Halogen-containing polyether ester polyol

Abstract

To provide a halogen-containing polyetherester polyol usable as a starting material for producing polyurethanes excellent in terms of mechanical property and flame retardancy.SOLUTION: The halogen-containing polyetherester polyol is represented by formula (1) and has a molecular weight of 500-3000. (In formula (1), R1 represents a polyester polyol residue having a molecular weight of 350-2500, excluding 2500, n is an integer of 1-25, excluding 25, m is 2 or 3, and X represents a halogen atom.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to halogen-containing polyether ester polyols that serve as raw materials for polyurethane, exhibiting excellent mechanical properties and flame retardancy, and having low levels of volatile components. [Background technology]

[0002] Polyether polyols can be obtained by ring-opening polymerization of alkylene oxides and are used as soft segments of polyurethane in a wide range of applications, including paints, adhesives, sealants, and foams for automotive seats.

[0003] Furthermore, halogen-containing polyether polyols are known as raw materials for polyurethane adhesives with excellent shear strength and flame retardancy (see, for example, Patent Document 1). Halogen-containing polyether polyols can be synthesized by ring-opening polymerization of halogen-containing alkylene oxides using an acid catalyst, such as a boron trifluoride compound. However, such halogen-containing polyether polyols contain many by-products, such as unsaturated components, generated by side reactions during production. As a result, the resulting polyurethane has many defects and a low crosslink density, leading to problems such as a decrease in physical properties like hysteresis loss and compressive residual strain.

[0004] As polymerization catalysts for alkylene oxides that yield polyols with a low degree of unsaturation, bimetallic cyanide complexes are known, and polymerization of halogen-containing alkylene oxides is also known (see, for example, Non-Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 202573 / 1999 [Non-patent literature]

[0006] [Non-Patent Document 1] RSC Advances, 2014, 4, 21765 - 2177

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, even if such a halogen - containing polyether polyol has a low degree of unsaturation and a small amount of impurities, due to its ether skeleton, when used as a raw material for polyurethane, it tends to form a soft resin, and further improvement in flame retardancy has been desired. Therefore, one aspect of the present invention is directed to providing a halogen - containing polyether ester polyol that serves as a raw material for producing polyurethane excellent in mechanical properties and flame retardancy.

Means for Solving the Problems

[0008] Each aspect of the present invention is as follows [1] to [6]. [1] A halogen - containing polyether ester polyol represented by the following formula (1) and having a molecular weight of 500 or more and 3,000 or less.

[0009]

Chemical Formula

[0010] (In the above formula (1), R ,

[0008] , , , <00000八十六>, , ,

[0010] , , , , ,

[0009] , , , , , represents a polyester polyol residue having a molecular weight of 350 or more and 2500 or less, n is an integer of 1 or more and less than 25, m is 2 or 3, and X represents a halogen atom.) [2] The halogen - containing polyether ester polyol according to [1], wherein X in the formula (1) is a chlorine atom. [3] A method for producing a halogen-containing polyether ester polyol, comprising ring-opening polymerization of an alkylene oxide in the presence of a composition comprising an onium salt, a Lewis acid, and a polyester polyol, wherein the amount of the onium salt used is in the range of 0.001 to 0.1 moles and the amount of the Lewis acid used is in the range of 0.002 to 0.2 moles per mole of hydroxyl groups of the polyester polyol, as described in [1] or [2]. [4] A flame retardant containing the halogen-containing polyether ester polyol described in [1] or [2]. [5] A polyurethane having a residue of the halogen-containing polyether ester polyol described in [1] or [2] in its molecular structure. [6] A polyurethane foam containing residues of the halogen-containing polyether polyol described in [1] or [2] in its molecular structure. [Effects of the Invention]

[0011] One embodiment of the present invention, a halogen-containing polyether ester polyol, serves as a raw material for polyurethane with excellent mechanical properties and flame retardancy.

[0012] Furthermore, the halogen-containing polyether ester polyol production method according to one aspect of the present invention allows for the efficient production of halogen-containing polyether ester polyols. [Modes for carrying out the invention]

[0013] The following describes in detail exemplary embodiments for carrying out the present invention.

[0014] <Halogen-containing polyether ester polyol> A halogen-containing polyether ester polyol according to one aspect of the present invention is represented by the above formula (1) and has a molecular weight of 500 or more and 3,000 or less.

[0015] In the above equation (1), R1 represents a polyester polyol residue with a molecular weight of 350 to 2500, n is an integer between 1 and 25, m is 2 or 3, and X represents a halogen atom.

[0016] R 1 The molecular weight of the polyester polyol containing the polyester polyol residue represented by is preferably between 350 and 2500, and is not particularly limited, but is preferably between 500 and 2000, and especially between 500 and 1500.

[0017] Polyester polyols are not particularly limited, but examples include those produced by esterifying an aromatic and / or aliphatic polybasic acid or acid anhydride with a compound having two or three hydroxyl groups (polyhydric alcohol) by a known method, or those produced by ring-opening polymerization of ε-caprolactone using a compound having two or three hydroxyl groups (polyhydric alcohol) as an initiator.

[0018] While not particularly limited, aromatic polybasic acids include orthophthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid. Due to the high versatility of the resulting polyester polyols, orthophthalic acid, isophthalic acid, or terephthalic acid are preferred.

