JP5776171B2 - Amine catalyst composition for producing polyurethane resin and method for producing polyurethane resin using the same - Google Patents

Description

  The present invention relates to an amine catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the same.

  The amine catalyst composition of the present invention is particularly expected to be used as a catalyst for producing a rigid polyurethane foam.

  The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination.

  In the production of polyurethane foam using water, a low-boiling organic compound, or both as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of excellent productivity and moldability. Yes. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine and the like. (For example, refer nonpatent literature 1). In most cases, metal-based compounds are often used in combination with a tertiary amine catalyst, because the productivity and formability deteriorate, and are rarely used alone.

  Polyurethane resins, especially rigid polyurethane foams, are lightweight and have excellent heat insulation performance, and are widely used as heat insulation and heat insulation for building materials, electric refrigerators, refrigerated warehouses, plants, etc. It is a urethane resin having an independent cell structure, that is, closed cells. Since each of the closed cells is confined with a gaseous foaming agent having a relatively low thermal conductivity, it has high heat insulation performance. Further, the cell structure has a smaller radiation heat transfer and higher heat insulation performance as the hard polyurethane foam having fine closed cells is smaller.

  The heat insulating property of the rigid polyurethane foam is generally expressed by a thermal conductivity called a K-factor value, and the smaller the K-factor value, the higher the heat insulating property. This is the reason why manufacturers of rigid polyurethane foam desire such a fine cell rigid polyurethane foam having a small K-factor value.

  Conventionally, as a method for producing this fine cell rigid polyurethane foam, foaming agents such as CFC11, HCFC141b and HFC245fa in the formulation are increased, the number of water parts is reduced, and the reaction rate at the time of foam production is increased. A so-called fine cell rigid polyurethane technology for making the cell diameter fine, a method for producing a fine cell rigid polyurethane foam using a salt of an amine compound and formic acid, and the like are known (for example, see Patent Document 1).

  However, the former technology using specific chlorofluorocarbons (CFC11, HCFC141b, HFC245fa, etc.) uses low-boiling hydrocarbons, mainly cyclopentane, while being avoided because of the prohibition of the use of specific chlorofluorocarbons and the high global warming potential. Therefore, it is not a technology that can be adopted in view of the fact that the heat insulation performance has deteriorated and that there is a limit to increasing the reaction rate at the time of foam production. Further, the latter technique using a salt of an amine compound and formic acid has a problem of causing corrosion of the foaming machine.

  Furthermore, as a method for producing the fine cell rigid polyurethane foam, a method using an amine carbonate (see, for example, Patent Document 2) has been proposed. Amine carbonate is usually a solid and is used in the form of a solution with a solvent to improve workability, but when added to a polyol to form a system, amine carbonate may precipitate depending on the polyol species. This technology is also not a sufficient solution.

JP-A-1-168717 JP 2000-239339 A

Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 118

  The present invention has been made in view of the above background art, and its purpose is to cause corrosion of a foaming machine without using a fluorocarbon foaming agent that adversely affects ozone layer destruction and global warming. The present invention provides a catalyst capable of producing a fine cell rigid polyurethane foam having excellent heat insulation performance without precipitation of a catalyst even when mixed with a polyol, and a method for producing a polyurethane resin using the catalyst. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific amine compound and a glycerin-based solvent forms an effective fine cell rigid polyurethane foam, and further corrosiveness to a foaming machine. The inventors found that there was no precipitation in the polyol, and completed the present invention.

  That is, this invention is the amine catalyst composition for polyurethane resin manufacture as shown below, and the manufacturing method of a polyurethane resin using the same.

  [1] The following formula (1)

［上記式（１）中、Ｒ_１はエチレン基、又は炭素数３〜１２の直鎖若しくは分岐鎖のアルキレン基を表す。］
で示されるアミン化合物と、グリセリン系溶媒を含有するポリウレタン樹脂製造用のアミン触媒組成物。

[In the above formula (1), R ₁ represents an ethylene group or a linear or branched alkylene group having 3 to 12 carbon atoms. ]
The amine catalyst composition for the polyurethane resin manufacture containing the amine compound shown by and glycerol solvent.

  [2] The amine catalyst composition as described in [1] above, wherein the glycerin solvent is one or more compounds selected from the group consisting of glycerin, diglycerin, and triglycerin.

