KR20150029464A - Catalyst composition for polyurethane resin comprising tertiary amine catalyst - Google Patents

Abstract

In the present invention, provided is a polyurethane resin made by using a reaction under a catalyst composition and a foaming agent. In the present invention, disclosed is a catalyst composition for manufacturing polyurethane resins including a tertiary amine catalyst which has at least one selected from chemical formula 1 or chemical formula 2 wherein the catalyst composition has a high activity, a high selectivity for a foaming reaction, less stink and an improved effect compared with an existing catalyst while having no volatile organic compounds, thereby being used as an eco-friendly urethane polymerization catalyst.

Description

[0001] The present invention relates to a catalyst composition for preparing polyurethane resin containing a tertiary amine catalyst,

The present invention relates to a catalyst composition for the production of a polyurethane resin containing a tertiary amine catalyst, and more particularly to a catalyst for the production of a polyurethane resin containing a tertiary amine catalyst useful for preparing a foamed polyurethane, ≪ / RTI >

Foamed polyurethanes are widely known and are used in automotive, residential and other industries. Such foams are prepared by reacting a polyisocyanate with a polyol in the presence of various additives. One such additive is a physical blowing agent which evaporates as a result of the exothermic reaction to form a bubble-rich foam. It was discovered that chlorofluorocarbons (CFCs) used in the past deplete ozone in the stratosphere and the order to discontinue the use of CFCs was legislated and production and use were discontinued.

Thus, it has become increasingly important to produce foams foamed in water by performing a foaming reaction using CO ₂ generated by the reaction of water with polyisocyanates. Tertiary amine catalysts are commonly used to promote foaming reactions (reactions that generate CO ₂ from water and isocyanates) and gelation reactions (reaction of polyols with isocyanates).

The fact that the tertiary amine catalyst can selectively promote the foaming or gelling reaction is an important consideration in selecting a catalyst for producing a particular foamed polyurethane. When the catalyst excessively promotes the foaming reaction, excessive CO ₂ is released before sufficient reaction between the isocyanate and the polyol occurs, and CO ₂ is exhausted from the preparation, so that the foam can be disintegrated and a foam having poor quality is produced . On the other hand, if the catalyst promotes the gelation reaction too strongly, most of the CO ₂ will be released after the polymerization has occurred to a considerable extent. Similarly, there is a problem that a foam having poor quality can be produced.

Tertiary amine catalysts are generally odorous, and the majority are volatile because of their low molecular weight. Severe safety and toxicity problems may arise if tertiary amines are released during the foaming process, and it is generally undesirable for residual amines to be released from the consumer.

An amine catalyst containing a urethane functional group has a high molecular weight, a high hydrogen bond, and a reduced volatility and odor when compared with a related structure having no functional group. In addition, catalysts containing urethane functional groups are chemically bonded into the urethane during the reaction and are not released from the article. Catalyst structures embodying this concept usually have low or moderate activity and promote both the foaming reaction (water-isocyanate) and the gelling reaction (polyol-isocyanate) to varying degrees.

Korean Patent No. 10-0274116 discloses a reactive catalyst composition for improving foamed polyurethane performance underwater foam. However, the above patent has a problem that the activity is not high and a volatile organic compound (Voc) is generated.

In order to solve the above problems,

The reaction of an isocyanate functional group with an active hydrogen atom-containing compound, that is, a reaction with an alcohol, a polyol, an amine or water, specifically a polyurethane by a urethane (gelling) reaction of a polyol hydroxy group and an isocyanate, or a foaming reaction of water with an isocyanate It is an object of the present invention to provide a catalyst composition for producing a polyurethane resin which promotes the reaction for producing foamed polyurethane by releasing carbon dioxide and does not generate volatile organic compounds (Voc).

Another object of the present invention is to provide a method for producing a polyurethane resin by using the catalyst composition for producing a polyurethane resin.

Another object of the present invention is to provide a polyurethane resin obtained by the reaction in the presence of the catalyst composition and the foaming agent.

In order to achieve the above object,

There is provided a catalyst composition for preparing a polyurethane resin comprising a tertiary amine catalyst, which comprises at least one selected from the following formulas (1) and (2):

≪ Formula 1 >

(2)

In this formula,

R ₁ And R ₃ is independently C ₁ -C ₆ respectively Alkyl group, R ₂ is C ₁ -C ₆ R ₄ is H or a C ₁ -C ₈ carbonyl group, a C ₁ -C ₆ dimethylalkylamine group or a C ₁ -C ₆ alkylcarbonyl group or a C ₁ -C ₆ alkylcarbonyl group, _1- C ₆ dimethylalkylaminocarbonate group.

