KR100840997B1 - Manufacturing method of Polyetherpolyol for polyurethane foam manufacturing - Google Patents

Abstract

The present invention is a polyether polyol for producing polyurethane foam, in which a secondary amine is reacted with a halogenated epoxy compound to obtain an amino alcohol having 2 to 3 amino groups, which is obtained by subjecting an epoxy compound to an epoxide polymerization reaction under a catalyst. It relates to a method for producing a polyether polyol having 2 to 3 amine groups in a molecule.

The polyether polyol prepared by the method of the present invention can greatly reduce the occurrence of odor and fogging phenomenon in the production of polyurethane foam, and can also reduce the amount of amine catalyst used by 50 to 100% and has various urethane reaction rates. Have

Polyurethane foam, polyol, amine catalyst, epoxy compound, polyether polyol

Description

Manufacturing method of Polyetherpolyol for polyurethane foam manufacturing

The present invention relates to a method for producing a novel polyether polyol for producing polyurethane foam. More particularly, the present invention relates to a method for producing a polyether polyol, in which odor and fogging phenomenon are reduced during polyurethane foam production.

Polyurethane foam has a wide range of applications such as automotive seats, insulation, building flooring, furniture, beds, and clothing.

Polyurethane foams are produced using polyether polyol and polyisocyanate as main ingredients and various catalysts with low molecular weight chain extenders, crosslinking agents, foaming agents, surfactants and the like.

Polymers having a plurality of hydroxyl groups are called polyols. Polyurethanes are prepared by condensation of an isocyanate compound with a polyol. The reaction of isocyanates with polyols is known to first produce an adduct of an isocyanate with a base which is a catalyst which in turn reacts with an alcohol to form a polyurethane.

A reaction in which a polyol and an isocyanate react to form a urethane bond having a three-dimensional bond structure is called a urethane reaction.

Polyols having ether bonds in the molecular structure, such as poly (oxypropylene ether) polyols and poly (oxyethylene-propylene ether) polyols, in polyols used in polyurethane products are called polyether polyols and polybasic acids such as phthalic acid and adipic acid. Polyols obtained by the reaction of alcohols are called polyesterpolyols and the present invention relates to polyetherpolyols.

Polyether polyols are prepared by epoxide polymerization using hydrocarbon hydroxides such as ethylene oxide and propylene oxide as alkali hydroxides and polymerization initiators.

As shown in the following scheme, a polymerization reaction for producing a polymer by ring-opening reaction of an epoxy group is called an epoxide polymerization reaction.

As a catalyst used for the urethane reaction of isocyanate and polyol, various bases such as dimethylethanolamine, triethylamine, triethylenediamine, hexamethylenetetraamine, cobalt naphthenate are used, but amine catalysts are mainly used.

Polyurethane foam produced by using an amine catalyst has a problem of emitting ammonia odor peculiar to the amine compound when foaming, and when used as a car seat, due to the fogging phenomenon, sun viser, armrest ( arm rest) There is a problem of polluting automobile interior materials and causing pollution phenomenon in products such as building materials.

Here, the fogging phenomenon refers to a phenomenon in which the microvolatile substances contained in the urethane foam are slowly volatilized to the outside and recrystallized by the glass or the ceiling of the automobile, resulting in staining of the glass or fiber and being contaminated.

In the past, various methods have been proposed to reduce odor generated in polyurethane foam using an amine catalyst and to suppress fogging.

Odor and fogging caused by polyurethane foams are due to unreacted amine catalysts remaining in the product. Therefore, amine catalysts are combined with isocyanate compounds or polyols to prevent amine catalysts from flowing out of polyurethane foams. The method has been proposed.

US Pat. No. 5,143,944 and US Pat. No. 5,710,191 suggest a method of introducing a hydroxyl group to an amine catalyst so that the amine catalyst having a hydroxyl group reacts with an isocyanate to be bonded.

Amine combined with isocyanate does not cause off-flavor or fogging.