  [3] In the above [1] to [2], the content of the amine compound represented by the formula (1) is in the range of 2 to 85% by weight based on the total amine catalyst composition. The amine catalyst composition as described.

  [4] A method for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the amine catalyst composition according to any one of [1] to [3].

  [5] A method for producing a rigid polyurethane foam in which a polyol and an organic polyisocyanate are reacted in the presence of a catalyst and a foaming agent, and the amine catalyst according to any one of the above [1] to [3] A method for producing a rigid polyurethane foam, comprising using the composition and using water, a hydrocarbon having a boiling point in the range of 0 to 50 ° C, or both as a blowing agent.

  [6] The amount of the compound represented by the formula (1) according to the above [1] in which the amount of the amine catalyst composition according to any one of the above [1] to [3] is an important part of the polyol 100 The production method according to [5] or [6] above, wherein the content is in the range of 0.1 to 10 parts by weight.

  Since the amine catalyst composition of the present invention has weak initial activity, the time from when the raw material polyol and the organic isocyanate are mixed to when the foam formation reaction is started can be extended. As a result, it is possible to improve the operability of the mixed liquid, the liquid flowability, and the like such that the raw material liquid can sufficiently flow to every corner of the large mold.

  In addition, since an ordinary retarding catalyst contains an acid blocking agent, there is a concern about corrosiveness to metal materials. However, since the amine catalyst composition of the present invention does not contain an acid blocking agent, it is corrosive to metal materials. It does not violate polyurethane manufacturing equipment such as catalyst storage tanks and foaming equipment, and helps to improve productivity.

  Moreover, since the amine catalyst composition of the present invention does not contain an amine carbonate, the catalyst component does not precipitate even when mixed with a polyol.

  Furthermore, when the amine catalyst composition of the present invention is used, a rigid polyurethane foam having a fine cell structure, low thermal conductivity (low K-factor value) and high heat insulation performance can be produced.

  Hereinafter, the present invention will be described in more detail.

  The amine catalyst composition for producing a polyurethane resin of the present invention contains an amine compound represented by the above formula (1) and a glycerin solvent.

  In the present invention, the amine compound represented by the above formula (1) is not particularly limited. For example, N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N -Dimethyl-1,4-butanediamine, N, N-dimethyl-1,6-hexanediamine and the like. Of these, N, N-dimethyl-1,3-propanediamine is particularly preferred. The amine compound represented by the above formula (1) can be produced by a conventionally known method. For example, N, N-dimethyl-1,3-propanediamine is obtained from a hydrogenation reaction of a dialkylaminopropionitrile obtained from the reaction of di, methylamine and acrylonitrile.

  In the present invention, examples of the glycerin solvent include glycerin, diglycerin, and triglycerin. Of these, glycerin and diglycerin are preferred.

  The content of the amine compound represented by the formula (1) in the amine catalyst composition of the present invention is in the range of 2 to 85% by weight, preferably 5 to 75% by weight, based on the whole amine catalyst composition. It is a range. When the content of the amine compound represented by the above formula (1) is 85% by weight or less, K-factor, which is an index of the heat insulating performance of the polyurethane resin, is reduced, and these synergistic effects are exhibited. On the other hand, when the content of the amine compound represented by the above formula (1) is 2% by weight or more, the catalytic activity is increased and the amount of catalyst used can be reduced.

  That is, even if the amine compound or glycerin solvent represented by the above formula (1) is used alone for the production of a polyurethane resin, the catalyst activity, the heat insulating performance, etc. are problematic, and the effects of the present invention are not achieved. The synergistic action of the present invention is achieved by using the amine compound shown in 1) and a glycerin solvent together.

  As described above, the synergistic effect of the present invention is achieved by using an amine compound represented by the above formula (1) and a glycerin-based solvent in combination, so that a catalyst other than the amine compound represented by the above formula (1) can be used. Furthermore, it is not necessary to contain. However, conventionally known tertiary amine compounds, quaternary ammonium salts, organometallic compounds and the like are used as catalysts other than the amine compound represented by the above formula (1) without departing from the spirit of the present invention. be able to.

  The tertiary amine compound is not particularly limited, but triethylenediamine, dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ′. '-Pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, N-dimethylaminoethyl-N'-methylpiperazine, N, N, N ′, N′-tetramethylhexamethylenediamine, 1,2-dimethylimidazole and the like are preferable.

