JP4004462B2 - Process for the production of polyurethane foams using tertiary aminoalkylamide catalysts derived from long chain alkyls and aliphatic carboxylic acids - Google Patents

Description

  The present invention relates to the use of tertiary aminoalkylamides as catalysts for the production of polyurethane foams.

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

The ability of a tertiary amine catalyst to selectively promote either foaming or gelation is an important consideration in selecting a catalyst for producing a particular polyurethane foam. If the catalyst accelerates the foaming reaction too significantly, much of the CO ₂ is generated before the reaction between the isocyanate and polyol takes place sufficiently, and the CO ₂ is foamed out of the formulation, resulting in a foam It will lead to the collapse of. A poor quality foam will be produced. In contrast, if the catalyst promotes the gelling reaction too strongly, a significant portion of CO ₂ will be generated after polymerization has occurred to a significant extent. Again, poor quality foam will be produced, which is characterized by high density, broken or poorly contoured cells and other undesirable shapes.

  Tertiary amine catalysts generally have malodors 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 issues, and the release of residual amines from customer products is generally undesirable.

Amine catalysts derived from carboxylic acids and fatty acids with long-chain alkyl groups (C ₆ or higher) and having amide functionality have molecular weight and hydrogen bonding capacity when compared to related structure materials lacking this functionality. And increased volatility and odor. Furthermore, catalysts containing amide functional groups chemically bond to the polyurethane polymer upon reaction and are not released from the finished product. Catalyst structures that embody this concept are typically low to moderate in activity and promote both 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 describes a number of stable compounds against diffusion with tertiary amino groups in the production of polyisocyanate addition products that do not discolor the surrounding material or change its composition. The use of such aminoalkylureas is disclosed. Specifically taught are Catalyst A and Catalyst D, which are the reaction products of dimethylamino-propylamine and urea.

  U.S. Pat. No. 4,007,140 discloses the use of 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 foams. 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 foam is also described.

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

  U.S. Pat. Nos. 5,302,303, 5,374,486 and 5,124,367 describe aliphatic amidoamines as components necessary for stabilization of isocyanate compositions containing flame retardants. The use of is disclosed. The storage stability of isocyanate-reactive compositions is often adversely affected by the addition of flame retardants, particularly those based on phosphorus, zinc, antimony, and aluminum. The use of an aliphatic aminoamide 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 process for producing a polyurethane foam comprising reacting an organic polyisocyanate and a polyol in the presence of water as a blowing agent, a cell stabilizer, and a tertiary aminoalkylamide catalyst composition. This 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- or represents an alkylene group having C _5, or a is may be an alkylene group of C ₂ -C ₅ containing NR ⁷ R ⁴ and R ⁵ together when represents CH or N, wherein R ⁷ is hydrogen A C ₁ -C ₄ linear or branched alkyl group and

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

  The present invention provides a reactive catalyst composition for producing flexible polyurethane foam foamed with water. This reactive catalyst contains an amide functionality that allows it to react to the polyurethane substrate. This reactive catalyst can be used as a gelling catalyst or foaming catalyst with complementary cocatalysts for foaming or gelling, respectively, which contain reactive functional groups to produce polyurethane foam materials. However, it does not have to be included. This reactive catalyst produces a polyurethane foam free of amine emissions.

  Use of this catalyst with a complementary gelling or foaming cocatalyst improves the physical properties of the foam and enhances processability. As a gelling catalyst, this amide catalyst with a foaming cocatalyst improves the air flow of the foam. Improved air flow means improved foam porosity and openness, which is an indicator of improved foam dimensional stability. As a gelling catalyst, this amide catalyst with a foamable cocatalyst improves the force leading to foam failure. In other words, this is reduced. The reduction in force leading to failure means that the foam is more easily compressed, which is an important advantage to minimize shrinkage of the foam during processing. As an effervescent catalyst, this amide catalyst with a gelling cocatalyst improves the load bearing properties of the foam. Such high molecular weight compounds have been suggested in the prior art to react during mixing and to be incorporated into the polymer matrix early in the polyurethane process, thus limiting the mobility of the compound. It is surprising that has a good catalytic activity in the production of polyurethanes.