However, such a catalyst exhibits the disadvantage of using an excessive amount of catalyst because the amine catalyst is combined with isocyanate during the polyurethane reaction, thereby reducing the mobility of the amine catalyst and decreasing the activity of the catalyst.

In order to compensate for the deterioration of the mobility of the amine catalyst as described above, US Pat. No. 5,436,969 and US Pat. No. 6,060,531 disclose N, N-dimethyl-1,4-diaminobutane (N, N-dimethyl-1,4-diaminobutane). ), N, N-dimethyl-1,3-diaminopropane (N, N-dimethyl-1,3-diaminopropane), N, N-dimethyldipropylene and N, N-dimethyldi A polyol having an amine group was prepared by reacting propylene triamine (N, N-dimethyldipropylene triamine) with a polyol. In US Pat. No. 6,762,274, 3,3′-diamino-N-methyldipropylamine (3,3′- diamino-N-methydipropylamine), 3,3'-diamino-N-ethyldipropylamine, 3,3'-diamion-N-ethyldipropylamine, 2,2'-diamino-N-methyldiethylamine (2 , 2'-diamino-N-methyldiethylamine) was used to prepare a polyol having an amine group.

In general, polyols are more mobile than isocyanates.

Flexible polyurethane foams are produced using additives such as reactive catalysts, surfactants, and crosslinking agents based on polyols and polyisocyanates. As polyols, polyetherpolyols having 2 to 4 functional groups and 20 to 100 mg KOH / g hydroxyl group are used. Particularly in slab products, those having a hydroxyl value of 56 to 35 and an ethylene oxide content of 0 to 10% are used. In mold products, polyester polyols having a hydroxyl value of 20 to 50, an ethylene oxide content of 10 to 20%, and ethylene oxide attached to the terminal are used. In the hard sector, products having 4 to 8 functional groups and 200 to 1200 hydroxyl groups are used. Polyol, the main raw material of polyurethane, has a functional group of 2 to 8 and a molecular weight of 500 to 7000. Depending on the application of polyurethane, industrially, glycerin, sugar, ethylene oxide, propylene oxide monomer, KOH, etc. Prepared by epoxide polymerization using a catalyst.

Starting materials for the production of polyols include propylene glycol, ethylene glycol, glycerin, methyl glucoside, glucose, trimethylol propane, pentaerythritol, ethylene diamine, toluenediamine, The substance which has polyhydric hydroxyl groups, such as sugar and sorbitol, is mentioned. Examples of the unit monomers of the polymer include substances having epoxide groups such as ethylene oxide, propylene oxide, and butylene oxide, and the catalysts include basic catalysts such as sodium hydroxide, potassium hydroxide, cesium oxide, trimethyl amine, triethylamine, and the like. AlCl ₃ Metal catalysts such as ZnCl ₂ , FeCl ₃ , BF ₃ , BCl ₃ , BeCl ₂ , FeBr ₃ , SnCl ₄ , TiCl ₄ , ZrCl ₄ , ZnCl ₂ , and the like. Al (OR) ₃ , Mg (OR) ₂ , Zn (OR) ₂ , Al (I-Pr) 3-ZnCl ₂ , Fe (Oet) ₃ , AlEt ₃ The epoxy reaction may also be carried out.

Polyols prepared with basic catalysts produce unsaturated polyols by side reactions during epoxide polymerization, and are difficult to produce polyols with molecular weights of 6000 or more, making them difficult to use for polyurethane production, such as high elasticity. There are difficulties and disadvantages of the odor problem of the remaining amine catalyst, but it is also used in some fields in polyols for producing rigid urethane foams. In addition, when the polyol is prepared using a metal catalyst such as AlCl ₃ , ZnCl ₂ , FeCl ₂ , BF ₃ , there is little side reaction of the monool due to the basic catalyst, and thus a very large polymer polyol can be produced. Low reactivity of propylene results in high usage and disadvantages in handling solid catalysts.