To achieve these and other objects,

There is provided a process for producing a polyurethane resin by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of a catalyst and a foaming agent, wherein the catalyst composition is used .

According to another aspect of the present invention,

A polyurethane resin obtained by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of the catalyst composition and a foaming agent.

The present invention provides a catalyst composition useful for producing polyurethane products, particularly foamed polyurethanes. The catalyst composition of the present invention has high activity, high selectivity to the foaming reaction, and low odor. It can be used as an environmentally friendly urethane polymerization catalyst since volatile organic compounds (Voc) are not generated while exhibiting an effect equal to or higher than that of existing catalysts.

Hereinafter, the present invention will be described in detail.

The present invention is to provide a reactive catalyst composition for use in producing flexible foam polyurethane foamed with water. The catalyst composition comprises a urethane containing a tertiary aminoalkyl group and / or a urethane containing a bis (tertiary aminoalkyl) group mixed with a gelling reaction catalyst or a foaming reaction catalyst. The use of such catalyst compositions is to improve the physical properties of the foamed polyurethane.

The reactive catalyst comprises a urethane functional group that allows the catalyst to react into the polyurethane matrix. These reactive catalysts can be used as a gelling reaction catalyst or a foaming reaction catalyst for use together with complementary foaming or gelling reaction co-catalysts, and the foaming or gelation reaction promoting catalysts can be used as catalysts for producing foamed polyurethane materials And may or may not include reactive functional groups. The reactive catalyst produces a foamed polyurethane that does not emit any amine at all.

Methods using reactive catalysts with gelation or foaming reaction promoters improve physical properties and enhance processability. As foaming reaction catalysts, reactive catalysts in combination with a gelling reaction promoter improve the airflow characteristics of the foam. The improved airflow properties mean improved porosity and openness of the foam which exhibit improved dimensional stability of the foam. As gelling catalysts, reactive catalysts in combination with blowing reaction promoters improve the force-to-crush characteristics of the foam. Reduced fracture stresses mean that the foam can be more easily compressed as an important advantage to minimize shrinkage of the foam during processing.

The present invention provides a catalyst composition for the production of a polyurethane resin comprising a tertiary amine catalyst, which comprises at least one selected from the following formulas (1) and (2)

≪ Formula 1 >

(2)

In the formula,

R ₁ And R ₃ is independently C ₁ -C ₆ respectively Alkyl group, R ₂ is C ₁ -C ₆ R ₄ is H or a C ₁ -C ₈ carbonyl group, a C ₁ -C ₆ dimethylalkylamine group or a C ₁ -C ₆ alkylcarbonyl group or a C ₁ -C ₆ alkylcarbonyl group, _1- C ₆ dimethylalkylaminocarbonate group.

Preferably, R ₁ and R ₃ are each independently an ethyl or propyl group, and R ₄ is preferably a C ₂ or C ₈ carbonyl group or a C ₂ -C ₃ dimethylalkylaminocarbonyl group.

Examples of suitable containing groups of mono-urethanes and bis-urethanes are 2-dimethylaminoethyl; N, N'-bis (2-dimethylaminoethyl); N, N-bis (2-dimethylaminoethyl); 3-dimethylaminopropyl; N, N'-bis (3-dimethylaminopropyl); N, N-bis (3-dimethylaminopropyl); 1- (N-methyl-3-pyrrolidino) methyl; 1,3-bis (N-methyl-3-pyrrolidino) methyl; 3-piperidinopropyl; N, N'-bis (3-piperidinopropyl); 3-morpholinopropyl; N, N'-bis (3-morpholinopropyl); 2-piperidinoethyl; N, N'-bis (2-piperidinoethyl); 2-morpholinoethyl; And N, N'-bis (2-morpholinoethyl).

Preferred substituents include 2-dimethylaminoethyl; N, N'-bis (2-dimethylaminoethyl); (N-methyl-3-pyrrolidino) methyl, 1,3-bis (N-methyl-3-pyrrolidino) (N-methyl-3-pyrrolidino) methyl urethane and 1,3- dimethylaminopropyl and N, N'-bis (3-dimethylaminopropyl) -Bis (N-methyl-3-pyrrolidino) methyl group, which mixtures have a molar ratio of mono substituted urethane to bis substituted urethane of from 95: 5 to 5:95.

