JP2013151635A - Raw material blending composition for manufacturing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a raw material blending composition for manufacturing a hard polyurethane foam having a high storage stability.SOLUTION: As a raw material blending composition for manufacturing a hard polyurethane foam, there is used a composition containing an aromatic polyester polyol, water and an amine compound represented by formula (1) (wherein Rto Rare each independently a methyl group or an ethyl group; and n is an integer of 2 to 6).

Description

  The present invention relates to a raw material-blended composition containing a polyol, water and a catalyst used when producing a rigid polyurethane foam, and a catalyst used therefor.

  Rigid polyurethane foam is widely used as a heat insulating material for electric refrigerators, building materials and the like because it has excellent heat insulating properties and self-adhesive properties. The rigid polyurethane foam used for these applications is generally obtained by a method in which a raw material blended composition in which a polyol, a foaming agent, a catalyst and other auxiliary agents are mixed and a polyisocyanate are mixed and subjected to a foaming reaction.

  In recent years, as a foaming agent for rigid polyurethane foam, it has been intended to use water instead of hydrofluorocarbon (HFC) having a low ozone depletion coefficient and low boiling point hydrocarbon (HC) having a low ozone depletion coefficient. . When water is used as the foaming agent, carbon dioxide gas generated by the reaction between water and the polyisocyanate component is used as the foaming component.

  However, several technical problems arise when using water as a blowing agent.

  For example, when a polyester polyol is used as a polyol in a raw material blend composition containing a polyol, water and a catalyst, hydrolysis tends to occur in the presence of water and a catalyst, and the storage stability of the raw material blend composition deteriorates. There was a problem that a normal foam product could not be made.

  The raw material blend composition for producing rigid polyurethane foam is often stored for a period of several weeks to six months from blending until actual use. Therefore, the storage stability of the raw material blend composition is extremely important.

  In an isocyanate-reactive composition containing a polyester polyol, water, and a urethane catalyst composition, a composition containing at least one compound that is a dialkyl (aliphatic alkyl) tertiary amine is used as the urethane catalyst composition. It is known that the hydrolysis of polyester polyol is reduced in the isocyanate-reactive composition (see Patent Document 1).

  However, even when the urethane catalyst composition disclosed in Patent Document 1 is used, the storage stability of the raw material-blended composition containing water is still not sufficient in consideration of the 6-month storage period described above.

  It is known that the ratio of bis (3-dimethylaminopropyl) urea and 3-dimethylaminopropylurea is adjusted and used as a catalyst in order to improve the processability of rigid polyurethane foam (for example, Patent Document 2). reference).

JP 2008-291260 A JP 2001-31734 A

  This invention is made | formed in view of said subject, The objective is to provide the raw material compounding composition with high storage stability for rigid polyurethane foam manufacture.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly improved the storage stability of the raw material composition by using a combination of polyester polyol, water and a specific amine compound. As a result, the present invention has been completed.

  That is, the present invention is a raw material blend composition for producing rigid polyurethane foam as shown below.

  [1] A raw material blend composition for producing a rigid polyurethane foam comprising a polyester polyol (A), water (B), and an amine compound (C) represented by the following general formula (1).

[Wherein, R _{1 to} R ₄ each independently represents a methyl group or an ethyl group, and n represents an integer of 2 to 6. ]
[2] The amine compound (C) represented by the general formula (1) is N, N′-bis [3- (dimethylamino) propyl] urea, N, N′-bis [3- (diethylamino) propyl]. It should be one or more selected from the group consisting of urea, N, N′-bis [3- (dimethylamino) ethyl] urea, and N, N′-bis [3- (diethylamino) ethyl] urea The raw material-blended composition as described in [1] above.

  [3] The polyester polyol is contained in a range of 30 to 100 parts by weight and water is contained in a range of 1 to 10 parts by weight with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition. The raw material-blended composition according to [1] or [2].

  [4] The raw material blend composition according to any one of [1] to [3], wherein the polyester polyol (A) is an aromatic polyester polyol.

  [5] As an aromatic polyester polyol, containing a polyester polyol starting from one or more selected from the group consisting of dimethyl terephthalate residue, phthalic anhydride, and wastes of phthalic polyester The raw material-blended composition as described in [4] above, which is characterized by the following.

  [6] One or two selected from the group consisting of hydrofluorocarbon (HFC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrocarbon (HC), and carbon dioxide as a foaming agent other than water The raw material-blended composition according to any one of the above [1] to [5], further comprising the above foaming agent.

  [7] As a foaming agent other than water, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,4,4,4-hexafluorobutane, The raw material according to any one of [1] to [5], further comprising one or more blowing agents selected from the group consisting of propane, butane, pentane, cyclopentane, and hexane Formulation composition.

  [8] The above [1] to [7], further comprising a tertiary amine compound (D) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more. The raw material compounding composition according to any one of the above.