In order to lower the concentration of the unsaturated polyol produced by the side reaction of epoxide polymerization, a CsOH catalyst or a bimetal cyanide catalyst was used instead of the basic catalyst. The CsOH catalyst reduced unsaturation by 50% compared to the conventional catalyst, and the bimetallic cyanide catalyst minimized side reactions of monools, so that the monool content was lower than 0.01 meq / g. Many polymer products have been made, including polyether, polyester and polyether ester polyols. Bimetallic cyanide catalysts generally have a structure of M _a [M '(CN) ₆ ] _b L _c L' _d . Metal salts generally have the general formula M (X) _n where M is Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb ( Ⅱ), Fe (III), Mo (IV), Mo (VI), Al (II), V (V), V (IV), Sr (II), W (IV), W (VI), Cu ( II) and Cr (III). X is a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate It is an anion selected from carboxylate and nitrate. The value of n is 1 to 3 and satisfies the valence of M. Zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II), and nickel formate (II) ), Nickel (II) nitrate and the like. The metal cyan salt M 'generally has a structural formula of (Y) _a M'C (N) _b (A) _c . M 'is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni ( II), Rh (III), Ru (II), V (V), V (IV), and the like. Y is an alkali metal ion or an alkali metal ion. A is an ion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, nitrates and the like. a and b are integers greater than one. The sum of the charges a, b and c balances the M 'charge. Potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), and potassium hexacyanoferrate (III). , Calcium hexacynocobaltate (II), lithium hexacyanoferrate (II), and the like.

Bimetallic cyanide catalysts for preparing polyols have been disclosed in detail in US Pat. No. 6,627,575.

 Isocyanates for preparing polyurethane foams include aromatic isocyanates, aliphatic isocyanates, arylaliphatic isocyanates and cycloaliphatic isocyanates. Aromatic isocyanates include 4,4'-diphenylmethande diisocyanate (hereinafter referred to as MDI), 2,2'-diphenylmethane diisocyanate, 1,3- Toluene-2,4-diisocyante, together with 1,3-phenyl diisocyanate and monomeric MDI and polymeric MDI mixed therewith, TDI such as toluene-4,4-diisocyante, P-phenylenediisocyanate, chlorophenylene-2,4-diisocyanate (chlorophenylene-2,4-diisocyante) ), Diphenylene-4,4-diisocyante, 4,4'- diisocyanate-3,3 'dimethyldiphenyl (4,4'-diisocayante-3,3'- dimehyldiphenyl), diphenyletherdiisocyanate, 2,4,6-triisocyanate (2,4,6-triisocyanatotoluene) and 2,4,4 -Tree and the like diisocyanate diphenyl ether (2,4,4'-triisocyantodiphenylether). In addition, isocyanate may be mixed with various isocyanates, and generally mixed with MDI / TDI, or isocyanate is reacted with a polyether polyol to prepare an isocyanated-terminated prepolymer. Aliphatic isocyanates include 1,6-hexamethylene diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, 1,12- Dodecane-diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane As diisocyanate (4,4; -dicyclohexylmethane diisocyanate) and cycloisocyanate, 1,3 or 1,4-cyclohexane diisocyanate, 1-isocyanate-3,3-5-trimethyl-5 1-isocyanateo-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4 or 2,6-hexahydrotoluylene diisocyanate (2,6-hexahydortoluylene diisocyanate), 4,4- Diisocyanate dicy To include cyclohexylmethyl (4,4-diisocyanatodicyclohexylmetane).

Catalysts used in polyurethane foam production include amine catalysts and metal catalysts as reactive catalysts. The amine catalysts are N, N-dimethylcyclohexylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, and penta. Methyldiethylenetriamine (pentamethyldiehtylenetriamine), tetramethylethylenediamine, bis-methylaminoethyl-ether (bis -methylaminoethylether), 1-methyl-4-dimethylaminoethyl-piperazine (1-methyl-4-dimetylaminoethyl -piperazine), 3-methoxy-N-dimethylpropylamine, dimethylethanolamine, N-cocomorpholine, N, N'-dimethyl-N , N′dimethylisopropylenediamine [NN′dimethyl-N′N′dimethyl isopropylpropylenediamine], N, N-dimethyl 1-3-dimethylamino-polyolamine [N, N-dimethyl-3-diethylamino-propylamine] and dimethylbenzyl Dimethylbenzylamine, N, N, N ', N'-tetraethyldiaminodiethyl ether (N, N, N', N '-Tetramethyldiaminodiethylether), bis- (dimethylaminopropyl) [bis- (dimethylaminopropyl)] urea and pyridine. Metal catalysts include stannous chloride, zinc chloride, lead octate, tin dioctate, diethyltin hexoate, dibutyltin dilaurate dilaurate).

