JP2013133393A - Raw material compounding composition for manufacturing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a raw material compounding composition for manufacturing a hard polyurethane foam having high storage stability.SOLUTION: The raw material compounding composition for manufacturing the hard polyurethane foam contains polyester polyol, water and an amine compound expressed by general formula (1) is used, [wherein each of R-Rindependently expresses methyl group or ethyl group; and n express an integer of 8-18].

Description

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

  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, for example, 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.

JP 2008-291260 A

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

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly been able to use the aromatic polyester polyol, water, and a specific amine compound in combination to achieve storage stability of the raw material composition. Has been found to be improved, and 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, water, and an amine compound 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 8 to 18. ]
[2] The amine compound represented by the general formula (1) is 1,8-bis (dimethylamino) octane, 1,9-bis (dimethylamino) nonane, 1,10-bis (dimethylamino) decane, 11-bis (dimethylamino) undecane, 1,12-bis (dimethylamino) dodecane, 1,13-bis (dimethylamino) tridecane, 1,14-bis (dimethylamino) tetradecane, 1,15-bis (dimethylamino) ) One or more amines selected from the group consisting of pentadecane, 1,16-bis (dimethylamino) hexadecane, 1,17-bis (dimethylamino) heptadecane, and 1,18-bis (dimethylamino) octadecane It is a compound, The raw material compounding composition as described in said [1] characterized by the above-mentioned.

  [3] The amine compound represented by the general formula (1) is 1,8-bis (dimethylamino) octane, 1,9-bis (dimethylamino) nonane, 1,10-bis (dimethylamino) decane, One selected from the group consisting of 12-bis (dimethylamino) dodecane, 1,14-bis (dimethylamino) tetradecane, 1,16-bis (dimethylamino) hexadecane, and 1,18-bis (dimethylamino) octadecane Or it is 2 or more types of amine compounds, The raw material compounding composition as described in said [1] characterized by the above-mentioned.

  [4] The above-mentioned [1], wherein the polyester polyol is in the range of 30 to 100 parts by weight and the water is in the range of 1 to 10 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. Thru | or the raw material compounding composition in any one of [3].

  [5] The raw material composition according to any one of [1] to [4], wherein the polyester polyol is an aromatic polyester polyol.

  [6] As the 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 according to [5], which is characterized by the above.

  [7] 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 [6], further comprising the above foaming agent.

  [8] 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, Propane, butane, pentane, cyclopentane, hexane, 1,1,1,3,3,3-hexafluorobut-2-ene (HFO-1366mzz), 1-chloro-3,3,3-trifluoropropene ( The raw material-blended composition according to any one of the above [1] to [6], further comprising one or more selected from the group consisting of HCFO-1233zd) and carbon dioxide.

  [9] A method for producing a rigid polyurethane foam, comprising mixing and reacting a polyisocyanate with the raw material blend composition according to any one of [1] to [8].

  [10] A flame retardant rigid polyurethane foam comprising the raw material-blended composition according to any one of [1] to [8].

  It is known that tetramethylalkylene diamine having an alkylene chain length of 10 to 15 is used as a catalyst for flexible and rigid polyurethane foams (see, for example, US Pat. No. 5,591,781). About the influence which diamine has on the hydrolysis of polyester polyol, it is not disclosed at all in the specification, and the present inventors have found for the first time.

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

  Moreover, since the raw material composition of the present invention has reduced storage stability problems, it is possible to increase the aromatic polyester polyol content in the raw material composition.

  Furthermore, 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.

  The raw material blend composition for producing the rigid polyurethane foam of the present invention contains an aromatic polyester polyol, water, and an amine compound represented by the above general formula (1). When producing a rigid polyurethane foam, the polyester polyol functions as all or part of the polyol, water functions as a foaming agent, and the amine compound represented by the general formula (1) functions as a catalyst.

  Although it does not specifically limit as polyester polyol, For example, what is obtained from reaction of a dibasic acid and a hydroxy compound (glycol etc.), a dimethyl terephthalate (DMT) residue, phthalic anhydride is used as a starting material. Polyester polyol, nylon waste, trimethylolpropane (TMP), pentaerythritol waste, phthalic polyester waste, polyester polyol derived from processing waste, etc. [For example, Keiji Iwata "Polyurethane resin Handbook "(1987 first edition) Nikkan Kogyo Shimbun, p. 116-117].

  In addition to the above-mentioned polyester polyols, those obtained by esterifying an aromatic dicarboxylic acid or a derivative thereof from phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or wastes and wastes thereof Can be illustrated.