Mono substituted urethanes and bis substituted urethanes can be prepared by reacting isocyanates and the corresponding tertiary alkyl amines in an appropriate molar ratio under an inert atmosphere at elevated temperatures of 50 to 120 캜, preferably 60 to 80 캜.

Mono- and / or bis-substituted urethanes are used with gelling or blowing reaction catalysts according to the advantages to be obtained in the process. The gelation promoter is any urethane catalyst known in the art having an initial selectivity of about 0.45 or less and a blowing reaction promoter is any urethane catalyst known in the art having an initial selectivity of about 0.8 or greater. The catalyst selectivity is defined as the ratio of the foaming reaction (urea formation) rate to the gelling reaction (urethane formation) rate [J. Cell. Plastics, Vol. 28, 1992, pp. 360-398].

Examples of suitable gelling catalysts include, but are not limited to, diazabicyclooctane (triethylenediamine), quinuclidine and substituted quinuclidines, substituted pyrrolizidines, and substituted pyrrolidines .

Examples of suitable blowing reaction catalysts include, but are not limited to, bisdimethylaminoethylether, pentamethyldiethylenetriamine and related compositions, permethylated higher polyamines, branched chain polyamines, 2- [N- (dimethylaminoethoxyethyl) -N- But are not limited to, methylaminoethanol and related structures (U.S. Patent No. 4,338,408), alkoxylated polyamines, imidazole-boron compositions, and aminopropyl-bis (aminoethyl) ether compositions .

A catalyst composition comprising urethane and a gelling or blowing reaction catalyst is used in the polyurethane formulation with a catalytically active amount. More specifically, the suitable amount of the catalyst composition may be about 0.01 to 10 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the polyol in the polyurethane formulation.

Soluble foam polyurethane products, slabs and moldings can be made from any suitable organic polyisocyanates known in the art such as hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4,4 ' -Diphenylmethane diisocyanate ("MDI"). It is particularly suitable to use 2,4-TDI and 2,6-TDI alone or in combination with a commercially available mixture. Other suitable isocyanates are commercially known as "crude MDI ", marketed by Kumho Mizui Chemical as M-200 and the like, with 4,4'-diphenylmethane diisocyanate and other isomers and similar higher There are mixtures of diisocyanates containing polyisocyanates. It is also possible to use a "prepolymer" of a polyisocyanate comprising a mixture of a polyisocyanate and a part of a polyether or polyester polyol.

Specific examples of polyols suitable as components of the polyurethane composition include polyalkylene ethers or polyester polyols.

Examples of polyalkylene ether polyols include poly (alkylene oxide) polymers such as poly (ethylene oxide) polymers and poly (propylene oxide) polymers, and diols and triols such as ethylene glycol, propylene glycol, Derived from polyfunctional compounds, including 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and similar low molecular weight polyols And a copolymer having a hydroxyl group.

In the present invention, a single high molecular weight polyether polyol can be used. It is also possible to use mixtures of high molecular weight polyether polyols, for example mixtures of bifunctional and trifunctional materials and / or mixtures of materials of different molecular weight or of different chemical composition.

Examples of the polyester polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, glycerol, Pentaerythritol or polyetherpolyols or mixtures of such polyhydric alcohols with polycarboxylic acids, especially dicarboxylic acids or ester-forming derivatives thereof, such as succinic acid, glutaric acid and adipic acid or dimethyl esters thereof, End reaction products with sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl tetraphenyl phthalate or mixtures thereof. Further, polyesters obtained by polymerization of a lactone such as caprolactone with a polyol or by polymerization of a hydroxycarboxylic acid such as hydroxycaproic acid can also be used.

By adding an amino alcohol such as ethanolamine in the polyesterification mixture, a polyester amide polyol can be obtained.

In addition to polyether polyols and polyester polyols, masterbatch or premix compositions often contain polymer polyols. Polymer polyols are used in foam polyurethanes to increase the resistance to deformation of the foam, i.e. to increase the load-bearing properties of the foam. At present, two different types of polymer polyols are used to improve the strength properties.

A first type of polymer polyol, graft polyol, consists of a vinyl monomer graft-copolymerized triol. Styrene and acrylonitrile are usually selected as monomers.