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

The present invention provides a process for producing polyurethane foam using a reactive catalyst composition comprising a tertiary aminoalkylamide. The amide is derived from a carboxylic acid of the R ⁶ —CO ₂ H type, where R ⁶ is a C ₅ -C ₃₅ linear or branched alkyl, alkenyl, or aryl group. Although the catalyst is typically used in the presence of a gelling catalyst, a combination of blowing catalyst and gelling catalyst is also possible. The catalyst may contain a reactive NH group derived from an amide function, which allows the catalyst to react with and immobilize into the polyurethane substrate. These catalysts can be used as gelling or blowing catalysts with or without the aid of complementary tertiary amine blowing or gelling cocatalysts, where The cocatalyst may or may not contain reactive functional groups that produce a polyurethane foam material. The reactive catalyst produces a polyurethane foam with no amine odor or amine emissions.

The reactive catalyst composition of the present invention may be represented by three moieties: a tertiary amine moiety, an amide moiety, and a long chain alkyl moiety (R ⁶ ). The tertiary amine moiety provides catalytic action to produce a polyurethane foam. The amide moiety provides a functional group that allows the catalyst to react into the polyurethane substrate so that the resulting polyurethane foam does not have an amine odor or amine emissions. The long chain alkyl moiety allows the catalyst to improve its performance by giving the foam better dimensional stability. That is, the air flow through the foam is improved with the length of the long chain alkyl moiety.

  Example 7 shows that conventional dialkylaminoamides in which the amide moiety is derived from a simple carboxylic acid such as formic acid 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, function by themselves when current industrial standards (DABCO® BLV catalyst) are used. do not do. The performance limits of these compounds are very well recognized in the art, and similar limits are expected for related structure materials. Addition that compounds such as N- (3-dimethylaminopropyl) -2-ethylhexamide or N- (3-dimethylaminopropyl) -lauramide have higher molecular weights resulting in higher levels of usage It would be expected to function similarly to N- (3-dimethylaminopropyl) -formamide and N- (3-dimethylaminopropyl) -acetamide with some limitations.

  Example 10 shows how the air-flow can be systematically changed depending on the catalyst selected. Example 10 shows that air flow through the foam improves sequentially with the length of the alkyl chain moiety with the amide functionality. Thus, increasing the size of an alkyl chain or aliphatic group with an amide moiety can intentionally increase air flow. Example 10 shows that a planned improvement in air flow can be achieved by appropriate selection of the reactive catalyst composition or by its usage level (see also Example 11).

The examples presented in this disclosure clearly show that long alkyl chain and fatty acid derivatives perform surprisingly better than their lower molecular weight counterparts, which indicates an expansion rate. This is because most profiles can overlap with fugitive working industrial standards (DABCO® BLV catalyst). N- (3- dimethylaminopropyl) - and in formamide N- (3- dimethylaminopropyl) - Me ₂ in acetamide - moiety, e.g., N- (3- dimethylaminopropyl) - Me in lauramide ₂ - It seems that the activity as a catalyst is smaller than the part. In addition, the amount of catalyst used remains moderate despite the molecular weight of the fatty acid catalyst being significantly greater than the molecular weight of the standard. The greater activity of the catalyst composition can explain the moderate level of its use, but the reason for this increase in activity is not clear or clearly understood. In addition, this benefit is not limited to dynamic velocity balance, but rather results in a planned improvement in foam quality as evidenced by air flow values.

  The catalyst composition of the present invention catalyzes a reaction between an isocyanate functional group and a compound containing active hydrogen, ie, an alcohol, polyol, amine or water. The catalyst composition performs a urethane (gelation) reaction with a hydroxyl group isocyanate of a polyol to form a polyurethane foam, and a foaming reaction with an isocyanate of water that releases carbon dioxide to produce a foamed polyurethane. After all it catalyzes.

  Flexible polyurethane foam products are suitable as known in the art including, for example, hexamethylene discarnate, phenylene carbonate, toluene carbonate (TDI) and 4,4'-diphenylmethane carbonate (MDI). Any organic polyisocyanate can be used. 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 contains about 60% of 4,4′-diphenylmethane carbonate. Contain with higher polyisocyanates of isomers and analogs. Also suitable are "prepolymers" of these polyisocyanates consisting of a pre-reacted mixture of polyisocyanate and polyether polyol or polyester polyol.

  Illustrative examples of suitable polyols as a component 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 such as 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 derivatized terminal hydroxyl groups.