  [9] The tertiary amine compound (D) is triethylamine, N, N, N ′, N ′, N ″, N ″ -hexamethyl- (4-aminomethyl) octane-1,8-diamine, bis ( N, N-dimethylaminoethylpiperazinyl) ethane, N, N ′, N′-trimethyl-N ′-(2-methoxyethyl) ethylenediamine, N, N, N ′, N ″ -tetramethyl-N ′ '-(2-hydroxyl) ethyltriethylenediamine, bisdimethylaminoethyl ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N-dimethylaminoethoxyethanol, N , N, N′-trimethylaminoethylethanolamine, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methyl Minoisopropanol, and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N- (3-aminopropyl) -N, N ′, N′-trimethyl- It should be one or more selected from the group consisting of [2,2′-oxybis (ethanamine)] and 1,3,6,9-tetramethyl-3,6,9-triaza-1-decanol. The raw material-blended composition as described in [8] above.

  [10] The mixing ratio of the amine compound (C) represented by the general formula (1) and the tertiary amine compound (D) is [amine compound (C)] / [tertiary amine compound (D )] = 1/30 to 30/1 (weight ratio) The raw material-blended composition as described in [8] or [9] above.

  [11] A method for producing a rigid polyurethane foam, comprising reacting the raw material blend composition according to any one of [1] to [10] above with a polyisocyanate.

  [12] A rigid polyurethane foam containing the raw material blend composition according to any one of [1] to [10].

[13] A rigid polyurethane foam having a core density of 8 to 80 kg / m ³ obtained by the production method according to [11] above.

  [14] An amine compound (C) represented by the following general formula (1) and a tertiary amine compound (D) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more: A catalyst composition for producing rigid polyurethane foam.

[Wherein, R _{1 to} R ₄ each independently represents a methyl group or an ethyl group, and n represents an integer of 2 to 6. ]

  The present invention has the following effects.

  The raw material-blended composition of the present invention can suppress the hydrolysis of the polyester polyol and enhance the storage stability of the raw material-blended composition.

  Since the raw material composition of the present invention has reduced storage stability problems, the polyester polyol content in the raw material composition can be increased.

  In the raw material blend composition of the present invention, by using an aromatic polyester polyol as the polyester polyol, a rigid urethane foam having further excellent flame retardancy can be produced.

  In the raw material blend composition of the present invention, by using the tertiary amine compound (D) as a catalyst other than the amine compound (C), the reactivity is further increased and the productivity of urethane foam is improved. Can do.

  Since the catalyst composition of the present invention contains the amine compound (C) and the tertiary amine compound (D), it has high reactivity and can improve the productivity of urethane foam, and polyester. The storage stability of the raw material blend composition containing a polyol can be improved.

  The raw material blend composition for producing the rigid polyurethane foam of the present invention contains a polyester polyol (A) as a polyol, water (B) as a foaming agent, and an amine compound (C) represented by the above general formula (1) as a catalyst. The feature is to do.

  Although it does not specifically limit as polyester polyol, For example, what is obtained from reaction of a dibasic acid and hydroxy compounds (glycol etc.), Keiji Iwata "Polyurethane resin handbook" (1987 first edition) Nikkan Kogyo Shimbun p. . 116-117, dimethyl terephthalate (DMT) residue, polyester polyol starting from phthalic anhydride, waste from the production of nylon, trimethylolpropane (TMP), pentaerythritol waste, phthalic acid And polyester polyols obtained by treating and inducing wastes of polyesters.

  In addition to the above, examples of the polyester polyol include those obtained by esterifying an aromatic dicarboxylic acid or a derivative thereof from phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, wastes thereof, or waste products.

  As starting materials for polyester polyols, dimethyl terephthalate residue, phthalic anhydride, and phthalic polyester wastes are particularly preferred because they are easily available industrially.

  Examples of the hydroxy compound forming the polyester polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, phenol, and the like. And derivatives thereof.

  In the present invention, the preferred hydroxyl value of the polyester polyol is in the range of 150 to 450.

  In the raw material blend composition of the present invention, the flame resistance of the resulting rigid polyurethane foam is significantly improved by using an aromatic polyester polyol instead of the aliphatic polyester polyol as the polyester polyol.

  In the raw material blend composition of the present invention, a polyol other than the polyester polyol may be used in combination as the polyol. Examples of polyols other than polyester polyols include phenolic polyols such as conventionally known Mannich base polyols, polyether polyols, flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols, and polymer polyols.

  The content of the polyester polyol in the raw material blend composition of the present invention is not particularly limited, but is preferably 20 to 100 with respect to a total of 100 parts by weight of all the polyol components contained in the raw material blend composition of the present invention. It is the range of a weight part, More preferably, it is the range of 30-100 weight part. For example, when the content of the aromatic polyester polyol is 20 parts by weight or more, the flame resistance of the obtained rigid polyurethane foam is sufficiently high.

  As a phenolic polyol such as Mannich base polyol, for example, a polyether polyol obtained by Mannich modification of phenol, a derivative thereof, or both of them (hereinafter referred to as “Mannich modified polyol”) may be used. good. Specifically, the Mannich-modified polyol is a phenol derivative such as phenol, nonylphenol, alkylphenol, etc., modified with Mannich using formaldehyde, secondary amine such as diethanolamine, ammonia, primary amine, etc., and then ethylene oxide, It can be obtained by ring-opening addition polymerization of alkylene oxide such as propylene oxide. Such Mannich-modified polyols have a high self-reactive activity and a relatively high flame retardancy, and therefore, in spray foamed rigid polyurethane foams, the reaction can proceed promptly without significantly impairing the flame retardant performance during spray foaming. Can do.