The crosslinking agent and chain extender used in the production of polyurethane foams are polyhydroxyl groups having a molecular weight of 17 to 600. Diol / triol, alkanolamine and amines There is. Aliphatic diols / triols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, and the like.Alkanolamines include diethanolamine, triethanolamine, and the amines include ethylenediamine, Butylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, 4,4'diaminodiphenylmethane, 2,6'-toluylenediamine (2,6'-toluylenediamin), methylene- polyamines such as bis- (o-chloroaniline) [Metylen-bis- (o-chloroaniline)].

Foaming agents used in the production of polyurethane foams include water, carbon dioxide and hydrocarbons. Hydrocarbons include methylene chloride, propane, butane, isobutane, ethers such as dimethyl ether and diethyl ether, dichloromethane, trichloro fluoromethane, dichlorodifluoromethane, 1,1,2- Halogenated hydrocarbons such as trichloro-1,2,2-trifluoromethane, dichlorotetrafluoroethane, acetone, MEK, ethyl acetate And ketones.

Surfactants, flame retardants, fillers, dyes, stabilizers, etc. may be used to impart special functions to polyurethane foams. Surfactants used to control the structure of the cell to the appropriate size during foam foaming include organosilicon compounds, alkylphenols (ethoxylated alkyl phenol), aliphatic alcohol (ethoxylated fatty alcohol), paraffin oil (paraffin oils), perm Castor oil. Flame retardants include tricresyl phosphate, tris- (1,3-dichloropropyl phosphate), tris (2,3-dibroropropyl) phosphate Phosphorus-based flame retardants such as (2,3-dibromopropyl) phosphat and tetrakis (2-chloroethyl) ethylene diphosphate, aluminum oxide hydrate, and antimony trioxide Inorganic flame retardants, such as melamine cyanurate (melamine cyanurate) is used in combination.

In order to reduce the amine catalyst in the manufacture of polyurethane foam, to prepare a polyol in which the amine is used to manufacture the foam, U.S. Patent No. 5,476,969 discloses N, N'-dimethyldipropylenetriamine (N, N'-Dimethyldipropylenetriamine). , U.S. Pat.No. 6,060,531 to N, N'-dimethyl-1,4-diaminobutane (N, N-dimethyl-1,4-diaminobutane), N, N-dimethyl-1,3-diaminopropane (N A polyol having an amine group was prepared using N-dimethyl-1,3-diaminopropane) and N, N-dimethyldipropylene triamine as starting materials. In US Pat. No. 6,762,274, 3, 3'-diamino-N-methylpropylpropyl (3,3'-diamino-N-methyldipropylamine), 3,3'-diamino-N-ethyldipropylamine (3,3'-diamino-N-ethyldipropylamine) A polyol was prepared using an amine such as 2,2'-diamino-N-methyldiethylamine. All of them have one amine group bonded to the polyol main chain, and thus, in the production of highly reactive polyurethane foams or in the automobile seat field using high-elastic polymer polyols, the number of moles of amine groups is less than one, resulting in a slow urethane curing rate. Commercially, there is a disadvantage in that an additional amine catalyst must be used.

An object of the present invention is to provide a polyether polyol for preparing urethane foam in which two to three amine catalyst compounds are bonded to a polyol main chain, and a method for preparing the same.

In order to reduce odor and fogging phenomenon in a polyurethane foam manufactured using an amine catalyst, a method of preparing a polyurethane foam by combining an amine catalyst compound to an isocyanate or a polyol and then reacting the polyol and an isocyanate is known. It has been proposed.