  In practicing the present invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols may be used, such as mixtures of 2-functional and 3-functional materials and / or mixtures of materials with different molecular weights or different chemical compositions.

  Useful polyester polyols include reacting a dicarboxylic acid with an excess of diol, such as reacting adipic acid with ethylene glycol or butanediol, or reacting a lactone with excess diol, such as reacting caprolactone with propylene glycol. That are manufactured by this.

  In addition to polyester polyols and polyether polyols, the main batch, or premix composition, often contains polymer polyols. Polymer polyols are used in polyurethane foams to increase the resistance to foam deformation, that is, to improve the load bearing properties of the foam. Two different types of polymer polyols are currently used to improve load bearing. The first type shown as a graft polyol consists of a triol in which a vinyl monomer is graft copolymerized. Styrene and acrylonitrile are commonly selected monomers. The polyol modified with the second type of polyurea is a polyol containing a polyurea dispersion produced by the reaction of a diamine and TDI. Since TDI is used in excess, some of the TDI will react with both the polyol and polyurea. This second type of polymer polyol has a variant called PIPA polyol, which is produced by in situ polymerization of TDI and alkanolamine in the polyol. Depending on the required load support, the polymer polyol may account for 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; cross-linking agents such as diethanolamine, diisopropanolamine, triethanolamine and tripropanolamine; water There are foaming agents such as CFCs, HCFCs, HFCs, pentane and the like; and cell stabilizers such as silicone surfactants.

A typical formulation of 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 to 2.5
Foaming agent 2-4.5
Cross-linking 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を表すときに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 to} 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 a is may be an alkylene group of C ₂ -C ₅ containing NR ⁷ R ⁴ and R ⁵ together when represents CH or N, wherein R ⁷ is Hydrogen, C ₁ -C ₄ linear or branched alkyl groups and

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

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

Illustrative examples of dialkylaminoamides derived from higher alkyl and fatty acids are N- (3-dimethylaminopropyl) -amide, N- (2-dimethylaminoethyl) -amide, N-methyl-3- aminoethyl pyrrolidine amides, 4,10-diaza -4,10,10- trimethyl-7-oxa - Dekaamin amide 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, tricosanoic acid, lignoceric acid, pentaco Acid, serotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melicic acid, hentriacontanoic acid, dotriacontanoic acid, tritriacontanoic acid, tetracontanic acid, hexatriacontanoic acid, or aliphatic or aromatic thereof Substituted dimethylamino-alkylamides or dialkylamino-alkylamides derived from 9-phenylstearic acid and 10-phenylstearic acid and related structure materials, 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 acid, and tall oil fatty acid.

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

  Amides can be used with gelling catalysts such as tertiary amines or suitable transition metal catalysts, and / or blowing catalysts, depending on the desired advantages in the process.

  Examples of suitable tertiary amine gelation catalysts include Air Products and Chemicals Inc. Include, but are not limited to, diazabicyclooctane (triethylenediamine), quinuclidine and substituted quinuclidine, substituted pyrrolidine and pyrrolizidine supplied commercially as DABCO 33LV® catalyst. 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 higher permethylated polyamines, 2- [N- (dimethylaminoethoxyethyl)- N-methylamino] ethanol and related structures, but are not limited to, 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 different acids to form a delayed action catalyst. Such acid-blocked catalysts, in addition to the inherent advantages of the compositions of the present invention, are expected to provide a delayed action that is an advantage in flexible cast and rigid polyurethane foams. Is done. The acid-blocked catalyst can be obtained by combining the catalyst composition with formic acid, acetic acid, 2-ethylhexanoic acid, gluconic acid, N- (2-hydroxyethyl) -iminodiacetic acid and similar 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 and salt decomposition begins to occur. The acid-block catalyst of the present invention finds its primary use in cast, flexible, rigid polyurethane foams where delayed reaction initiation is desired. This delay moderates the increase in viscosity so that the mold can be properly filled and the maximum productivity can be maintained while keeping the overall casting time as short as possible.