  However, if the content of Mannich-modified polyol exceeds 70 parts by weight with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition of the present invention, flame retardancy may be deteriorated. Therefore, when using a Mannich modified polyol, the content thereof is preferably 70 parts by weight or less, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of all polyol components in the raw material blend composition of the present invention. Part range.

  As the polyether polyol, for example, ring opening addition polymerization of alkylene oxide such as ethylene oxide and propylene oxide with an initiator different from Mannich modified polyol such as ethylenediamine, tolylenediamine, sucrose, amino alcohol, diethylene glycol and the like. A polyether polyol compound obtained in this manner may be used.

  However, if the content of the polyether polyol exceeds 70 parts by weight with respect to a total of 100 parts by weight of all the polyol components contained in the raw material blend composition of the present invention, flame retardancy may be deteriorated. Therefore, when using a polyether polyol, the content thereof is preferably 70 parts by weight or less, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of all polyol components contained in the raw material blend composition of the present invention. Part range.

  Examples of flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols include phosphorus-containing polyols obtained by adding alkylene oxide to phosphoric acid compounds, ring-containing polymerization obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide. Examples include halogen polyols, halogenated polyols such as brominated pentaerythritol / sucrose polyols, tetrabromophthalic acid polyesters, and phenol polyols such as Mannich base polyols.

  However, if the content of the above-mentioned flame retardant polyol or the like exceeds 70 parts by weight with respect to a total of 100 parts by weight of all the polyol components contained in the raw material blend composition of the present invention, the amount of smoke generated during combustion increases, There is a risk that flame retardancy will deteriorate. Therefore, when using the above-described flame retardant polyol, the content thereof is preferably 70 parts by weight or less, more preferably 20 parts by weight, based on 100 parts by weight of all polyol components in the raw material blend composition of the present invention. It is in the range of ˜50 parts by weight.

  The foaming agent used in the raw material blend composition of the present invention is water (B).

  The water content in the raw material blend composition of the present invention is not particularly limited, but is preferably 1 to 30 weights with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition of the present invention. Part range, more preferably 1 to 10 parts by weight. By setting the water content to 1 part by weight or more, the density of the obtained rigid polyurethane foam is sufficiently low. In addition, by setting the water content to 30 parts by weight or less, the foam during foaming maintains the stability of the foam, and so-called deformation or collapse in which the foam collapses can be suppressed.

  In the raw material blend composition of the present invention, a foaming agent other than water may be used in combination as the foaming agent. Preferred examples of the foaming agent other than water include hydrofluorocarbon (HFC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrocarbon (HC), and carbon dioxide.

  Examples of the HFC include 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1, 1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,4,4,4-hexafluorobutane, etc. It is preferable to use one or more selected from the group consisting of these. Of these, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2-tetrafluoroethane is particularly preferred.

  Examples of HFO include 3,3,3-trifluoropropene (HFO-1234zf), E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze), Z-1,3,3, 3-tetrafluoropropene (Z-HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2,3,3-pentafluoropropene (E-HFO-1255ye) Z-1,2,3,3,3-pentafluoropropene (Z-HFO-125ye), E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO- 1336mzz), Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z-HFO-1336mzz), 1,1,1,4,4,5,5,5-octafluoro Penta - ene (HFO-1438mzz), and the like, it is preferable to use one or more selected from the group consisting. Of these, 1,1,1,3,3,3-hexafluorobut-2-ene is particularly preferred.

  Examples of HCFO include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), its trans isomer, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichloro -Propylene fluoride etc. are mentioned, It is preferable to use 1 type, or 2 or more types chosen from the group which consists of these. Of these, 1-chloro-3,3,3-trifluoropropene is particularly preferred.

  As HC, it is preferable to use a hydrocarbon having a boiling point of −30 to 70 ° C. Specific examples thereof include propane, butane, pentane, cyclopentane, hexane and the like, and it is preferable to use one or more selected from the group consisting of these.

  In the present invention, when a foaming agent other than water, such as HFC, HFO, HCFO, and HC, is used in combination, the total amount of the foaming agent other than water is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the polyol component. And more preferably in the range of 2 to 30 parts by weight.

  In the raw material blend composition of the present invention, the amine compound (C) represented by the general formula (1) is not particularly limited, but specifically, N, N′-bis [3- (dimethyl) Amino) ethyl] urea, N, N′-bis [3- (diethylamino) ethyl] urea, N, N′-bis [3- (dimethylamino) propyl] urea, N, N′-bis [3- (diethylamino) ) Propyl] urea, N, N′-bis [3- (dimethylamino) butyl] urea, N, N′-bis [3- (diethylamino) butyl] urea, N, N′-bis [3- (dimethylamino) ) Pentyl] urea, N, N′-bis [3- (diethylamino) pentyl] urea, N, N′-bis [3- (dimethylamino) hexyl] urea, N, N′-bis [3- (diethylamino) Hexyl] urea, etc. It can be used in combination of two or more thereof.

  The above-described amine compound (C), for example, reacts urea with the corresponding amine at an appropriate molar ratio at a temperature of 80 to 150 ° C., preferably 100 to 130 ° C., under an inert atmosphere to remove ammonia. It is prepared by.