  Although it does not specifically limit as quaternary ammonium salts, Tetraalkylammonium halides, such as tetramethylammonium chloride, Tetraalkylammonium hydroxides, such as a tetramethylammonium hydroxide, Tetramethylammonium 2-ethylhexane And tetraalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  The organometallic compound is not particularly limited. , Dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

  Next, the manufacturing method of the polyurethane resin of this invention is demonstrated.

  The method for producing a polyurethane resin of the present invention comprises a polyol and an organic polyisocyanate in the presence of the above-described amine catalyst composition of the present invention and, if necessary, a blowing agent, a foam stabilizer, and other conventionally known auxiliaries. It is characterized by reacting.

  In the method of the present invention, the amount of the amine catalyst composition of the present invention is not particularly limited, but the content of the compound represented by the above formula (1) is usually 0 with respect to 100 parts by weight of the polyol. .1-10 parts by weight, preferably 0.5-5 parts by weight.

  In the method of the present invention, examples of the polyol include compounds having a hydroxyl value of 200 mgKOH / g to 800 mgKOH / g having two or more reactive hydroxyl groups in the molecule. Specific examples include polyether polyols, polyester polyols, phenol polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used alone or in combination of two or more.

  Examples of the polyether polyol include polyhydric alcohols (for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerin. , Trimethylol bropan, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc., polyphenols (eg, pyrogallol, hydroquinone, etc.), bisphenols (eg, bisphenol A, bisphenol S, bisphenol F, phenol and formaldehyde Low condensate, etc.), aliphatic amines (eg, propylene diamine, hexamethylene diamine, ethylene diamine, diethylene triamine, triethylene tetate) Min, pentamethylenehexamine, ethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, etc.), aromatic amines (eg, aniline, phenylenediamine, xylylenediamine, methylenedianiline, diphenyletherdiamine, etc.), alicyclic amines (Eg, isophorone diamine, cyclohexylene diamine, etc.), heteroalicyclic amines (eg, aminoethylpiperazine, etc.), Mannich polyols (eg, compounds obtained by reaction of the polyhydric phenol, the aliphatic amine and formalin, etc.) The compound etc. which added the alkylene oxide to active hydrogen compounds, such as these.

  Examples of the alkylene oxide added to the active hydrogen compound include ethylene oxide, propylene oxide, and butylene oxide. These may be used alone or in combination of two or more. Among these, ethylene oxide, propylene oxide, or a combination thereof is preferable.

  Examples of polyester polyols include condensed polyester polyols obtained by reacting polybasic acids (for example, succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid, trimellitic acid, etc.) and polyhydric alcohols, and ε -Polylactone polyol obtained by ring-opening polymerization of lactone such as caprolactone.

  Examples of the polymer polyol include a polymer polyol obtained by reacting the above-described polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

  In the method of the present invention, the organic polyisocyanate is not particularly limited, and conventionally known compounds can be used. For example, aromatic polyisocyanates, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, aliphatic polyisocyanates such as 4,4-dicyclohexylmethane diisocyanate, aromatic polyisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like Modified products (for example, carbodiimide modification, allophanate modification, urea modification, burette modification, isocyanurate modification, oxazolidone modification, etc.), isocyanate group-terminated prepolymers, and the like.

  Examples of aromatic polyisocyanates include 4- or 2,6-toluene diisocyanate (TDI), crude TDI, diphenylmethane 2,4′- or 4,4′-diisocyanate (MDI), and polymethylene polyphenyl isocyanate (crude MDI). ) And the like.

  Examples of the aliphatic polyisocyanate include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and the like. These can be used in combination as appropriate.

  In the method of the present invention, the amount of the organic polyisocyanate used is not particularly limited, but considering the foam strength, completion of the isocyanurate reaction, etc., in the production of rigid polyurethane foam, the activity capable of reacting with the polyisocyanate The isocyanate index [= (isocyanate group / active hydrogen group capable of reacting with isocyanate group) (molar ratio) × 100] with a hydrogen compound (for example, polyol, water, etc.) is generally preferably in the range of 70 to 400.