  A catalytically effective amount of a catalyst composition comprising an amine and tertiary amine gelling or foaming catalyst may be used in the polyurethane formulation. A more particularly suitable amount of catalyst composition is in the range of about 0.01 to 10 parts per hundred parts by weight of 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 it has been stated that the present invention is useful for producing flexible polyurethane foams, the present invention may also be used to produce semi-flexible and rigid foams. Rigid polyurethane foam can be distinguished from flexible polyurethane foam by the higher level of isocyanurate present in the rigid foam. For flexible foams, as part of the total polymer polyol in the foam composition, a conventional triol in which the polymer polyol has a weight average molecular weight (Mw) of 4000 to 5000 and a hydroxyl number (OH #) of 28 to 35 Used with. In contrast, rigid polyurethane foam compositions use polyols with Mw of 500-1000 having 3-9 hydroxyl functional groups and OH # of 160-700. Rigid foam can still be distinguished from flexible foam by the isocyanate (NCO) index of the foam composition. Rigid foam compositions typically employ an NCO index of 100-300, while flexible foam compositions typically require an NCO index of 70-115.

  A typical rigid rigid 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 0.5-15
Isocyanate index 80-300

  To produce foam for laminates (insulation boards) and appliances, the NCO index is typically 100-300, and to produce open cell foam, the NCO index is typically 100-120. Yes, and usually all foam is foamed with water.

  Semi-flexible molded foam is utilized for many applications in the automotive area. Major 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
Crosslinker 1.5
Water 2.2
Catalyst 0.5-10
Black colorant 0.3
Adhesion promoter 2.0
Cell opener 1.0
Polymer MDI, index 105

  The two main components are a base polyol and a copolymer polyol (CPP). The base polyol is utilized at a level of 70-100%. The molecular weight of the base polyol is from 4500 to 6000 for triol and from 2000 to 4000 for diol. Polyether polyols capped with ethylene oxide as the base polyol replace most polyester polyols. The main hydroxyl content is usually above 75% and the range of capping is typically 10-20%. The other major component is CPP, which is used at a level of 0-20%. Base polyols and CPPs are formulated with low molecular weight crosslinkers to increase hardness and make mold removal faster. The level of crosslinker will vary depending on the hardness requirements of the part to be finished. The water level is chosen to give a free expansion density of 3-6 pounds. In semi-flexible foams, cell openers are also utilized to reduce the internal pressure of the foam during the cure cycle and thus reduce pressure release vacancies and “parting lines”. In order to improve the adhesion between the polyurethane foam and the vinyl film, an adhesion promoter may be added depending on the nature of the vinyl film. Since the N—H group of the amine functional group can react with the isocyanate to form a covalent bond with the polyurethane polymer, the use of the catalyst composition of the present invention results in a vinyl film discoloration typically observed for conventional amine catalysts. To reduce.

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

N- (3- dimethylaminopropyl) - the acetamide (DMAPA- acetamido) Synthesis Teflon three 500ml equipped with a magnetic stir bar and pressure equalizing dropping funnel coated with neck round bottom flask, 3 -83.3 g of dimethylaminopropylamine (DMAPA) was added. 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.

N- (3- dimethylaminopropyl) - formamide (DMAPA- formamide) Synthesis Teflon coated magnetic stir bar and 3-neck round bottom flask 500ml equipped with a pressure-equalizing dropping funnel, DMAPA80g Put. 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 for 2 hours to reflux and the progress of the reaction was monitored by GC. The product was distilled under reduced pressure to obtain 93.4 g of N, N-dimethylaminopropylamino-formamide as a clear and colorless liquid.

N- (3- dimethylaminopropyl) -2-ethyl - Hekisamido - Three 500ml equipped with a magnetic stir bar and pressure equalizing dropping funnel coated with (DMAPA-2-ethyl Hekisamido) Synthesis Teflon (registered trademark) In a round neck flask, 100 g of DMAPA was placed. 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) propyronamide as a transparent yellow liquid.

N- (3- dimethylaminopropyl) - the lauramide (DMAPA- lauramide) Synthesis Teflon coated magnetic stir bar and 3-neck round bottom flask 500ml equipped with a pressure-equalizing dropping funnel, DMAPA88g Put. 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 proceeded. Once the reaction was complete, excess DMAPA was removed under reduced pressure to give 141 g of 3- (N, N-dimethylamino) -1- (lauroyl) propionamide as a yellow solid. As a catalyst, 52% in DPG (dipropylene glycol) was used as a catalyst.