[0019] While not particularly limited, aliphatic polybasic acids include succinic acid, glutaric acid, sebacic acid, and adipic acid. Due to the high versatility of the resulting polyester polyols, adipic acid, sebacic acid, or succinic acid are preferred.

[0020] Aromatic and / or aliphatic polybasic acids may be used individually or in combination of two or more types. Since the resulting polyurethane has high flame retardancy, it is preferable to use an aromatic polybasic acid alone or a combination of two or more aromatic and aliphatic polybasic acids.

[0021] Examples of acid anhydrides include, but are not limited to, maleic anhydride or phthalic anhydride.

[0022] Compounds having two or three hydroxyl groups (polyhydric alcohols) are not particularly limited, but include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, bis Examples include short-chain diols such as phenol A; and short-chain triols such as glycerin, hexanetriol, and trimethylolpropane. Due to the high versatility of the polyester polyols produced, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and 3-methyl-1,5-pentanediol are preferred, with 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and 3-methyl-1,5-pentanediol being particularly preferred. These can be used individually or in combination of two or more.

[0023] In formula (1) above, the halogen atom represented by X is not particularly limited, but examples include fluorine, chlorine, bromine, and iodine atoms. Of these, fluorine, chlorine, and bromine atoms are preferred due to their ease of handling, and bromine or chlorine atoms are particularly preferred. Each can be used alone or in combination of two or more types.

[0024] The degree of unsaturation of the halogen-containing polyether ester polyol according to one aspect of the present invention is not particularly limited, but is preferably 0.2 meq / g or less, and is particularly preferably 0.05 meq / g or less, as this improves the physical properties of the resulting polyurethane, such as hysteresis loss and compression residual strain.

[0025] In one aspect of the present invention, the Mw / Mn ratio of the halogen-containing polyether ester polyol is preferably 2.00 or less, and more preferably 1.80 or less, because it improves moldability when used as a polyurethane resin (wherein Mn is the number-average molecular weight and Mw is the weight-average molecular weight, determined by gel permittation chromatography using polystyrene as a standard substance).

[0026] A halogen-containing polyether ester polyol according to one aspect of the present invention is not particularly limited and can be produced by conventionally known production methods. For example, it can be obtained by ring-opening polymerization of a halogen-containing alkylene oxide using a polyester polyol as an initiator in the presence of a composition containing an onium salt, a Lewis acid, and a polyester polyol.

[0027] Examples of halogen-containing alkylene oxides include epichlorohydrin, epibromohydrin, and epifluorohydrin. Among these, epichlorohydrin is preferred because it is readily available and the resulting polyalkylene oxide has high industrial value.

[0028] Furthermore, halogen-containing alkylene oxides can be used alone or in combination of two or more types. While not specifically limited, examples of onium salts include phosphazenium salts, ammonium salts, and phosphonium salts.

[0029] The structure of the phosphazenium salt is not particularly limited, but for example, it can be represented by the following formula (2).

[0030] [ka]

[0031] In the above formula (2), R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 may form a ring structure bonded to each other, and R 2 themselves or R 3 themselves may form a ring structure bonded to each other. Z - represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, an iodine anion or a hydrogen carbonate anion.

[0032] R 2 and R 3 The hydrocarbon group having 1 to 20 carbon atoms represented by is not particularly limited, and examples thereof include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, etc.

[0033] R 2 and R 3 When R and R are bonded to each other to form a ring structure, examples thereof include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, an isoindolyl group, etc.

[0034] R 2 themselves or R 3 themselves, the ring structure bonded to each other is not particularly limited, and examples thereof include a ring structure in which one substituent is an alkylene group such as an ethylene group, a propylene group, a butylene group, etc. and is bonded to the other substituent.

[0035] Among these, R 2 and R 3 In particular, methyl, ethyl, and isopropyl groups are preferred as alkylene oxide polymerization catalysts that exhibit excellent catalytic activity and are readily available as raw materials.

[0036] Also, Z in equation (2) above - These are hydroxy anions, alkoxy anions with 1 to 4 carbon atoms, carboxy anions, alkyl carboxy anions with 2 to 5 carbon atoms, or bicarbonate anions.

[0037] While not particularly limited, examples of alkoxy anions having 1 to 4 carbon atoms include methoxy anions, ethoxy anions, n-propoxy anions, isopropoxy anions, n-butoxy anions, isobutoxy anions, and t-butoxy anions.

[0038] The alkyl carboxyanions having 2 to 5 carbon atoms are not particularly limited, but examples include acetoxyanion, ethyl carboxyanion, n-propyl carboxyanion, isopropyl carboxyanion, n-butyl carboxyanion, isobutyl carboxyanion, t-butyl carboxyanion, and the like.

[0039] Among these, Z - As such, hydroxy anions and bicarbonate anions are particularly preferred because they serve as halogen-containing alkylene oxide polymerization catalysts with excellent catalytic activity.

[0040] The phosphazenium salt represented by formula (2) above is not particularly limited, but specifically includes tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide, and Trakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydroxide, tetrakis(1,1 ,3,3-tetramethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium Examples include phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydrogen carbonate, tetrakis(1,3-dimethylimidazolidined-2-imino)phosphonium hydrogen carbonate, and tetrakis(1,3-dimethylimidazolidined-2-imino)phosphonium hydrogen carbonate.

