acid, hentriacontanic acid, dotriacontanic acid, tritriacontanic acid, tetracontanic acid, hexatriacontanic acid, 9-phenylstearic acid, and 10-phenylstearic acid Selected Derived from that acid N- (3- dimethylaminopropyl) - The method of claim 1 which is an amide.   7. The method of claim 6, wherein the acid is selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acids, and tall oil fatty acids.   The tertiary amine amide catalyst composition comprises 2-ethylhexanoic acid, coconut oil fatty acid, tall oil fatty acid, caproic acid, heptyl acid, caprylic acid, pelargonic acid, capric acid, hedecanoic acid, lauric acid, tridecanoic acid, myristic acid, Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, serotinic acid, heptacosanoic acid , Montanic acid, nonacosanoic acid, mericic acid, hentriacontanic acid, dotriacontanic acid, tritriacontanic acid, tetracontanic acid, hexatriacontanic acid, 9-phenylstearic acid, and 10-phenylstearic acid Selected Derived from that acid N-(2-dimethylaminoethyl) - The method of claim 1 which is an amide.   9. The method according to claim 8, wherein the acid is selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acids, and tall oil fatty acids.   The tertiary amine amide catalyst composition comprises 2-ethylhexanoic acid, coconut oil fatty acid, tall oil fatty acid, caproic acid, heptyl acid, caprylic acid, pelargonic acid, capric acid, hedecanoic acid, lauric acid, tridecanoic acid, myristic acid, Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, serotinic acid, heptacosanoic acid , Montanic acid, nonacosanoic acid, mericic acid, hentriacontanic acid, dotriacontanic acid, tritriacontanic acid, tetracontanic acid, hexatriacontanic acid, 9-phenylstearic acid, and 10-phenylstearic acid Selected The method of claim 1 which is N- methyl-3-aminoethyl pyrrolidine amide derived from that acid.   The method of claim 10, wherein the acid is selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acids, and tall oil fatty acids. The tertiary amine amide catalyst composition comprises 2-ethylhexanoic acid, coconut oil fatty acid, tall oil fatty acid, caproic acid, heptyl acid, caprylic acid, pelargonic acid, capric acid, hedecanoic acid, lauric acid, tridecanoic acid, myristic acid, Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, serotinic acid, heptacosanoic acid , Montanic acid, nonacosanoic acid, mericic acid, hentriacontanic acid, dotriacontanic acid, tritriacontanic acid, tetracontanic acid, hexatriacontanic acid, 9-phenylstearic acid, and 10-phenylstearic acid Selected Is the 4,10-diaza -4,10,10- trimethyl-7-oxa derived from that acid - The method of claim 1 undecamethylene amine amides.   13. The method of claim 12, wherein the acid is selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acids, and tall oil fatty acids.   The method of claim 1, wherein the tertiary amine amide catalyst composition is N- (3-dimethylaminopropyl) -2-ethyl-hexamide.   The method of claim 1, wherein the tertiary amine amide catalyst composition is N- (3-dimethylaminopropyl) -cocoamide.   The method of claim 1, wherein the tertiary amine amide catalyst composition is N- (3-dimethylaminopropyl) -tall oil amide.   The gelling catalyst is a mono- and / or bis- (tertiary aminoalkyl) urea selected from the group consisting of diazabicyclooctane (triethylenediamine), quinuclidine, substituted quinuclidine, substituted pyrrolidine and substituted pyrrolididine. 2. The method according to 1. The following components in parts by weight (pbw):
Polyol 20-100
Polymer polyol 80-0
Silicone surfactant 1-2.5
Blowing agent 2 to 4.5
Crosslinking agent 0.5-2
Catalyst 0.25-2
Isocyanate index 70-115
2. The method according to claim 1, comprising reacting   The method of claim 1, wherein the tertiary amine amide catalyst composition is acid-blocked.   20. The method of claim 19, wherein the catalyst composition is acid-blocked with a carboxylic acid.   21. The method according to claim 20, wherein the carboxylic acid is formic acid, acetic acid, 2-ethyl-hexanoic acid, gluconic acid or N- (2-hydroxyethyl) -iminodiacetic acid. In a process for producing a polyurethane foam, comprising reacting an organic polyisocyanate with a polyol in the presence of water as a blowing agent, a cell stabilizer, a gelling catalyst and a catalyst composition, a compound of formula I:

(Wherein A represents CH or N;
R ¹ is hydrogen or

Represents
n represents an integer of 1 to 3,
R ² and R ³ each represent hydrogen or a C ₁ -C ₆ linear or branched alkyl group;
When A represents N, R ⁴ and R ⁵ each represent a C ₁ -C ₆ linear or branched alkyl group, or when A represents N, R ⁴ and R ⁵ together represent C ₂ or represents an alkylene group having -C _5, or when a represents CH or N, R ⁴ and R ⁵ may be an alkylene group of C ₂ -C ₅ containing NR ⁷ together, wherein R ⁷ hydrogen, an alkyl group of C ₁ -C ₄ linear or branched and are

Selected from the group consisting of
And R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group)
Using a tertiary aminoalkylamide catalyst composition represented by or a catalyst composition in which the tertiary aminoalkylamide catalyst is acid-blocked with a carboxylic acid, while maintaining and controlling the physical properties of the foam The above method wherein the reaction of water with the isocyanate allows foaming of the foam.