In this case, polyols or isocyanates cannot be bonded to more than one amine group, and thus, polyurethane foams are prepared using polyols or isocyanates combined with a catalyst compound containing one amine group. In the urethane reaction, it was not possible to provide a sufficient amine catalyst compound, the reaction time was long, or there was a disadvantage that an additional amine compound had to be used.

The present inventors react with a secondary amine (= NH) with a halogenated epoxy compound to obtain a monovalent halogenated aminoalcohol, and then react with a polyvalent aminoalcohol to obtain a compound having two or three amino groups, which are reacted with an epoxy compound. When the polyester polyol was prepared, it was confirmed that a polyether polyol obtained by combining two or three amine catalyst compounds was completed, thereby completing the present invention.

The present invention is a polyurethane foam by developing a method that can combine up to three amine groups in the polyol main chain in order to reduce the number of moles of the amine catalyst compound bonded to the polyol to show the disadvantages such as delay in curing rate of the polyurethane foam The purpose of the present invention is to reduce the occurrence of off-flavor and fogging without additionally using an amine catalyst.

In the present invention

의 구조를 가지는 에폭시 화합물과

의 구조를 갖는 2차 아민과 일차 반응시켜 1가의 아미노알콜을 얻은 후 이를 (HO)n-N-R의 일반식으로 표시되는 다가의 아미노알콜과 2차 반응시켜 2~3개의 아미노기를 갖는 화합물을 얻고 이를 중합개시제로 하여 프로필렌옥사이드나 에틸렌옥사이드를 에폭사이드 중합반응시켜 폴리올을 제조한다.

An epoxy compound having a structure of

First reaction with a secondary amine having the structure of to obtain a monovalent aminoalcohol and then secondary reaction with a polyvalent aminoalcohol represented by the general formula of (HO) nNR to obtain a compound having 2 to 3 amino groups to polymerize it An epoxide polymerization reaction of propylene oxide or ethylene oxide is used as an initiator to prepare a polyol.

delete

In the above chemical formula, X is halogenalkyl or arylsulfonate, and R, R ₁ , R ₂ represent an alkyl group.

Examples of the epoxy compound include halogenated epoxy compounds such as epichlorohydrin, epibromohydrine, and epifluorohydrin, glycidyl methyl sulfonate, and the like depending on the kind of x. Glycidylethanesulfonate, glycidyl propanesulfonate, glycidylbutanesulfonate, glycidylbenzenesulfonate, glycidyl p-toluesulfonate (glycidyl p-toluenesulfonate), glycidyl m-nitrobenzenesulfonate, glycidyl p-nitrobenzenesulfonate, glycidyl trichlorobenzensulfonate , Glycidyl-1-naphthesulfonate, and the like. Secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, diphenylamine, dicyclohexylamine, 3-methyldi Phenylamine and the like. Amino alcohols include methanolamine, ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, sec-butanolamine, t-butanolamine, pentanolamine, 2-amino-1-phenylethanol, dimethanolamine, di Ethanolamine, dipropanolamine, diisopropanolamine, diisobutanolamine, di-sec-butanolamine, dibutanolamine, dipentanolamine, N-methylethanolamine and the like.

The present invention is to solve the problem of reactivity control in which a polyol grafted with one amine catalyst causes a reaction rate and delay in curing reaction. In the present invention, amino alcohol having a plurality of amine groups is grafted onto a polyol. In addition, the foam reactivity was improved and odor and fogging by the volatile amine catalyst were improved. Amines grafted with monoalcohols such as aminomethanol and aminoethanol and amines with dialcoholamines such as dimethanolamine, diethanolamine, etc. to graf the amine catalyst from 2 to 3 on the polyol main chain The content of the catalyst can be adjusted. In addition, in order to control the reactivity of the amine catalyst, the type of the alkyl group substituted in the secondary amine can be controlled as C ₁ to C ₁₀ such as dimethylamine and diphenylamine.