  As the starting material for the polyester polyol component, dimethyl terephthalate residue, phthalic anhydride, and phthalic polyester waste 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.

  The raw material blend composition of the present invention may contain a polyol other than the polyester polyol. Examples of polyols other than polyester polyols include conventionally known phenolic polyols such as 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. By setting the content of the aromatic polyester polyol to 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 polyether polyol, the content thereof is preferably 70 parts by weight or less, more preferably 20 to 50 parts per 100 parts by weight in total of all polyol components contained in the raw material blend composition of the present invention. The range is parts by weight.

  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.

  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 represented by the general formula (1) is not particularly limited, but specifically, 1,8-bis (dimethylamino) octane, 1,9 -Bis (dimethylamino) nonane, 1,10-bis (dimethylamino) decane, 1,11-bis (dimethylamino) undecane, 1,12-bis (dimethylamino) dodecane, 1,13-bis (dimethylamino) Tridecane, 1,14-bis (dimethylamino) tetradecane, 1,15-bis (dimethylamino) pentadecane, 1,16-bis (dimethylamino) hexadecane, 1,17-bis (dimethylamino) heptadecane, 1,18- Bis (dimethylamino) octadecane is exemplified, and one or more of these can be used in combination.

  The amine compound represented by the general formula (1) is, for example, a method in which a corresponding primary diamine is reacted with formaldehyde to reduce methylation, or a corresponding primary diol and dimethylamine are reacted to form dimethylamino. It is prepared by the method of

  The content of the amine compound represented by the general formula (1) in the raw material blend composition of the present invention is not particularly limited, but a total of 100 weights 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 with respect to a part. By setting the content of the amine compound represented by the general formula (1) to 0.5 parts by weight or more, the reaction rate between the raw material blend composition and the polyisocyanate is sufficiently high, and the productivity is improved. Even if it is used in excess of parts by weight, such an 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 amine compound represented by the above general formula (1) may be used in combination without departing from the effects of the present invention.

  Examples of the catalyst other than the amine compound represented by the general formula (1) 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 amine compound represented by the general formula (1), for example, a conventionally known isocyanurate-forming 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.

  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.

  When a catalyst other than the amine compound represented by the general formula (1) is used in combination, the amount used is not particularly limited, but a total of 100 weights of all polyol components contained in the raw material blend composition of the present invention. The range of 0.5 to 10 parts by weight with respect to parts is preferred, and the total amount of use with the amine compound represented by the general formula (1) is preferably in the range of 1 to 30 parts by weight.

  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 an isocyanate index (isocyanate group / active hydrogen group capable of reacting with isocyanate group × 100). When expressed, 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.

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 1,8-bis (dimethylamino) octane.
Synthetic zeolite is charged into a 1 liter flask, and an aqueous solution of copper nitrate, nickel nitrate and palladium chloride (at the molar ratio of each metal, Cu: Ni: Pd = 4: 1: 0.1) is added and the mixture is stirred up. Warm up. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 80 ° C. for 10 hours, and calcined at 400 ° C. for 3 hours. The amount of the obtained metal oxide supported on the carrier was 50%. Next, in a 1 liter flask equipped with a condenser and a separator, 60 g of 1,8-octanediol and 0.24 g of the above three-way catalyst (4% by weight of raw material diol) were charged, and 10 liters of hydrogen gas was added while stirring. The air was blown into the system at a flow rate of / Hr and the temperature was raised to 180 ° C. Next, a mixed gas of dimethylamine and hydrogen gas was introduced into the flask at a flow rate of 40 liters / hr. After reacting for 9 hours under reduced pressure, the three way catalyst was separated by filtration. By precision distillation, 1,8-bis (dimethylamino) octane was obtained with a yield of 70% and a purity of 98%.

Synthesis Example 2 Synthesis of 1,9-bis (dimethylamino) nonane.
1,9-bis (dimethylamino) nonane was obtained in the same manner as in Synthesis Example 1, except that 1,9-nonanediol was used instead of 1,8-octanediol.

Synthesis Example 3 Synthesis of 1,10-bis (dimethylamino) decane.
1,10-bis (dimethylamino) decane was obtained in the same manner as in Synthesis Example 1 except that 1,10-decanediol was used instead of 1,8-octanediol.

Synthesis Example 4 Synthesis of 1,12-bis (dimethylamino) dodecane.
1,12-bis (dimethylamino) dodecane was obtained in the same manner as in Synthesis Example 1 except that 1,12-dodecanediol was used instead of 1,8-octanediol.