[0041] Also, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene), tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(1,3-dimethylimidazolidin-2-imino)phosphoranylidene Examples include [mino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, and tetrakis[tris(1,3-dimethylimidazolidined-2-imino)phosphoranylideneamino]phosphonium hydrogen carbonate.

[0042] Among these, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydroxide, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydrogen carbonate, and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide are particularly preferred because they serve as catalysts for producing halogen-containing polyether ester polyols with excellent catalytic performance.

[0043] The structure of an ammonium salt or phosphonium salt can be represented, for example, by the following formula (3).

[0044] [ka]

[0045] In formula (3) above, D represents a nitrogen atom or a phosphorus atom, and R 4 , R 5 , R 6 and R 7 Each of these independently represents an alkyl group, aryl group, alkoxy group, dialkylamino group, halogen atom, or hydrogen atom having 1 to 20 carbon atoms, which may contain heteroatoms, and E represents a counterion consisting of an inorganic or organic group. 4 ~R 7 Two to four of these atoms may bond together to form a cyclic structure, and this cyclic structure may also contain heteroatoms.

[0046] R 4 , R 5 , R 6 and R 7Examples of alkyl or aryl groups having 1 to 20 carbon atoms represented by are not particularly limited, but include methyl, ethyl, vinyl, n-propyl, isopropyl, cyclopropyl, allyl, n-butyl, isobutyl, t-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, benzyl, tolyl, octyl, cyclooctyl, xylyl, etc. Examples of alkoxy groups include methoxy, ethoxy, vinyloxy, n-propoxy, isopropoxy, cyclopropyl Examples of dialkylamino groups include ropoxy group, allyloxy group, n-butoxy group, isobutoxy group, t-butoxy group, cyclobutoxy group, n-pentyloxy group, neopentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, phenoxy group, heptyloxy group, cycloheptyloxy group, octyloxy group, benzyloxy group, tolyloxy group, cyclooctyloxy group, and xylyloxy group. Examples of dialkylamino groups include dimethylamino group, diethylamino group, pyrrolidino group, piperidino group, di-n-propylamino group, diisopropylamino group, and dicyclopropylamino group.

[0047] Because it is a halogen-containing polyether ester polyol production catalyst with excellent catalytic activity, R 4 , R 5 , R 6 and R 7 Each of these groups is preferably an alkyl or aryl group having 1 to 10 carbon atoms, which may contain heteroatoms, and is particularly preferably a methyl group, an ethyl group, a n-butyl group, a n-octyl group, or a phenyl group.

[0048] R 4 ~R 7 Examples of ammonium salt structures in which two or three of these molecules are bonded to form a cyclic structure include pyridinium salts and imidazolium salts. Imidazolium salts are preferred because they serve as catalysts for the production of halogen-containing polyether ester polyols with excellent catalytic activity.

[0049] In formula (3) above, E is either an inorganic or organic group.

[0050] Among these, while not particularly limited, examples include halogen atoms, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfonic acid groups, boron hydride groups, and hexafluorophosphate groups. Since these serve as catalysts for producing halogen-containing polyether ester polyols with excellent catalytic activity, it is preferable that they be bromine atoms, chlorine atoms, iodine atoms, or hexafluorophosphate groups.

[0051] The ammonium salt or phosphonium salt represented by formula (3) above is not particularly limited, but specifically includes tetramethylammonium bromide, tetraethylammonium bromide, tetran-propylammonium bromide, tetran-butylammonium bromide, tetran-pentylammonium bromide, tetran-hexylammonium bromide, tetran-heptylammonium bromide, tetran-octylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetran-propylammonium chloride, tetran-butylammonium chloride, tetran-pentylammonium chloride, tetran-hexylammonium chloride, tetran-heptylammonium chloride, tetran-octylammonium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3- Examples include dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetran-propylphosphonium bromide, tetran-butylphosphonium bromide, tetran-pentylphosphonium bromide, tetran-hexylphosphonium bromide, tetran-heptylphosphonium bromide, tetran-octylphosphonium bromide, tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetran-propylphosphonium chloride, tetran-butylphosphonium chloride, tetran-pentylphosphonium chloride, tetran-hexylphosphonium chloride, tetran-heptylphosphonium chloride, tetran-octylphosphonium chloride, bromotris(dimethylamino)phosphonium hexafluorophosphate, and others.

[0052] Among these, tetran-octylammonium chloride, tetran-octylammonium bromide, and tetran-butylphosphonium bromide are preferred because they serve as catalysts for producing halogen-containing polyether ester polyols with excellent catalytic activity.

[0053] In a method for producing halogen-containing polyether ester polyols according to one aspect of the present invention, examples of Lewis acids include aluminum compounds, zinc compounds, boron compounds, and the like.

[0054] Examples of aluminum compounds include organoaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-normalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, and monophenyldiisobutylaluminum; aluminoxanes such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

[0055] Examples of zinc compounds include organozincs such as dimethylzinc, diethylzinc, and diphenylzinc; and inorganic zincs such as zinc chloride and zinc oxide.