  The content of the above-described amine compound (C) in the raw material blend composition of the present invention is not particularly limited, but with respect to a total of 100 parts by weight of all the polyol components contained in the raw material blend composition of the present invention, Preferably it is the range of 0.5-20 weight part. By making the content of the amine compound (C) 0.5 parts by weight or more, the reaction rate between the raw material blended composition and the polyisocyanate is sufficiently increased, and the productivity is improved. However, it exceeds 20 parts by weight. Even if it is used, the improvement effect is not seen, and the amount of catalyst used increases, which is economically disadvantageous.

  In the raw material blend composition of the present invention, a catalyst other than the above-described amine compound (C) may be used in combination without departing from the effects of the present invention.

  Examples of the catalyst other than the amine compound (C) described above include conventionally known tertiary amines.

  Conventionally known tertiary amines are not particularly limited, and examples thereof include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] Undecene-7, N, N′-dimethylpiperazine, bis (2-dimethylaminoethyl) ether, tris (dimethylaminopropyl) amine, 1 Dimethylaminopropyl imidazole, dimethyl dodecylamine, tertiary amine compounds such as dimethyl oleyl amine.

  In addition, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-, which has high catalytic activity and isocyanate trimerization (hereinafter referred to as “isocyanurate conversion”) activity, and can reduce the total amount of catalyst used. S-triazine, 2,4,6-tris (dimethylaminomethyl) phenol and the like can also be used.

  Furthermore, as a catalyst other than the above-described amine compound (C), for example, a conventionally known isocyanuration catalyst or the like can be used. Although it does not specifically limit as a conventionally well-known isocyanurate formation catalyst, In addition to the above-mentioned tertiary amines, quaternary ammonium salts, etc., organometallic catalysts, quaternary ammonium salts, tertiary phosphine In particular, phosphorus onium salt compounds can be used.

  Examples of such quaternary ammonium salts include, but are not limited to, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and tetramethyl. Examples include tetraalkylammonium organic acid salts such as ammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In addition, the organometallic catalyst is not particularly limited. For example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin Examples include dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.

  Although it does not specifically limit as carboxylic acid metal salt, For example, the alkali metal salt and alkaline-earth metal salt of carboxylic acid are mentioned. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  When using a catalyst other than the amine compound (C) described above, the amount used is not particularly limited, but with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition of the present invention, A range of 0.5 to 10 parts by weight is preferred. Moreover, as a total usage-amount with above-described amine compound (C), it is preferable to set it as the range of 1-30 weight part.

  In the raw material blend composition of the present invention, as a catalyst other than the above-described amine compound (C), the value of [foaming reaction rate constant / resinization reaction rate constant] is 0.5 or more in consideration of reactivity. It is particularly preferable to use a tertiary amine compound (D).

  In the present invention, the resinification reaction rate constant (k1w) is a parameter calculated by the following method.

  That is, toluene diisocyanate and diethylene glycol are charged so that the molar ratio of isocyanate group / hydroxyl group is 1.0, a certain amount of a tertiary amine compound is added as a catalyst, and the reaction is carried out at a constant temperature in a benzene solvent. The amount of unreacted isocyanate is measured. Here, assuming that the reaction between toluene diisocyanate and diethylene glycol is first-order at each concentration, the following equation holds.

dx / dt = k (ax) ² (2)
[In the above formula (2), x: concentration of reacted NCO group (mol / L), a: initial concentration of NCO group (mol / L), k: reaction rate constant (L / mol · h), t: Reaction time (h)].

  Substituting the initial conditions t = 0 and X = 0 into the above equation (2) and integrating, the following equation is established.

1 / (ax) = kt + 1 / a (3)
k = ko + KcC (4)
[In the above formula (4), ko: catalyst-free reaction rate constant (L / mol · h), Kc: catalyst constant (L ² / g · mol · h), C: catalyst concentration in the reaction system (mol / L ]].

  The reaction rate constant k is obtained from the above equation (3), and is substituted into the following equation (4) to obtain the catalyst constant Kc.

The obtained catalyst constant Kc is divided by the molecular weight of the catalyst to obtain a resination reaction rate constant k1w (L ² / g · mol · h) that can be regarded as an activity capacity per weight (see the following formula).

Kc / mc = k1w (5)
On the other hand, the foaming reaction constant (k2w) is obtained in the same manner as described above by reacting toluene diisocyanate and water in a benzene solvent under the same conditions as in the above-mentioned resinification reaction.

  Examples of the tertiary amine compound (D) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more include triethylamine, N, N, N ′, N ′, N ″, N ″ -hexamethyl- (4-aminomethyl) octane-1,8-diamine, bis (N, N-dimethylaminoethylpiperazinyl) ethane, N, N ′, N′-trimethyl-N ′-(2- Methoxyethyl) ethylenediamine, N, N, N ′, N ″ -tetramethyl-N ″-(2-hydroxyl) ethyltriethylenediamine, bisdimethylaminoethyl ether, N, N, N ′, N ″, N ″ -Pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N— (3-Aminopropyl) -N, N ′, N′-trimethyl- [2,2′-oxybis (ethanamine)] and 1,3,6,9-tetramethyl-3,6,9-triaza-1 -Decanol and the like are exemplified.

  The above-mentioned tertiary amine compound (D) can be easily produced by methods known in the literature. For example, a method by reaction of diol and diamine, amination of alcohol, a method by reductive methylation of monoamino alcohol or diamine, a method by reaction of amine compound and alkylene oxide, and the like can be mentioned.