N- (3- dimethylaminopropyl) - to cocamide (DMAPA- Cocamide) Synthesis Teflon coated magnetic stir bar and 3-neck round bottom flask 500ml equipped with a pressure-equalizing dropping funnel, DMAPA88g Put. While monitoring the temperature with a thermocouple, coconut oil fatty acid (100 g) was slowly added to the reaction mixture and, at the end of the addition, the liquid was heated to reflux. Water was removed periodically as the reaction progressed. Once finished, excess DMAPA was removed under reduced pressure, yielding 147 g of amide product as a pale yellow liquid that slowly solidified when placed on a table.

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

Rate of rise of foam: DMAPA-formamide and DMAPA-acetamide vs. DABCO® BLV catalyst-industrial standard In this example, polyurethane foam was prepared in a conventional manner. The polyurethane formulation in parts by weight was as follows.

  For each foam made, the catalyst was added to 159 grams of the above premix in a 32 ounce (951 ml) paper cup and overhead stirring with a 2 inch (5.1 cm) diameter stirring rod. The machine was used to mix the formulation at 6,000 RPM for 10 seconds. Sufficient TDI 80 was added to make an index 108 foam [index = (mole NCO / mole active hydrogen) × 100] and the formulation was thoroughly mixed for 6 seconds at 6,000 RPM using the same stirrer. . A 32 oz (951 ml) cup was dropped through a hole in the bottom of a 128 oz (3804 ml) paper cup on the table. This hole is dimensioned to capture the edge of a 32 ounce cup. The total volume of the foam container was 160 ounces (4755 ml). The foam approached this volume at the end of the molding process. The maximum foam height was recorded.

  The following data shows a comparison with DABCO® BLV catalyst (industrial standard, hereinafter “BLV”) and 3- (N, N-dimethylamino) -1-formyl-propionamide.

  This data shows that DMAPA-formamide is not as effective as BLV. The rise time is too long (103.6 seconds for BLV versus 122.8 seconds for DMAPA-formamide at 0.11 pphp) and it cannot be corrected by the addition of more catalyst. In fact, the rise time increases with further catalyst addition. The maximum height was also lower for the DMAPA-formamide example.

  The following data shows a comparison between BLV (industrial standard) and 3- (N, N-dimethylamino) -1-acetyl-propionamide.

  The data show that DMAPA-formamide is not as effective as BLV. Both catalysts have similar rise times (102.3 seconds for DMAPA-acetamide using 0.22 pphp versus 103.3 seconds for BLV), but the final foam height is the case for acetamide Was significantly lower (279.9 seconds for DMAPA-acetamide versus 289.2 mm for BLV).

Rate of foam rise: DMAPA-2-ethyl-hexamide and DMAPA-lauramide vs. BLV industrial standard The following data is for BLV catalyst (industrial standard) and lauric acid and of 2-ethyl-hexanoic acid A comparison with DMAPA amide is shown.

  The table above shows the results obtained for two controls of BLV and DMAPA-lauramide and DMAPA-2-ethylhexamide. Under these conditions, dialkylamine catalysts are typically expected to be less active than the standard, but surprisingly both amide derivatives showed rise times and maximum heights.

Rate of foam rise: DMAPA-amide of tall oil fatty acid vs. industrial standard of BLV The following data is from BLV catalyst (industrial standard) and 3- (N, N-dimethylamino) -1-toll oil -Shows a comparison with propionamide.

  The table above shows the results obtained for the BLV control and DMAPA-TOFA amide. This amide shows a rise time on the shoulder with BLV, but the foam height is improved. Despite the fact that the number of catalytically active nitrogens in the case of amides is almost the same as in BLV, the superior performance of this amide composition is demonstrated.

Physical Properties of Polyurethane Foam In this example, various amides of formula Me ₂ N— (CH ₂ ) ₃ NHCO—R were evaluated to illustrate the effect of alkyl chain R size on the air flow of the foam. The following formulation was used to produce a larger foam (scale factor = 3.2).

  For each foam, add the catalyst to 339.2 g of the above premix in a 32 oz (951 ml) paper cup and add an overhead stirrer with a 2 inch (5.1 cm) diameter stirrer. Used and mixed at 6,000 RPM for 10 seconds. Add enough TDI 80 to make an index 108 form [index = (mole NCO / mole active hydrogen) × 100] and mix the formulation well at 6,000 RPM for 6 seconds using the same stirrer did. The contents were poured into a 3.5 gallon container. The foam approached this volume at the end of the foam molding process. The maximum foam height was recorded and the physical properties were evaluated. The catalysts evaluated were all amides derived from DMAPA (3-N, N-dimethylamino-propylamine).