[0056] Examples of boron compounds include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane, and trifluoroborane.

[0057] Among these, organoaluminum, aluminoxane, and organozinc are preferred, with organoaluminum being particularly preferred, as they serve as catalysts for producing halogen-containing polyether ester polyols with excellent catalytic performance.

[0058] In a method for producing halogen-containing polyether ester polyols according to one aspect of the present invention, it is possible to efficiently produce halogen-containing polyether ester polyols, so the amount of onium salt is preferably 0.001 to 0.1 moles, and particularly preferably 0.001 to 0.05 moles, per mole of hydroxyl groups in the polyester polyol.

[0059] Furthermore, since halogen-containing polyether ester polyols can be efficiently produced, the amount of Lewis acid is preferably 0.002 to 0.2 moles, and particularly preferably 0.002 to 0.1 moles, per mole of hydroxyl groups in the polyester polyol.

[0060] In a method for producing a halogen-containing polyether ester polyol according to one aspect of the present invention, the polymerization pressure is in the range of atmospheric pressure to 1.0 MPa, preferably in the range of atmospheric pressure to 0.5 MPa. In a method for producing a halogen-containing polyether ester polyol according to one aspect of the present invention, the polymerization temperature is in the range of 0 to 180°C, and more preferably in the range of 50 to 130°C.

[0061] In a method for producing halogen-containing polyether ester polyols according to one aspect of the present invention, the polymerization reaction can be carried out without a solvent or in a solvent. When using a solvent, examples of solvents include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1,2-dimethoxyethane. <Flame retardant> The flame retardant according to one aspect of the present invention is not particularly limited as long as it contains a halogen-containing polyether ester polyol according to one aspect of the present invention. For example, when used as a flame retardant for polyurethane foam, it is characterized by having few volatile components because it contains active hydrogen groups in the flame retardant structure and is incorporated into the polyurethane structure by chemical bonds. The application is not particularly limited, but it can be used for urethane foam applications such as flexible polyurethane foam and rigid polyurethane foam. It can also be used in applications referred to as CASE in the art, taking the first letters of the four applications: coatings, adhesives, sealants, and thermoplastic or thermosetting elastomers. <Polyurethane> The structure of the polyurethane according to one aspect of the present invention is not particularly limited as long as it contains residues of the halogen-containing polyether ester polyol according to one aspect of the present invention in its molecular structure, and may be a crosslinked product, linear, or branched.

[0062] Furthermore, while the method for producing polyurethane according to one aspect of the present invention is not particularly limited, one method is to react a halogen-containing polyether ester polyol with a polyisocyanate compound according to one aspect of the present invention.

[0063] Here, the polyisocyanate compound is not particularly limited and includes, for example, aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

[0064] Among these, aromatic isocyanate compounds include, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or mixtures thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), tetramethylxyl Examples include reylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc.

[0065] Examples of aliphatic isocyanate compounds include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0066] Examples of monocyclic alicyclic isocyanate compounds include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate), or mixtures thereof). Examples include hydrogenated MDI (compound), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane (1,3- or 1,4-bis(isocyanate-methyl)cyclohexane, or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), etc.

[0067] Examples of cross-linked cyclic alicyclic isocyanate compounds include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane.

[0068] Furthermore, examples of derivatives of these polyisocyanates include polymers of the above-mentioned isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinedione, uretonimine, isosynurate modified, polycarbodiimide, etc.), urethane modified (for example, urethane modified in which a portion of the isocyanate groups in the above-mentioned isocyanate compound or polymer is modified or reacted with a monool or polyol), biuret modified (for example, biuret modified produced by the reaction of the above-mentioned isocyanate compound with water), allophanate modified (for example, allophanate modified produced by the reaction of the above-mentioned isocyanate compound with a monool or polyol component), urea modified (for example, urea modified produced by the reaction of the above-mentioned isocyanate compound with a diamine), oxadiazinetrione (for example, oxadiazinetrione produced by the reaction of the above-mentioned isocyanate compound with carbon dioxide, etc.).

[0069] The above-mentioned isocyanate compounds or their derivatives may be used individually or in combination of two or more.

[0070] When obtaining polyurethane by reacting a halogen-containing polyether ester polyol with a polyisocyanate compound, for example, heating the composition to a maximum of 200°C or adding catalysts such as dioctyltin dilaurate, dibutyltin dilaurate, triethylamine, triethylenediamine, stanus octoate, dibutyltin di-2-ethylhexanoate, sodium o-phenylphenate, potassium oleate, tetra(2-ethylhexyl) titanate, stannous chloride, ferric chloride, or antimony trichloride can accelerate the reaction between the halogen-containing polyether ester polyol and the isocyanate compound, allowing polyurethane to be obtained in a short time.

[0071] When producing polyurethane according to one aspect of the present invention, the halogen-containing polyether ester polyol according to one aspect of the present invention may be optionally blended with other known polyols, stabilizers, antioxidants, foam stabilizers, crosslinking agents, blowing agents, connecting agents, etc.