A second type of polymeric polyol, a polyurea modified polyol, is a polyol containing a polyurea dispersion formed by the reaction of a diamine with TDI. Because TDI is used in excess, some TDIs can react with both polyols and polyureas. Such a second type of polymer polyol has a modification called PIPA polyol and PHD polyol, which is formed by the same phase polymerization of TDI with an alkanolamine in silver polyol. Depending on the strength requirements, the polymer polyol may constitute 20 to 80% of the amount of polyol in the master batch.

Other common reagents found in foamed polyurethane formulations include chain extenders such as ethylene glycol and butanediol; Cross-linking agents such as diethanolamine, diisopropanolamine, triethanolamine and tripropanolamine; Foaming agents such as water, CFC, HCFC, HFC, pentane and the like; And foam stabilizers such as silicone.

Typical flexible foamed polyurethane formulations containing a catalyst such as the catalyst composition of the present invention having a density of 16 to 65 kg / m < ³ >, such as materials for automotive seats, :

Soluble foaming agent Weight portion Polyol 50 ~ 100 Polymer polyol 0 to 50 Silicone surfactant 0.5 to 1.5 blowing agent 2 to 5 Cross-linking agent 0.5 to 4 Catalyst composition 0.5 to 3 Isocyanate Index 80 to 110

The catalyst composition comprises a urethane containing a mono (tertiary aminoalkyl) group and / or a urethane containing a bis (tertiary aminoalkyl) group together with a gelling or blowing reaction catalyst. The mono- and bis-urethanes may be represented by the following formulas (1) and (2): < EMI ID =

The catalyst composition may be used in combination with other tertiary amines, organotin or carboxy dicarboxylic urethane catalysts known in the art, or may further comprise such catalysts.

According to another embodiment of the present invention, there is provided a process for producing a polyurethane resin by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of a catalyst and a foaming agent, to provide.

According to another embodiment of the present invention, there is provided a polyurethane resin obtained by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of the catalyst composition and a foaming agent.

Example

Example 1

Substituted by 2-dimethylaminoethyl Urethane (formula 1a) and  N, N ' -Bis (2- Dimethylaminoethyl ) ≪ / RTI > (1b)

<Formula 1a>

&Lt; EMI ID =

Using a 1 liter, 3 neck round bottom flask equipped with a mechanical stirrer, reflux condenser, nitrogen bubbling apparatus, dropping panel and temperature controlled mantle was added urethane (2-dimethylaminoethyl) A mixture of urethane substituted with N, N'-bis (2-dimethylaminoethyl) (Formula 1a) and Formula 1b) was prepared. When 168 g of hexamethylene diisocyanate was added to the flask and stirred at a constant rate, 91.4 g of N, N'-dimethylaminoethyl alcohol was added dropwise using a dropping panel. The reaction was allowed to proceed slowly while adjusting the temperature. The mixture was slowly heated to 80 ° C. for 1 hour, and 57.6 g of acetic acid was added dropwise to remove carbon dioxide. The reaction was continued until the sign of carbon dioxide disappeared and the reaction mixture was stirred for an additional 1 hour. The synthesized pale yellow liquid was sampled and the trace isocyanate content was measured to confirm that the isocyanate value was 0, and the reaction was terminated. The flask containing the liquid was evacuated with a vacuum pump and refilled with N ₂ three times to remove any volatiles that were present until then.

According to 13 C NMR quantitative analysis, 94.5% by mol of the urethane (formula 1a) substituted with 2-dimethylaminoethyl and 4.8 mol% of the urethane substituted by N, N'-bis (2-dimethylaminoethyl) % And other 0.7 mol%.

Example 2

A mixture of a urethane substituted with 2-dimethylaminoethyl (Formula 1a) and a urethane substituted with N, N'-bis (2-dimethylaminoethyl) (Formula 1b)

Using a 1 liter, 3 neck round bottom flask equipped with a mechanical stirrer, reflux condenser, nitrogen bubbling apparatus, dropping panel and temperature controlled mantle, 2-dimethylaminoethyl substituted urethanes with a molar ratio of 5:95 ( A mixture of urethane substituted with N, N'-bis (2-dimethylaminoethyl) (Formula 1a) and Formula 1b) was prepared. When 168 g of hexamethylene diisocyanate was added to the flask and stirred at a constant rate, 169.7 g of N, N'-dimethylaminoethyl alcohol was added dropwise using a dropping panel. The reaction mixture was slowly heated to 80 ° C. After heating slowly to 80 ° C for 1 hour, 3.1 g of acetic acid was added dropwise to remove carbon dioxide. The reaction was continued until the sign of carbon dioxide disappeared and the reaction mixture was stirred for an additional 1 hour. The synthesized pale yellow liquid is sampled and the trace isocyanate content is measured to confirm that the isocyanate value is 0, and the reaction is terminated. The flask containing the liquid was evacuated with a vacuum pump and refilled with N ₂ three times to remove any volatiles that were present until then.