  In the method of the present invention, a foaming agent can be used if necessary. As the blowing agent, low-boiling hydrocarbons, water, or both are used. The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of 0 to 50 ° C., and specifically, propane, butane, pentane, cyclopentane, or a mixture thereof is exemplified. When using low-boiling point hydrocarbons and water together, the amount of water is not particularly limited because it is used by appropriately changing according to the desired foam density and the amount of low-boiling point hydrocarbons. 0.5 parts by weight or more with respect to 100 parts by weight of polyol, and particularly when it is desired to reduce the amount of low-boiling hydrocarbons from the viewpoint of cost, 0.8 parts by weight or more is preferably used.

  In the method of the present invention, if necessary, a foam stabilizer can be used. As the foam stabilizer, for example, nonionic surfactants such as organopolysiloxane-polyoxyalkylene copolymer and silicone-glycol copolymer, or mixtures thereof are used. The amount of the foam stabilizer is not particularly limited, but is usually in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyol.

  Moreover, if necessary, a crosslinking agent or chain extender, a colorant, a flame retardant, an anti-aging agent and other known additives can be added.

  In the method of the present invention, for example, a polyurethane resin is prepared by mixing two liquids of a polyol premix containing a catalyst, a foaming agent, a foam stabilizer and the like and a polyisocyanate using a low pressure foaming machine, a high pressure foaming machine, and a spray machine. Can be manufactured.

Rigid polyurethane foam obtained by the process of the present invention, which is suitably used as a heat insulating material, the density is usually 0.1 g / cm ³ or less, preferably 0.05 g / cm ³ or less.

In the present invention, the rigid polyurethane foam refers to a foam having a highly crosslinked closed cell structure and cannot be reversibly deformed [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany) , P. 234-313, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 224-283]. The physical properties are not particularly limited, but generally, the density is in the range of 10 to 100 kg / m ³ and the compressive strength is in the range of 50 to 1000 kPa.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is limited to only these Examples and is not interpreted.

  An example in which the catalyst composition of the present invention and a conventional amine catalyst are used in the production of a rigid polyurethane foam product is shown below.

Examples 1-11, Comparative Examples 1-15.
A rigid polyurethane foam was prepared by changing the catalyst and blending the polyol and polyisocyanate shown in Table 1 (isocyanate index = 110).

硬質ポリウレタンフォームの反応性（クリームタイム、ゲルタイム）を２Ｌポリエチレンカップで、アルミニウム製モールドを用いて発泡したフォームは物性［密度、熱伝導率（Ｋ−ｆａｃｔｏｒ）、フォームの平均セル面積］を測定及び評価した。その評価結果を表２〜表４に併せて示す。

The foam foamed with a 2L polyethylene cup and an aluminum mold was used to measure the physical properties [density, thermal conductivity (K-factor), average cell area of the foam] and the reactivity (cream time, gel time) of the rigid polyurethane foam. evaluated. The evaluation results are also shown in Tables 2 to 4.

ここで、硬質ポリウレタンフォームは以下の発泡条件で調製した。

Here, the rigid polyurethane foam was prepared under the following foaming conditions.

<Foaming conditions>
Raw material temperature: 20 ± 1 ° C
Stirring speed: 6000 rpm (5 seconds),
Mold: 2L polyethylene cup, foam in aluminum mold (dimensions: 25 x 25 x 5 cm),
Mold temperature: 40 ° C.

  In addition, the following items were measured.

<Measurement item>
・ Reactivity.
Cream time: Forming start time (seconds), and the time for foam to start rising was measured visually.

  Gel time: The time (seconds) during which the forming state changed to a resinous composition was measured. The gel time is a visual judgment, and when an operation of pushing a rod-like object (match bar) into the foam being formed by about several millimeters and drawing it out is repeated, a stringing phenomenon occurs when the resin-like composition is changed. This time is defined as gel time.

• Foam density.
A free rise foam was produced with an aluminum mold, the portion protruding from the mold was cut, and the total density of a 25 × 25 × 8 cm sample was measured. Furthermore, using the foam whose total density was measured, the core density was measured with a foam sample of 20 × 20 × 3 cm in which the skin portion was cut.

-Form K-factor.
K-factor was measured for the foam (20 × 20 × 3 cm) whose core density was measured by using a thermal conductivity measuring device (HC-074 manufactured by Eihiro Seiki).