[0072] Polyurethane according to one aspect of the present invention can be used in urethane foam applications such as rigid foam or flexible foam. It can also be used in coatings, adhesives, sealants, thermoplastic or thermosetting elastomers, leather, spandex, various inks, etc. <Polyurethane foam> A polyurethane foam according to one aspect of the present invention contains residues of the halogen-containing polyether polyol in its molecular structure.

[0073] Polyurethane foams are broadly classified into flexible and rigid types. However, when obtaining polyurethane foam using a halogen-containing polyether ester polyol according to one aspect of the present invention, conventionally known manufacturing methods can be applied to both flexible and rigid foams.

[0074] For example, one method involves stirring and mixing a room-temperature liquid mixture of a halogen-containing polyether ester polyol according to one aspect of the present invention with, if necessary, other known polyols, stabilizers, antioxidants, catalysts, foam stabilizers, crosslinking agents, foaming agents, and connecting agents, and then stirring and mixing it with a polyisocyanate compound, injecting it into a suitable mold, and allowing it to foam and harden.

[0075] Another method involves preparing a foaming mixture by mixing a halogen-containing polyether ester polyol according to one aspect of the present invention with other known polyols, catalysts, foam stabilizers, blowing agents, and polyisocyanate compounds using a known stirring mixer, injecting this mixture into a mold with an open top, allowing it to foam freely, and curing it as a slab.

[0076] The foaming ratio of the polyurethane foam according to one aspect of the present invention is not particularly limited, but is preferably 1.2 times or more and 100 times or less, and particularly preferably 10 times or more and 80 times or less, as this results in good handling properties.

[0077] Polyurethane foam is not subject to any special restrictions on its applications. Due to the characteristics of polyurethane foam composed of reaction products of a composition according to one aspect of the present invention, it can be used in applications where soft polyurethane foam is typically applied, such as ceiling materials and seats for automobiles and vehicles, pillows, furniture and interiors, bedding, shoe soles, sponges, various cushions, tennis balls, landing mats, etc. Furthermore, polyurethane foam according to one aspect of the present invention can be used in applications where rigid polyurethane foam is typically applied, such as heat insulation and cooling materials, vibration damping and sound absorbing materials, cushioning materials, and buoyancy materials. For example, it can be used for marine applications such as insulation for fishing boats, large vessels, refrigerated cargo ships, LNG carriers, LPG carriers, liquefied gas carriers, and containers, as well as core materials for FRP boats and buoyancy materials for large vessels, lifeboats, buoys, and floats; for automotive applications such as insulation for refrigerated trucks, insulated trucks, railway containers, tank trucks, and roof insulation for vehicles and trucks; for plant applications such as insulation for chemical industry equipment tanks and piping, heat insulation for heavy oil tanks and piping, insulation for LPG and LNG low-temperature liquefied gas refrigeration and piping, insulation covers, and tank lids; for refrigerators and freezers, insulation components for air conditioners, and insulation for various insulated equipment such as showcases, storage units, vending machines, water heaters, and hot water storage tanks; and furthermore, for residential use. Applications include insulation for residential and office buildings (walls, underfloors, ceilings, under roofs, etc.), insulating building materials (laminated boards, composite panels, siding materials, etc.), insulation for bathtubs (stainless steel, FRP, enamel), insulation for cold storage warehouses, agricultural warehouses, livestock barns, etc., void filling (insulated sashes), insulation for constant temperature rooms and district heating and cooling systems, civil engineering applications such as road floor insulation and vibration damping materials, and other applications such as chair cores, door panels, decorative crafts, recreational equipment (cooler boxes, water bottles), educational materials (3D maps, etc.), molds and jigs, surfboard cores, RIM method products (ski cores, racket cores, housings, etc.), and packaging materials. [Examples]

[0078] The present invention will be described below with reference to examples, but these examples are not intended to limit the present invention in any way. First, the details of the raw materials used in the production of halogen-containing polyether ester polyols, as well as the analytical method and production method of halogen-containing polyether ester polyols, will be described. <Polyester Polyol> Polyester polyol 1; Product name: Maximol RLK-087, manufactured by Kawasaki Chemical Co., Ltd., weight-average molecular weight: 550, number of functional groups: 2 Polyester polyol 2; Product name: Nipponran 4065, manufactured by Tosoh Corporation, weight-average molecular weight: 1000, number of functional groups: 2 Polyester polyol 3; Product name: Nipponran 164, manufactured by Tosoh Corporation, weight-average molecular weight: 1000, number of functional groups: 2 Polyester polyol 4; Product name: Kuraray Polyol P-520, manufactured by Kuraray Co., Ltd., weight-average molecular weight: 500, number of functional groups: 2 Polyester polyol 5; Product name: Maximol RDK-142, manufactured by Kawasaki Chemical Co., Ltd., weight-average molecular weight: 280, number of functional groups: 2 <Polyether polyol> Polyether polyol 1; Product name: Sannix PP-600, manufactured by Sanyo Chemical Industries, Ltd., weight-average molecular weight: 600, number of functional groups: 2 (Analytical method for halogen-containing polyether ester polyols) (1) Molecular weight of halogen-containing polyether ester polyols (unit: g / mol) The hydroxyl value d (unit: mgKOH / g) of halogen-containing polyether ester polyols was measured according to the method described in JIS K-1557. The number of functional groups in the obtained halogen-containing polyether ester polyol was denoted as e, and the molecular weight of the halogen-containing polyether ester polyol was calculated using the following formula.