  In the present invention, the mixing ratio of the above-described amine compound (C) and the above-described tertiary amine compound (D) is not particularly limited, but the above-described amine compound (C) and the above-described third compound are not limited. So that the weight ratio of the secondary amine compound (D) ([above amine compound (C)] / [above tertiary amine compound (D)]) is in the range of 1/30 to 30/1. The ratio is preferably adjusted, and more preferably in the range of 1/20 to 20/1. By setting the weight ratio within this range, satisfactory performance can be exhibited in terms of catalytic activity and physical properties of the polyurethane resin.

  In the raw material blend composition of the present invention, the amine compound (C) and the tertiary amine compound (D) described above may be added to the raw material blend composition prepared in advance, You may add each to a raw material composition simultaneously. Moreover, when mixing them, it can also be melt | dissolved and used for a solvent. Although it does not specifically limit as a solvent, For example, alcohol, such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, and 2-methyl-1,3-propanediol, toluene, xylene, mineral terpene, Hydrocarbons such as mineral spirits, esters such as ethyl acetate, butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide Examples include solvable organic solvents such as amides, β-diketones such as acetylacetone and fluorinated substituents thereof, chelating solvents such as ketoesters such as methyl acetoacetate and ethyl acetoacetate, and water. .

  In addition, the raw material compounding composition of the present invention does not need to contain a dialkyl (aliphatic alkyl) tertiary amine described in Patent Document 1 as a catalyst.

  Examples of such dialkyl (aliphatic alkyl) tertiary amines include dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethylcocoamine, dimethyloleylamine, and dimethylricino. Railamine, diethyldecylamine, diethyldodecylamine, diethyltetradecylamine, diethylhexadecylamine, diethyloctadecylamine, diethylcocoamine, diethyloleylamine, diethylricinoleylamine, dipropyldecylamine, dipropyldodecylamine, dipropyl Tetradecylamine, dipropylhexadecylamine, dipropyloctadecylamine, dipropylcocoamine, dipropyloleylamine, dipro Ricinoleate rail amine, dibutyl-decyl amine, dibutyl dodecylamine, di-butyl tetradecyl amine, dibutyl hexadecylamine, dibutyl octadecylamine, dibutyl cocoamine, dibutyl Luo rail amines and dibutyltin ricinoleate rail amine.

  The raw material-blended composition of the present invention may contain other auxiliary agents without departing from the spirit of the present invention. Examples of such auxiliaries include foam stabilizers, flame retardants, crosslinking agents, chain extenders and the like.

  In the present invention, if necessary, a surfactant can be used as a foam stabilizer. Examples of the surfactant used include organic silicone surfactants, and specifically, nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Or a mixture thereof. The amount used thereof is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight in total of all the polyol components contained in the raw material composition of the present invention.

  The raw material blend composition of the present invention may contain a flame retardant if necessary. Although the flame retardant used is not particularly limited, for example, a reactive flame retardant such as a phosphorus-containing polyol such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, Tertiary phosphate esters such as tricresyl phosphate, halogen-containing tertiary phosphate esters such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A And halogen-containing organic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The content varies depending on the required flame retardancy and is not particularly limited, but is 4 to 30 weights with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition of the present invention. A range of parts is preferred.

  In the present invention, if necessary, a crosslinking agent or a chain extender can be used. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylenebisorthochloroaniline.

  In the present invention, a colorant, an antiaging agent, and other conventionally known additives can be further used as necessary. The type and amount of these additives may be within the normal usage range of the additive used.

  The method for producing a rigid polyurethane foam of the present invention is characterized by reacting the above-described raw material blend composition of the present invention with a polyisocyanate.

  In the method of the present invention, the polyisocyanate is not particularly limited. For example, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate and tolylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hexamethylene One or more selected from aliphatic polyisocyanates such as diisocyanate can be used.

  In the method of the present invention, the mixing ratio of the polyol component and the polyisocyanate in the raw material composition is not particularly limited, but is isocyanate index [(isocyanate group / active hydrogen group capable of reacting with isocyanate group) × 100. ], It is preferably in the range of 70 to 500.

  When producing a rigid polyurethane foam using the raw material blend composition of the present invention, the above-mentioned raw material blend composition and polyisocyanate are rapidly mixed and stirred, and then injected into an appropriate container or mold for foam molding. Thus, the foam can be produced. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. Moreover, high pressure, low pressure, and a spray type apparatus can be used as a polyurethane foaming machine to blow and foam the target substrate.

  Moreover, when manufacturing a rigid polyurethane foam using the raw material compounding composition of this invention, you may use a foaming agent further. Examples of such a foaming agent include water and foaming agents other than the above-described water.

The rigid polyurethane foam of the present invention thus obtained preferably has a core density in the range of 8 to 80 kg / m ³ . When the core density exceeds 80 kg / m ³ , the combustion components increase, the flame retardancy deteriorates, and the cost increases. When the core density is less than 8 kg / m ³ , strength characteristics and the like are inferior.