In the present invention, to synthesize a polyol grafted with amine, epichlorohydrin is added to a reactor and reacted while maintaining the reaction temperature below 40 ° C while adding 1 equivalent of dimethylamine to the reactor for 2 to 4 hours. After the addition of the diamine is complete, it is aged for 30 minutes to complete the reaction of the unreacted diamine. After the completion of aging, 1 equivalent of diethanolamine was added to the reactor, nitrogen was substituted, and the temperature of the reactor was raised to 95-120 ° C., and the reaction temperature and pressure were maintained for 2 to 4 hours. After the reaction of diethanolamine, 1 to 1.2 equivalents of 48% aqueous KOH solution was added to the reactor and mixed at high speed. After mixing, the reaction is filtered through a filter. This reactant is dimethylaminoalcohol, while adding 1 equivalent of dimethylaminoalcohol and KOH aqueous solution into the reactor and mixing, while removing the water with a vacuum pump while raising the reaction temperature of the reactor to 95 ~ 120 ℃. After the water is removed, a certain amount of PO / EO is added to the reactor so that the polyol has a weight average molecular weight of 3000 to 6000 and an EO content of 5 to 20% wt%. After the addition of PO is completed, the unreacted PO is aged, and the remaining amount of PO / EO is removed with a vacuum pump. Magnesol (magnesium silicate) is added to the reactor to remove the KOH catalyst.

Polyurethane foam in the present invention is a polyol and polyisocyanate and 0.5 to 2 equivalents of polyisocyanate so as to have a density of 10 ~ 150 kg / m ³ after mixing the chain extender, surfactant, water, etc. in the polyol at a temperature of 15 ~ 50 ℃ After mixing for 5 ~ 10 seconds at a high speed of more than 7000 rpm at a rate of pour into a square frame of 30 * 30 * 10 cm to form foam with a free rise (free rise). Polyols are polypropylene / ethylene oxide polyols having a hydroxyl value of 25 to 56 mg KOH / g, ethylene oxide 0 to 20%, functional group 3, styrene and acrylonitrile, and a hydroxyl value of 20 to 40 mg KOH / g. g polymer polyol is used at a ratio of 0 to 20 wt% of the polypropylene / ethylene oxide polyol.
<Synthesis example of amino alcohol>

Synthesis of Dimethylamino Alcohol (Synthesis Example 1)

Put 74 g of epichlorohydrin in a 2 L high-pressure reactor and replace nitrogen with stirring. Epichlorohydrin and dimethylamine are reacted at a reaction temperature of 40 ° C. while injecting 72 g of a 50% aqueous solution of dimethylamine into the reactor for 60 minutes. After the dimethylamine addition is completed, the reaction is aged for 30 minutes to obtain 110 g of dimethylamine-3-chloro-2-propanol. If this is expressed as a reaction scheme, it is as follows.
_{CH 2 CH 2 0 - CH 2} Cl + CH 3 · CH 3 NH →
(Epichlorohydrin) (dimethylamine)
CH ₃ CH ₃ NCH ₂ -CH (OH) -CH ₂ Cl
(Dimethylamine-3chloro-2propanol)
88 g of diethanolamine was added thereto, followed by nitrogen substitution, and the reaction temperature of the reactor was increased to 120 ° C., followed by reaction for 2 hours. 1-dimethylamine-3-aminodiethanol-2-propanol [CH ₃ CH ₃ N-CH 198 g of ₂ -CH (OH) -CH ₂ -N- (CH ₂ CH ₂ OH) ₂ ] are obtained. 104.2 g of 48% aqueous solution of KOH was added to the reactor, and the reaction temperature was reduced to 112 ° C., and the water in the reactor was removed with a vacuum pump for 3 hours until the concentration was less than 1000 ppm. Potassium chloride is removed using a pressure filter.

The OH value, KOH content, weight average molecular weight and chlorine content of the diamino alcohol (1-dimethylamine-3-amino diethanol-2propanol) obtained here were as follows.