[0079] Molecular weight = (56100 / d) x e. (2) Molecular weight distribution of halogen-containing polyether ester polyols (unit: none) Using a gel permeation chromatograph (GPC) (HLC8020, manufactured by Tosoh Corporation), measurements were performed at 40°C with tetrahydrofuran as the solvent. Polystyrene was used as the standard substance to determine the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of halogen-containing polyether ester polyols.

[0080] The molecular weight distribution (Mw / Mn) of the halogen-containing polyether ester polyol was calculated from the Mn and Mw values ​​obtained using the method described above. (3) Degree of unsaturation of halogen-containing polyether ester polyols (unit: meq / g) The degree of unsaturation of halogen-containing polyether ester polyols was calculated according to the method described in JIS K-1557.

[0081] Example 1. 788.3 g of polyester polyol 1 and 23.0 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere inside the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 107 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [A-1]. The obtained composition [A-1] was heated to 98°C, and 540 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying epichlorohydrin, the mixture was aged for 2 hours at an internal temperature of 90-100°C, and then the residual epichlorohydrin was removed under reduced pressure of 0.5 kPa at 100°C to obtain a pale yellow halogen-containing polyether ester polyol [A-1]. The obtained halogen-containing polyether ester polyol [A-1] had a molecular weight of 1020 g / mol, a degree of unsaturation of 0.022 meq / g, and a Mw / Mn ratio of 1.55.

[0082] Example 2. 708.0 g of polyester polyol 2 and 5.71 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere inside the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 70.8 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [A-2]. The obtained composition [A-2] was heated to 98°C, and 360 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying epichlorohydrin, the mixture was aged for 2 hours at an internal temperature of 90-100°C, and then the residual epichlorohydrin was removed under reduced pressure of 0.5 kPa at 100°C to obtain a pale yellow halogen-containing polyether ester polyol [A-2]. The obtained halogen-containing polyether ester polyol [A-2] had a molecular weight of 1610 g / mol, a degree of unsaturation of 0.032 meq / g, and a Mw / Mn ratio of 1.65.

[0083] Example 3. 849.6 g of polyester polyol 3 and 6.85 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere inside the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 13.02 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals, Ltd., PADM) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [A-3]. The obtained composition [A-3] was heated to 98°C, and 360 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying epichlorohydrin, the mixture was aged for 2 hours at an internal temperature of 90-100°C, and then the residual epichlorohydrin was removed under reduced pressure of 0.5 kPa at 100°C to obtain a pale yellow halogen-containing polyether ester polyol [A-3]. The obtained halogen-containing polyether ester polyol [A-3] had a molecular weight of 1500 g / mol, a degree of unsaturation of 0.040 meq / g, and a Mw / Mn ratio of 1.80.

[0084] Example 4. 708.0 g of polyester polyol 4 and 11.41 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere inside the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 21.70 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals, Ltd., PADM) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [A-4]. The obtained composition [A-4] was heated to 98°C, and 720 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying epichlorohydrin, the mixture was aged for 2 hours at an internal temperature of 90-100°C, and then the residual epichlorohydrin was removed under reduced pressure of 0.5 kPa at 100°C to obtain a pale yellow halogen-containing polyether ester polyol [A-4]. The molecular weight of the obtained halogen-containing polyether ester polyol [A-4] was 1120 g / mol, the degree of unsaturation was 0.052 meq / g, and the Mw / Mn ratio was 1.75.

[0085] The results of Examples 1 to 4 described above are shown in Table 1.

[0086] [Table 1]

[0087] Comparative Example 1. 955.8 g of polyether polyol 1 and 12.84 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere in the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 119.5 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [B-1]. The obtained composition [B-1] was heated to 95°C, and 540 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying epichlorohydrin, the mixture was aged for 2 hours at an internal temperature of 85-90°C, followed by removal of residual epichlorohydrin under reduced pressure of 0.5 kPa at 95°C to obtain a pale yellow halogen-containing polyether polyol [B-1]. The obtained halogen-containing polyether polyol [B-1] had a molecular weight of 1060 g / mol, a degree of unsaturation of 0.005 meq / g, and an Mw / Mn ratio of 1.46.

[0088] Comparative Example 2. 330.4 g of polyester polyol 5 and 9.51 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-necked flask equipped with a stirring blade. After creating a nitrogen atmosphere inside the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 88.5 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (TiBAL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [B-2]. The obtained composition [B-2] was heated to 95°C, and 540 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying the epichlorohydrin, the mixture was aged for 8 hours at an internal temperature of 85-90°C. Following this, residual epichlorohydrin was removed under reduced pressure of 0.5 kPa at 95°C. However, the reaction had barely progressed, resulting in the recovery of almost all of the supplied epichlorohydrin.