In the present invention, the rigid polyurethane foam refers to Gunter Oertel, "Polyurethane Handbook" (1985 edition), Hanser Publishers (Germany), p. 234-313, Keiji Iwata, "Polyurethane resin handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. A foam having a highly crosslinked closed cell structure described in 224 to 283 and not reversibly deformable. The physical properties of the rigid urethane foam are not particularly limited, but are generally in the range of a density of 10 to 100 kg / m ³ and a compressive strength of 50 to 1000 kPa.

  The rigid urethane foam product manufactured using the raw material blend composition of the present invention can be used for various applications. For example, heat insulation and structural materials related to construction, civil engineering, electrical equipment related, heat insulating materials such as freezer, refrigerator, freezer showcase, etc., plant and ship related, LPG, LNG tanker and pipeline heat insulating materials, vehicle related Applications such as cold storage and heat insulation for refrigerated vehicles can be mentioned.

  Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. However, the present invention is not construed as being limited to these examples.

Synthesis Example 1 Synthesis of N, N′-bis [3- (dimethylamino) propyl] urea
In a 1 liter three-necked round bottom flask equipped with a reflux condenser, 60.1 g of urea (1.0 mol) and 306.5 g of N, N-dimethylaminopropylamine (3.0 mol) were placed in the flask. The mixture was slowly heated to 120 ° C. with constant stirring. The reaction was controlled at 120 ° C. for 1.5 hours, then the reaction temperature was increased to 140 ° C., 160 ° C. and finally 180 ° C. In each stage, the temperature was increased after the evolution of ammonia had ceased. Excess N, N-dimethylaminopropylamine was removed by distillation to obtain N, N′-bis [3- (dimethylamino) propyl] urea.

Synthesis Example 2 Synthesis of N, N′-bis [3- (diethylamino) propyl] urea
N, N′-bis [3- (diethylamino) propyl] urea was obtained in the same manner as in Synthesis Example 1 except that N, N-diethylaminopropylamine was used instead of N, N-dimethylaminopropylamine.

Synthesis Example 3 Synthesis of N, N′-bis [3- (diethylamino) ethyl] urea
N, N′-bis [3- (dimethyllamino) ethyl] urea was obtained in the same manner as in Synthesis Example 1 except that N, N-dimethylaminoethylamine was used instead of N, N-dimethylaminopropylamine. .

Synthesis Example 4 Synthesis of N- (3-aminopropyl) -N, N ′, N′-trimethyl- [2,2′-oxybis (ethanamine)].
A 2-liter stainless steel autoclave (hereinafter referred to as “reaction vessel 1”) was charged with 499 g of dimethylaminoethoxyethanol (3.8 mol) and 38 g of a copper / zinc oxide / alumina catalyst. After purging the reaction vessel 1 with nitrogen and hydrogen, the catalyst was reduced in the system over 9 hours under conditions of 5.6 MPa and 195 ° C. The reaction vessel 1 was cooled to 25 ° C. and depressurized to atmospheric pressure, and then 177 g of monomethylamine (5.7 mol) was injected using a nitrogen pressure of 0.7 MPa. Again, the pressure in the reaction vessel 1 was increased to 1.5 MPa with hydrogen, the temperature was raised to 195 ° C., and the temperature and pressure were maintained for 24 hours. The obtained reaction solution was completely removed from the low-boiling compound, the high-boiling compound and a very small amount of the components derived from the copper / zinc oxide / alumina catalyst by distillation. The main components of 326 g of the distilled product were N, N, N′-trimethylbis (aminoethyl) ether and dimethylaminoethoxyethanol.

  Next, 326 g of the distilled product was charged into a three-necked flask equipped with a refluxer, heated to 55 ° C., and 71 g of acrylonitrile (1.3 mol) was charged over 2 hours. By continuing the reaction for further 5 hours, unreacted N, N, N′-trimethylbis (aminoethyl) ether was reduced to 1% or less.

  Thereafter, 20 g of a chromium-promoted sponge nickel catalyst and 150 g of a 28% ammonium hydroxide aqueous solution were charged into a 1 liter stainless steel autoclave (hereinafter, reaction vessel 2). After purging the reaction vessel 2 with nitrogen and hydrogen, the temperature was raised to 90 ° C. and pressurized to 8.2 MPa with hydrogen. After supplying 326 g of the reaction solution obtained in the previous reaction to the reaction vessel 2 with a pump over 3.5 hours, the reaction was continued for another hour. After removing the catalyst by filtration, the obtained reaction solution was subjected to distillation under reduced pressure (top temperature: 124 to 133 ° C., degree of vacuum: 13 hPa) to obtain 140 g of N- (3-aminopropyl) -N, N ', N'-trimethyl- [2,2'-oxybis (ethanamine)] was obtained.

(Calculation of resinification reaction rate constant)
Reference Example 1
In a 200 ml Erlenmeyer flask purged with nitrogen, 50 ml of DEG-containing benzene solution prepared so that the concentration of diethylene glycol (DEG) is 0.15 mol / L is collected, and N, N, N ', N ", N" -60.7 mg (0.35 mmol) of pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, TOYOCAT-DT) was added to prepare Liquid A.
Next, 50 ml of a TDI-containing benzene solution prepared so that the concentration of 2,6-toluene diisocyanate (TDI) was 0.15 mol / L was collected in a 100 ml Erlenmeyer flask purged with nitrogen and used as solution B.