• Average cell area of the foam.
A 5 × 5 × 1 cm size foam was cut from the center of the foam where the K-factor was measured, and a cell measuring device [Goldluce (Germany), product name: PORE! The average cell area was measured using SCAN.

  As is apparent from these tables, Examples 1 to 8 are dimethylcyclohexylamine and N, N, N ′, N ″, N ″ − which are generally used for molding a rigid polyurethane foam as a main catalyst. It can be seen that the use of the amine catalyst composition of the present invention in the blend composition of pentamethyldiethylenetriamine delayed the cream time, and the formed rigid polyurethane foam had a small K-factor and excellent heat insulation.

  Examples 9 and 10 are examples in which the amine catalyst composition of the present invention was used alone, the cream time was delayed, and the formed rigid polyurethane foam had a small K-factor and excellent heat insulating properties. I understand.

  Example 11 is a mixture of dimethylcyclohexylamine and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, which is commonly used in molding rigid polyurethane foam as a main catalyst. This is an example in which a catalyst composition is used and a conventionally known tertiary amine is used in combination. It can be seen that the cream time is delayed and the formed rigid polyurethane foam has a small K-factor and excellent heat insulation.

  In any of these cases, it was confirmed that the average cell area value was small and the foam was fine-celled, and it was found that the amine catalyst composition of the present invention improved the heat insulating performance of the foam.

  On the other hand, Comparative Example 1 is a blend composition of dimethylcyclohexylamine and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, which forms a rigid polyurethane foam, but K-factor Is large and inferior in heat insulation.

  Comparative Examples 2 to 7 and Comparative Examples 9 to 11 are blends of dimethylcyclohexylamine and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, ethyleneamines, or primary And an amine compound having a secondary amino group, it can be seen that the K-factor is large and the heat insulation is poor.

  Comparative Example 8 is a blend composition of dimethylcyclohexylamine and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, which is part of the catalyst system of the present invention, N, N-dimethyl-1,3- Although the composition is a blend of propanediamine and the K-factor is smaller than the other comparative examples, the heat insulation performance shown in the examples cannot be obtained and it cannot be said that it is sufficient.

  Comparative Examples 12 to 14 are glycerin-based solvents that are components of the amine catalyst composition of the present invention in blend compositions of dimethylcyclohexylamine and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. This is an example of using together. Although the K-factor is smaller than the other comparative examples, the heat insulation performance shown in the examples cannot be obtained and it cannot be said that it is sufficient.

  Comparative Example 15 is an example in which a rigid polyurethane foam was formed using N, N-dimethyl-1,3-propanediamine, which is one component in the amine catalyst composition of the present invention, alone. Although K-factor is smaller than the other comparative examples, the heat insulating performance shown in the examples cannot be obtained and it cannot be said that it is sufficient.

  By using the amine catalyst composition of the present invention, it is possible to produce a rigid polyurethane foam having a fine cell structure and low thermal conductivity, that is, high heat insulation performance. In addition, according to the production method of the present invention, the catalyst of the present invention is particularly hard polyurethane because it is not corrosive and does not impair polyurethane production equipment such as catalyst storage tanks and foaming devices, and can produce rigid polyurethane foam. Use as a catalyst for foam production is expected.

Claims (3)

A polyol and an organic polyisocyanate, a process for the preparation of the catalyst and rigid polyurethane foams are reacted in the presence of a blowing agent, as a catalyst, the following formula (1)

[In the above formula (1), R ₁ represents an ethylene group or a linear or branched alkylene group having 3 to 12 carbon atoms. ]
And an amine catalyst composition for producing a polyurethane resin containing one or two or more compounds selected from the group consisting of glycerin, diglycerin, and triglycerin , and a foaming agent , Water, a hydrocarbon having a boiling point in the range of 0 to 50 ° C., or both, and a method for producing a rigid polyurethane foam. The usage-amount of an amine catalyst composition is the range of 0.1-10 weight part as a usage-amount of the compound shown by Formula (1) of Claim 1 with respect to 100 weight part of polyols. The manufacturing method of the rigid polyurethane foam of Claim 1. The hard compound according to claim 1, wherein the content of the amine compound represented by the formula (1) according to claim 1 is in the range of 2 to 85% by weight with respect to the whole amine catalyst composition. A method for producing polyurethane foam.