Synthesis Example 5 Synthesis of 1,16-bis (dimethylamino) hexadecane.
1,16-bis (dimethylamino) hexadecane was obtained in the same manner as in Synthesis Example 1 except that 1,16-hexadecanediol was used instead of 1,8-octanediol.

Synthesis Example 6 Synthesis of 1,18-bis (dimethylamino) octadecane.
1,18-bis (dimethylamino) octadecane was obtained in the same manner as in Synthesis Example 1 except that 1,18-octadecanediol was used instead of 1,8-octanediol.

Example 1 to Example 10, Comparative Example 1 to Comparative Example 4.
A raw material compounded solution is prepared according to the formulation shown in Tables 1 and 2, and the weight ratio of the raw material compounded solution and the polyisocyanate is determined 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 2.

  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.

Example 1 to Example 9:
As is apparent from Table 2, Examples 1 to 9 using the raw material blend composition containing the amine compound represented by the above general formula (1) as the catalyst all have a gel time change rate of 100%. It was the following and was excellent in storage stability. Moreover, when the external appearance of the raw material compounding composition was visually confirmed, all were transparent and uniform, and the compatibility with other raw materials was good.

Example 10:
The composition of the raw material composition was 20 parts by weight of the aromatic polyester polyol, and the change rate of the gel time was small. However, the oxygen index of the obtained rigid polyurethane foam was less than 20%, and the flame retardancy was slightly low.

Comparative Example 1, Comparative Example 3 and Comparative Example 4:
As the catalyst, Comparative Example 1, Comparative Example 3 and Comparative Example 4 using the raw material blend composition not containing the amine compound represented by the general formula (1) described above all have a gel time change rate exceeding 100%. In addition, since the time required for the reaction curing is more than twice as long as that before storage, it cannot withstand practical use.

Comparative Example 2:
In Comparative Example 2 using a raw material blend composition containing N, N-dimethylhexadecylamine (a compound corresponding to a dialkyl (aliphatic alkyl) tertiary amine described in Patent Document 1) as a catalyst, the rate of change in gel time Was 100% or less, and although the storage stability was excellent, the amount of the catalyst used for obtaining the equivalent reactivity increased beyond both 20 parts. Moreover, when the external appearance of the raw material composition was confirmed by visual observation, clear turbidity occurred, and the compatibility between N, N-dimethylhexadecylamine and other raw materials was poor. Furthermore, the oxygen index of the obtained rigid polyurethane foam was less than 20%, and the flame retardancy was low.

Claims (10)

A raw material blend composition for producing a rigid polyurethane foam, comprising a polyester polyol, water, and an amine compound 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 8 to 18. ] The amine compound represented by the general formula (1) is 1,8-bis (dimethylamino) octane, 1,9-bis (dimethylamino) nonane, 1,10-bis (dimethylamino) decane, 1,11-bis. (Dimethylamino) undecane, 1,12-bis (dimethylamino) dodecane, 1,13-bis (dimethylamino) tridecane, 1,14-bis (dimethylamino) tetradecane, 1,15-bis (dimethylamino) pentadecane, It is one or two or more amine compounds selected from the group consisting of 1,16-bis (dimethylamino) hexadecane, 1,17-bis (dimethylamino) heptadecane, and 1,18-bis (dimethylamino) octadecane. The raw material-blended composition according to claim 1. The amine compound represented by the general formula (1) is 1,8-bis (dimethylamino) octane, 1,9-bis (dimethylamino) nonane, 1,10-bis (dimethylamino) decane, 1,12-bis. One or two selected from the group consisting of (dimethylamino) dodecane, 1,14-bis (dimethylamino) tetradecane, 1,16-bis (dimethylamino) hexadecane, and 1,18-bis (dimethylamino) octadecane It is the above amine compound, The raw material compounding composition of Claim 1 characterized by the above-mentioned. The polyester polyol is in the range of 30 to 100 parts by weight and the water is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the total polyol components contained in the raw material blend composition. The raw material compounding composition as described in 2. The raw material blend composition according to any one of claims 1 to 4, wherein the polyester polyol 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 5. 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 6, further comprising a foaming agent. 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 6, further comprising a foaming agent. A method for producing a rigid polyurethane foam, comprising mixing a polyisocyanate with the raw material-blended composition according to any one of claims 1 to 8 and reacting it. A rigid polyurethane foam containing the raw material-blended composition according to any one of claims 1 to 8.