The liquid A and the liquid B were each kept at 30 ° C. for 30 minutes, and then the liquid B was added to the liquid A and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 10 minutes after the reaction starts, the unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is back titrated with 0.2 N hydrochloric acid ethanol solution. Thus, the amount of unreacted isocyanate was quantified.
As described above, the reaction rate constant k (L / mol · h) was determined on the assumption that the reaction between the isocyanate and alcohol (resinification reaction) was first-order at each concentration. Further, the rate constant Kc (L ² / eq · mol · h) per catalyst was obtained by dividing the reaction rate constant k by the catalyst concentration. Furthermore, the resination rate constant k1w (L ² / g · mol · h) that can be regarded as the activity capacity per weight was determined by dividing Kc by the molecular weight of the catalyst. The results are shown in Table 1.

Reference Examples 2 to 11
The resination reaction rate constant k1w was calculated in the same manner as in Reference Example 1 except that the tertiary amine compound shown in Table 1 was used as the catalyst. The results are shown in Table 1.

(Calculation of foaming reaction rate constant)
Reference Example 12.
In a 200 ml Erlenmeyer flask purged with nitrogen, 100 ml of a water-containing benzene solution prepared so that the concentration of water becomes 0.078 mol / L was collected, and this was collected with N, N, N ′, N ″, N ″ -pentamethyl. 60.7 mg (0.35 mmol) of diethylenetriamine (manufactured by Tosoh Corporation, TOYOCAT-DT) was added to prepare a solution A.

  Next, 10 ml of a TDI-containing benzene solution prepared so that the concentration of 2,6-toluene diisocyanate (TDI) was 0.78 mol / L was collected into a 100 ml Erlenmeyer flask purged with nitrogen, and used as solution B.

The liquid A and the liquid B were each kept at 30 ° C. for 30 minutes, and then the liquid B was added to the liquid A and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 10 minutes after the reaction starts, the unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is back titrated with 0.2 N hydrochloric acid ethanol solution. Thus, the amount of unreacted isocyanate was quantified.
As described above, the reaction rate constant k (L / mol · h) was determined on the assumption that the reaction between the isocyanate and water (foaming reaction) was first-order at each concentration. The rate constant Kc (L ² / eq · mol · h) per catalyst was determined by dividing the rate constant k by the catalyst concentration. Furthermore, k2w (L ² / g · mol · h) that can be regarded as the activity ability per weight was determined by dividing Kc by the molecular weight of the catalyst. The results are shown in Table 1.

Reference Example 13 to Reference Example 22.
The foaming reaction rate constant k2w was calculated in the same manner as in Reference Example 10 except that the tertiary amine compound shown in Table 1 was used as the catalyst. The results are shown in Table 1.

(Calculation of foaming / resinization activity ratio)
From the results in Table 1, the ratio of foaming / resinization activity of the tertiary amine compound (= [resinization reaction rate constant k1w / foaming reaction rate constant k2w]) was determined. The results are also shown in Table 2.

Example 1 to Example 8, Comparative Example 1 to Comparative Example 4.
A raw material mixture is prepared by mixing shown in Tables 3 and 4, and the weight ratio of this raw material mixture and polyisocyanate is determined so as to be a predetermined index, and 9000 rpm using a lab mixer at a liquid temperature of 20 ° C. The mixture was stirred for 2 seconds to cause a foaming reaction to produce a rigid polyurethane foam. The gel time at this time was measured and used as the gel time before the storage stability test.

  Next, after putting the raw material composition containing the amine compound in a sealed container and heating at 70 ° C. for 10 days, the gel time when the mixture is foamed by mixing with isocyanate at a liquid temperature of 20 ° C. is stored stably. The gel time after the sex test was taken. The results are shown in Table 4.

  In the following examples and comparative examples, the measurement methods of measurement items other than those described above are as follows.

・ Measurement items for reactivity.
Gel time: Measures the time required for the reaction to progress to a resinous substance from a liquid substance.

  Change rate of gel time: The change rate of gel time was determined by the following equation.

  Change rate of gel time = 100 × (gel time after storage stability test−gel time before storage stability test) ÷ (gel time before storage stability test).

-Flame retardant measurement item Oxygen index: The center part of the obtained rigid polyurethane foam was sampled and measured according to JIS K7201.

  As is apparent from Table 4, in Examples 1 to 7 using the above-described amine compound (C) as a catalyst, the change rate of the gel time was 100% or less.

  On the other hand, in Comparative Examples 1 to 4 which do not use the amine compound represented by the general formula (1) as a catalyst, the change rate of the gel time exceeds 100%, and is necessary for the reaction curing. Since it takes more than twice as long as before storage, it could not withstand actual use. The catalyst (N, N-dimethylhexadecylamine) used in Comparative Example 1 is a compound corresponding to the dialkyl (aliphatic alkyl) tertiary amine described in Patent Document 1.

  Example 8 was a composition that did not contain an aromatic polyester polyol as a polyol, and the rate of change in gel time was small, but the oxygen index of the resulting rigid polyurethane foam was less than 20%. That is, it is understood that flame retardancy is further improved when an aromatic polyester polyol is used.