[0089] Comparative Example 3. 519.2 g of polyester polyol 1 and 7.61 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter autoclave equipped with a stirring blade. After creating a nitrogen atmosphere in the flask, the internal temperature was set to 100°C and dehydration was carried out under reduced pressure of 0.5 kPa for 2 hours. Then, 70.8 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100°C, and reduced pressure treatment at 0.5 kPa was carried out for 2 hours to obtain composition [B-3]. The obtained composition [B-3] was heated to 98°C, and 1080 mL of propylene oxide (PO, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After supplying PO, the mixture was aged for 2 hours at an internal temperature of 90-100°C, and then the residual PO was removed under reduced pressure of 0.5 kPa at 100°C to obtain a pale yellow polyether ester polyol [B-3]. The obtained polyether ester polyol [B-3] had a molecular weight of 1520 g / mol, a degree of unsaturation of 0.006 meq / g, and a Mw / Mn ratio of 1.44.

[0090] Comparative Example 4. An initiator (polyoxypropylene diol, 300 mg-KOH / g, 46.7 g), ε-caprolactone monomer (εCl, 25 g), and hybrid catalyst (DMC, 0.0313 g and Ti(OBu)4, 0.0188 g) were placed in a 0.5 liter autoclave equipped with a stirring blade. The reactor was then heated to 160°C in a nitrogen atmosphere, and propylene oxide (PO, 53.3 g) was gradually added over 3 hours. This reaction was continued at this temperature for a further 2 hours. After the reaction was complete, a pale yellow polyether ester polyol (εCl-PO copolymer) [B-4] was obtained. The molecular weight of the obtained polyether ester polyol [B-4] was 990 g / mol, the degree of unsaturation was 0.01 meq / g, and the Mw / Mn was 1.15.

[0091] The results for Comparative Examples 1, 3, and 4 are also shown in Table 2.

[0092] [Table 2]

[0093] The following describes the evaluation method and fabrication of polyurethane containing the halogen-containing polyol of the present invention as monomer units. (Method for producing polyurethane) (1) Raw materials <<Commercially available PPG>> In all examples and comparative examples, Sanyo Chemical Industries' Sannix GP-3000 was used. <Foaming agent> In all of the examples and comparative examples, deionized water was used as the foaming agent. <Foam stabilizer> In all of the examples and comparative examples, SRX280A manufactured by Toray Dow Corning was used as the silicone-based foam stabilizer. <Catalyst> In all examples and comparative examples, a solution of triethylenediamine dissolved in dipropylene glycol at a concentration of 33% by weight (TEDA-L33, manufactured by Tosoh Corporation) and tin octoate (Nikka Octix Tin, manufactured by Nippon Chemical Industrial Co., Ltd.) were used as catalysts. <Isocyanate compounds> In all examples and comparative examples, tolylene diisocyanate (Tosoh Corporation, Coronate T-80) with a 2,4 / 2,6 isomer mixing ratio of 80 / 20 was used. <Flame retardant> In Comparative Example 9, a halogen-containing additive-type flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd., CR-504L) was used.

[0094] A halogen-containing polyether ester polyol and water were mixed in the proportions shown in Tables 3 and 4. A catalyst and a foam stabilizer were then added to this mixture. The mixture was then stirred using a small high-speed stirrer (PRIMIX, manufactured by Primix Corporation) at 2000 revolutions per minute for 20 minutes to obtain a stirred mixture (hereinafter referred to as the premix) excluding the isocyanate compound. <Preparation of polyurethane foam> The premix prepared as described above was mixed with a predetermined amount of isocyanate compound so that the ratio of isocyanate-reactive groups (NCO-reactive groups) that can react with the NCO groups, including the total amount of isocyanate groups (NCO groups) and the hydroxyl groups (OH groups) contained in water, was NCO / NCO-reactive groups = 1.0. The mixture was then stirred and mixed for 8 seconds at 4000 revolutions per minute using a small high-speed stirrer (PRIMIX, manufactured by Primix Corporation), and immediately poured into a 250mm x 250mm x 250mm acrylic tank to obtain polyurethane foam. (Method for measuring the physical properties of polyurethane) (1) Tensile breaking strength The prepared polyurethane foam was left to stand for 24 hours in a constant temperature room at 23°C and 50 Rh%, and then its tensile breaking strength was measured using a method compliant with JIS K-6400. A: 85kPa or higher B: 70kPa or higher, less than 85kPa C: Below 70kPa (2) Tensile elongation at fracture The prepared polyurethane foam was left to stand for 24 hours in a constant temperature room at 23°C and 50 Rh%, and then the tensile elongation at break was measured using a method compliant with JIS K-6400. A: Over 230% B: 210% or more, 230% or less C: 210% or less (3) Compression hardness The prepared polyurethane foam was left to stand for 24 hours in a constant temperature room at 23°C and 50 Rh%, and then its 25% compression hardness was measured using a method compliant with JIS K-6400. A: 100N / 314cm 2 That's all. B:85N / 314cm 2 More than 100N / 314cm 2 less than C:85N / 314cm 2 less than (4) Flame retardancy (burning distance) The fabricated polyurethane foam was held horizontally as a test specimen measuring 200mm x 100mm x 10mm, and a flame was applied from 38mm from the left edge for 15 seconds. The burning distance from mark A (38mm from the left edge) was measured. The test was repeated 10 times, and the maximum value was taken as the burning distance of that test specimen. A: Less than 51mm B: 51mm or more, less than 127mm C:127mm or more (5) Volatile components (VOCs, FOGs) The prepared polyurethane foam was left to stand for 24 hours in a constant temperature chamber at 23°C and 50 Rh%, and then 15 ± 2 mg test pieces were prepared. VOCs and FOGs were measured using a method compliant with VDA278 standards. Qualitative and quantitative analysis of VOC and FOG components was performed using GC / MS (Agilent 7890B / 5975C), and the amount of volatile components excluding 2-ethylhexanoic acid and triethylamine derived from the catalyst was calculated. VOCs (excluding catalyst-derived components) A: Less than 350 ppm B: 350 ppm or more, less than 500 ppm C: 500ppm or more FOG (excluding catalyst-derived components) A: Less than 200 ppm B: 200 or higher, less than 500 ppm C: 500ppm or more Example 5. Following the above-described method for producing polyurethane foam, a polyurethane foam was prepared using halogen-containing polyether ester polyol [A-1] and evaluated. This polyurethane foam exhibited excellent tensile strength, tensile elongation, compressive hardness, and flame retardancy, and contained low levels of volatile components (especially VOCs).