According to 13 C NMR quantitative analysis, the urethane (Formula 1a) substituted with 2-dimethylaminoethyl was 4.6 mol% and the urethane (Formula 1b) substituted with N, N'-bis (2-dimethylaminoethyl) % And other 0.6%.

Example 3

The foamed polyurethane was prepared in a conventional manner. The following components of the polyurethane formulation are specifically shown in Table 2:

ingredient Weight portion KE-810 80 FA-733 20 KE-825 3.0 B-8734 0.8 Diethanolamine 1.5 water 3.5 TDI 80 Index 105 KE-810, KE-825: a polyether polyol having an ordinary ethylene oxide terminal (commercially available from KPI X-Chemicals Co.). FA-733: styrene-acrylonitrile copolymer filled polyether polyol (commercially available from Chemie KPI X-Chemical Co.). B-8434: silicone surfactant (available from Degussa Korea). TDI-80: a mixture of 80% by weight of 2,4-TDI and 20% by weight of 2,6-TDI.

For the foaming formulation, the catalyst according to Table 3 was added to a 500 ml polyethylene cup to the initial compound of 202 g and mixed for 20 seconds at 5000 RPM using a top stirrer with 5.1 cm diameter stirring paddles. A sufficient amount of TDI 80 was added to make a foam having an index of 105 (index = (number of moles of NCO) / (number of moles of active hydrogen atoms) x 100) and mixed well for 5 seconds using the same top stirrer for the preparation 150g was dropped in the center of the 2000 ml polyethylene cup placed on the back balance. The time to start the initial inflation was set to T1 (sec), the time to inflate to the maximum was set to T2 (sec), and the maximum swollen height was recorded. The catalysts used and the heights of T1, T2 and foam are shown in Table 3.

catalyst T1 (sec) T2 (sec) Foam height (mm) Triethylenediamine 0.1 pphp /
Bisdimethylaminoethyl ether 0.1 pphp 11 117 252 Triethylenediamine 0.1 pphp /
The catalyst of Example 1 0.2 pphp 12 105 269

According to Table 3, when the catalyst composition of Example 1 is used, catalysts whose initial reactivity pattern is comparable to the bis-dimethylaminoethyl ether as the control catalyst, as measured by T1 and T2, and which can reach the total foam height more quickly Activity is provided. Particularly, since the volatile organic compound (Voc) is not generated while exhibiting an effect equal to or higher than that of the existing catalyst, it can be used as an environmentally friendly urethane polymerization catalyst.

Claims (5)

A catalyst composition for preparing a polyurethane resin comprising a tertiary amine catalyst, the catalyst composition comprising at least one selected from the group consisting of:

&Lt; Formula 1 >

(2)

In this formula,
R ₁ And R ₃ is independently C ₁ -C ₆ respectively Alkyl group, R ₂ is C ₁ -C ₆ R ₄ is H or a C ₁ -C ₈ carbonyl group, a C ₁ -C ₆ dimethylalkylamine group or a C ₁ -C ₆ alkylcarbonyl group or a C ₁ -C ₆ alkylcarbonyl group, _1- C ₆ dimethylalkylaminocarbonate group.
The method according to claim 1,
Wherein R ₁ and R ₃ are each independently an ethyl or propyl group and R ₄ is a C ₂ or C ₈ carbonyl group or a C ₂ -C ₃ dimethylalkylaminocarbonyl group. A catalyst composition for producing a resin.
The method according to claim 1,
The catalyst composition for producing a polyurethane resin according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (1a) or (1b)
<Formula 1a>

&Lt; EMI ID =

A process for producing a polyurethane resin by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of a catalyst and a foaming agent, wherein the catalyst composition according to any one of claims 1 to 3 is used Wherein the polyurethane resin is a polyurethane resin.
A polyurethane resin obtained by reacting a polyol and a polyisocyanate and / or an isocyanate prepolymer in the presence of a catalyst composition according to any one of claims 1 to 3 and a foaming agent.