Example 9 to Example 24, Comparative Example 5, Example 25 to Example 29.
Prepare the raw material compounded liquid by the composition shown in Table 5 and Table 6, determine the weight ratio of this raw material compounded liquid and polyisocyanate so as to be a predetermined index, and use a lab mixer at a liquid temperature of 20 ° C., 9000 rpm The mixture was stirred for 2 seconds to cause a foaming reaction to produce a rigid polyurethane foam. The gel time at this time was measured and used as the gel time before the storage stability test.

  Next, after putting the raw material composition containing the amine compound in a sealed container and heating at 70 ° C. for 10 days, the gel time when the mixture is foamed by mixing with isocyanate at a liquid temperature of 20 ° C. is stored stably. The gel time after the sex test was taken. The results are shown in Table 6.

  As apparent from Table 6, when the above-mentioned amine compound (C) and the above-mentioned tertiary amine compound (D) were combined as a catalyst (Examples 9 to 24), before the storage stability test The cream time was as fast as 15 seconds or less, and urethane foam could be produced with good productivity. Moreover, when the storage stability test was implemented, the change rate of gel time was 150% or less in any case.

  On the other hand, when the above-mentioned tertiary amine compound (D) is used alone without using the above-described amine compound (C) as a catalyst (Comparative Example 5), the rate of change in gel time after the storage stability test Was over 150% and could not withstand practical use.

  In addition, when the above-described amine compound (C) and an amine catalyst other than the above-described tertiary amine compound (D) are used in combination (Example 25 to Example 29), the rate of change in gel time is small. , Cream time is slower than 15 seconds. That is, it can be seen that when the above-described amine compound (C) and the above-mentioned tertiary amine compound (D) are used in combination, a foam can be obtained with higher productivity.

Claims (14)

A raw material blend composition for producing a rigid polyurethane foam comprising a polyester polyol (A), water (B), and an amine compound (C) represented by the following general formula (1).

[Wherein, R _{1 to} R ₄ each independently represents a methyl group or an ethyl group, and n represents an integer of 2 to 6. ] The amine compound (C) represented by the general formula (1) is N, N′-bis [3- (dimethylamino) propyl] urea, N, N′-bis [3- (diethylamino) propyl] urea, N, One or more selected from the group consisting of N′-bis [3- (dimethylamino) ethyl] urea and N, N′-bis [3- (diethylamino) ethyl] urea The raw material blend composition according to the above [1]. The polyester polyol is contained in a range of 30 to 100 parts by weight and water is contained in a range of 1 to 10 parts by weight with respect to a total of 100 parts by weight of all polyol components contained in the raw material blend composition. The raw material compound composition according to claim 2. The raw material blend composition according to any one of claims 1 to 3, wherein the polyester polyol (A) is an aromatic polyester polyol. The aromatic polyester polyol is characterized by containing a polyester polyol starting from one or more selected from the group consisting of dimethyl terephthalate residue, phthalic anhydride, and phthalic polyester wastes. The raw material composition according to claim 4. As a foaming agent other than water, one or more selected from the group consisting of hydrofluorocarbon (HFC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrocarbon (HC), and carbon dioxide gas The raw material blend composition according to any one of claims 1 to 5, further comprising a foaming agent. As foaming agents other than water, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1 , 1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,4,4,4-hexafluorobutane, propane, butane The raw material blend composition according to any one of claims 1 to 5, further comprising one or more foaming agents selected from the group consisting of styrene, pentane, cyclopentane, and hexane. Furthermore, the tertiary amine compound (D) whose value of [foaming reaction rate constant / resinization reaction rate constant] is 0.5 or more is contained. The raw material blend composition described. The tertiary amine compound (D) is triethylamine, N, N, N ′, N ′, N ″, N ″ -hexamethyl- (4-aminomethyl) octane-1,8-diamine, bis (N, N— Dimethylaminoethylpiperazinyl) ethane, N, N ′, N′-trimethyl-N ′-(2-methoxyethyl) ethylenediamine, N, N, N ′, N ″ -tetramethyl-N ″-(2 -Hydroxyl) ethyltriethylenediamine, bisdimethylaminoethyl ether, N, N, N ', N ", N" -pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N, N-dimethylaminoethoxyethanol, N, N, N '-Trimethylaminoethylethanolamine, N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoiso Lopanol, and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N- (3-aminopropyl) -N, N ′, N′-trimethyl- [ 2,2′-oxybis (ethanamine)] and 1,3,6,9-tetramethyl-3,6,9-triaza-1-decanol, or one or more selected from the group consisting of The raw material-blended composition according to claim 8, The mixing ratio of the amine compound (C) represented by the general formula (1) and the tertiary amine compound (D) is [amine compound (C)] / [tertiary amine compound (D)] = 1 / It is the range of 30-30 / 1 (weight ratio), The raw material compounding composition of Claim 8 or Claim 9 characterized by the above-mentioned. A method for producing a rigid polyurethane foam, comprising reacting the raw material-blended composition according to any one of claims 1 to 10 with a polyisocyanate. A rigid polyurethane foam containing the raw material-blended composition according to any one of claims 1 to 10. A rigid polyurethane foam having a core density in the range of 8 to 80 kg / m ³ obtained by the production method according to claim 11. Rigid polyurethane containing an amine compound (C) represented by the following general formula (1) and a tertiary amine compound (D) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 0.5 or more Catalyst composition for foam production.

[Wherein, R _{1 to} R ₄ each independently represents a methyl group or an ethyl group, and n represents an integer of 2 to 6. ]