DMAPA-2-EHA: DMAPA amide from 2-ethyl-hexanoic acid DMAPA-O: DMAPA amide from octanoic acid DMAPA-L: 52% DPG solution of DMAPA amide from lauric acid DMAPA-T: tall oil fatty acid (TOFA) DMAPA amide from) DMAPA-C: DMAPA amide from coconut oil fatty acid

  The above table shows that air flow in the polyurethane foam can be systematically controlled by selecting a tertiary aminoalkylamide catalyst. As the alkyl chain length in the amide increases, the air flow of the foam improves. Improved air flow means improved foam porosity and openness, which indicates improved dimensional stability of the foam.

Polyurethane Foam Physical Properties In this example, foams were made using various loadings of DMAPA-TOFA catalyst and the physical properties were evaluated. The foam was made according to the recipe of Example 10.

  The results show that the air flow can still be deliberately changed by changing the loading of the amino-amide catalyst.

  While many aspects of the invention have been shown, it is apparent that the basic structure can be varied to show other aspects of utilizing the invention without departing from the spirit and scope of the invention. Such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims rather than in the specific embodiments illustrated by the examples.

Claims (8)

Water as a blowing agent, cell stabilizer, 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 to} C ₆ linear or branched alkyl group, or when A represents N, R ⁴ and R ⁵ together represent C ₂ When -C ₅ represents an alkylene group, or A represents CH or N, R ⁴ and R ⁵ together are a C ₂ -C ₅ alkylene group containing NR ⁷ , where R ⁷ is hydrogen A C ₁ -C ₄ linear or branched alkyl group and

Selected from the group consisting of
R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group.
Reacting an organic polyisocyanate with a polyol in the presence of a catalyst composition containing a tertiary aminoalkylamide catalyst represented by or a catalyst composition in which the tertiary aminoalkylamide catalyst is blocked with an acid. A process for producing a polyurethane foam comprising: Tertiary aminoalkylamide catalyst is 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, serotic acid, heptacosanoic acid , Montanic acid, nonacosanoic acid, mericic acid, hentriacontanoic acid, dotriacontanoic acid, tritriacontanoic acid, tetracontanic acid, hexatriacontanoic acid, 9-phenylstearic acid, and 10-phenylstearic acid Choice N- (3-dimethylaminopropyl) -amide, N- (2-dimethylaminoethyl) -amide, N-methyl-3-aminoethylpyrrolidine amide, or 4,10-diaza-4, 10,10-trimethyl-7-oxa - Dekaamin method according to claim 1 is an amide.   The method of claim 2, wherein the acid is selected from the group consisting of 2-ethylhexanoic acid, coconut oil fatty acid, and tall oil fatty acid.   Tertiary aminoalkylamide catalyst is N- (3-dimethylaminopropyl) -2-ethyl-hexamide, N- (3-dimethylaminopropyl) -cocoamide, or N- (3-dimethylaminopropyl) -tolu oil amide The method of claim 1, wherein The following components in parts by weight (pbw):
Polyol 20-100
Polymer polyol 80-0
Silicone surfactant 1 to 2.5
Foaming agent 2-4.5
Cross-linking agent 0.5-2
Catalyst 0.25-2
Isocyanate index 70-115
A process according to claim 1 comprising reacting.   The process according to claim 1, wherein the catalyst is acid-blocked with a carboxylic acid.   The process according to claim 6, 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 and a polyol in the presence of water as a blowing agent, a cell stabilizer, 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 to} 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 together an alkylene group of C ₂ -C ₅ including NR ^7, wherein R ⁷ is Hydrogen, C ₁ -C ₄ linear or branched alkyl groups and

Selected from the group consisting of
R ⁶ represents a C ₅ -C ₃₅ linear or branched alkyl, alkenyl or aryl group.
A catalyst composition comprising a tertiary aminoalkylamide catalyst represented by: or a porosity of the foam, comprising using a catalyst composition wherein the tertiary aminoalkylamide catalyst is acid-blocked with a carboxylic acid, and A method as described above with the improvement in controlling and improving the degree of openness.