[0095] Example 6. Following the above-described method for producing polyurethane foam, a polyurethane foam was prepared using halogen-containing polyether ester polyol [A-2] and evaluated. This polyurethane foam exhibited excellent tensile strength, tensile elongation, compressive hardness, and flame retardancy, and contained low levels of volatile components (VOCs, FOGs).

[0096] Example 7. A polyurethane foam was prepared using halogen-containing polyether ester polyol [A-3] according to the described method for preparing polyurethane foam, and then evaluated. This polyurethane foam exhibited excellent tensile strength, tensile elongation, compressive hardness, and flame retardancy, and contained low levels of volatile components (VOCs, FOGs).

[0097] Example 8. A polyurethane foam was prepared using halogen-containing polyether ester polyol [A-4] according to the described method for preparing polyurethane foam, and then evaluated. This polyurethane foam exhibited excellent tensile strength, tensile elongation, compressive hardness, and flame retardancy, and contained low levels of volatile components (VOCs, FOGs). The results of Examples 5 to 8 described above are also shown in Table 3.

[0098] [Table 3]

[0099] Comparative Example 5. A polyurethane foam was prepared using halogen-containing polyether polyol [B-1] according to the described method for preparing polyurethane foam, and then evaluated. The polyurethane foam showed good tensile strength and tensile elongation, and had low levels of volatile components (VOCs, FOGs), but it was inferior in compressive hardness and flame retardancy.

[0100] Comparative Example 6. A polyurethane foam was prepared using polyether ester polyol [B-3] according to the above-described method for preparing polyurethane foam, and then evaluated. The polyurethane foam exhibited good tensile elongation and low levels of volatile components (VOCs, FOGs), but it was found to have poor flame retardancy.

[0101] Comparative Example 7. Following the above method for producing polyurethane foam, a polyurethane foam was prepared using polyether ester polyol [B-4] and evaluated. Although the polyurethane foam exhibited good tensile elongation at break, it was inferior in tensile strength and flame retardancy.

[0102] Comparative Example 8. Following the above method for producing polyurethane foam, a polyurethane foam was prepared and evaluated without using halogen-containing polyols. Although the polyurethane foam exhibited good compression hardness, it was inferior in tensile fracture strength, tensile elongation, and flame retardancy.

[0103] Comparative Example 9 Following the above method for producing polyurethane foam, a polyurethane foam was prepared using a commercially available flame retardant without using halogen-containing polyols, and then evaluated. This polyurethane foam exhibited excellent tensile strength, tensile elongation, compressive hardness, and flame retardancy, but it was a polyurethane foam with high levels of volatile components (VOCs, FOGs).

[0104] The results for Comparative Examples 5-9 are also shown in Table 4.

[0105] [Table 4]

Claims

1. A halogen-containing polyether ester polyol represented by the following formula (1), having a molecular weight of 500 or more and 3,000 or less. 【Chemistry 1】 (In the above formula (1), R １ (where n represents a polyester polyol residue containing a structure derived from an aromatic polybasic acid and having a molecular weight of 350 or more and less than 2500, n is an integer between 1 and 25, m is 2 or 3, and X represents a chlorine atom.)

2. A method for producing a halogen-containing polyether ester polyol by ring-opening polymerization of an alkylene oxide in the presence of a composition comprising an onium salt, a Lewis acid, and a polyester polyol, wherein the amount of the onium salt used per mole of hydroxyl groups of the polyester polyol is in the range of 0.001 to 0.1 moles, and the amount of the Lewis acid used is in the range of 0.002 to 0.2 moles, according to claim 1.

3. A flame retardant containing the halogen-containing polyether ester polyol described in claim 1.

4. A polyurethane containing a residue of the halogen-containing polyether ester polyol described in claim 1 in its molecular structure.

5. A polyurethane foam containing a residue of the halogen-containing polyether polyol described in claim 1 in its molecular structure.

6. The polyurethane foam according to claim 5, wherein the VOC (excluding catalyst-derived components) measured by a method compliant with VDA 278 after being left to stand for 24 hours in a constant temperature room at 23°C and 50 Rh%, is less than 350 ppm, and a 15 ± 2 mg test piece is prepared.

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