OHV: 815 meqKOH / g, MW: 206g Cl: 0.2 ppm

Synthesis of Trimethylamino Alcohol (Synthesis Example 2)

74 g of epichlorohydrin was added to a 2 L high-pressure reactor, and nitrogen was replaced with stirring. 72 g of a 50% aqueous solution of dimethylamine is injected into the reactor for 60 minutes and reacted at a reaction temperature of 40 ° C. After completion of the dimethylamine addition, the reaction is aged for 30 minutes to obtain 110 g of dimethylamine-3chloro-2-propanol. 25.1 g of monoethanolamine was added thereto, followed by nitrogen replacement. The reaction temperature of the reactor was increased to 120 ° C., and then reacted for 2 hours to obtain 136 g of di (1-dimethylamine-2-propanol) -ethanolamine. Can be. If this is expressed as a reaction scheme, it is as follows.
CH ₃ CH ₃ N-CH ₂ -CH (OH)-CH ₂ Cl + (HOCH ₂ CH ₂ ) NH →
(Dimethylamine-3chloro-2propanol) (monoethanolamine)
(CH ₃ CH ₃ N-CH ₂ -CH (OH) -CH ₂ ) ₂ -NCH ₂ CH ₂ OH
[Di (1-dimethylamine-propanol) -ethanolamine]
104.2 g of 48% aqueous solution of KOH was added to the reactor, and the reaction temperature was reduced to 112 ° C., and the water in the reactor was removed with a vacuum pump for 3 hours until the concentration was less than 1000 ppm. Potassium chloride is removed using a pressure filter.

The OH value, KOH content, weight average molecular weight and chlorine content of the trimethylamino alcohol (di (1-dimethylamine-propanol) -ethanolamine) obtained here were as follows.

OHV: 635 meqKOH / g, MW: 1176.1 Cl: 0.5 ppm
<Polyol Production Example>

Example 1

66 g of 1-dimethylamine-3-aminodiethanol-2-propanol and 7 g of 48% KOH were added to a 2 L high-pressure reactor, and the temperature was heated to 112 ° C. While stirring the mixture, a small amount of water is removed under reduced pressure with a vacuum pump. In vacuum, 847.8 g of propylene oxide monomer (PO) and 84.5 g of ethylene oxide (EO) are introduced into the reactor for 5 hours. After the completion of the injection, in order to mature the reaction of unreacted propylene oxide and ethylene oxide, the reaction temperature of the reactor is increased to 125 ° C for 1 hour. After completion of the reaction, the reactor was kept in vacuum at 112 ^° C. for 30 minutes to remove unreacted PO and EO. In order to remove the residual catalyst, 50g and 5g of magnesol and a filter agent were added to the reactor, stirred for 1 hour, passed through a pressure filter to remove the catalyst, and 1 kg of a polyether polyol having two amine groups in the molecule was obtained.

Example 2

8 kg of di (1-dimethylamine-2-propanol) -ethanolamine and 912 g of PO were used as starting materials to obtain 1 kg of polyether polyol having three amine groups in the molecule.
Example 2 uses di (1-dimethylamine-2-propanol) -ethanolamine instead of 1-dimethylamine-3-aminodiethanol-2-propanol as a starting material and changes the amount of PO used. Was carried out in the same manner as in Example 1.

Example 3

27.5 g of 1-dimethylamine-3-aminodiethanol-2-propanol and 6.7 g of 48% KOH aqueous solution are added to a 2 L high-pressure reactor and the temperature is heated to 112 ° C. While stirring the mixture, a small amount of water is removed under reduced pressure with a vacuum pump. In vacuum, 809.3 g of propylene oxide monomer (PO) is injected into the reactor for 9 hours. After the completion of the injection, in order to mature the reaction of the unreacted propylene oxide, the reaction temperature of the reactor is raised to 125 ° C. for 1 hour. After completion of the reaction, the reactor was kept in vacuum at 112 ^° C. for 30 minutes to remove unreacted PO. 164.7 g of ethylene oxide monomer (EO) was injected thereto for 2 hours. After the completion of the injection, in order to mature the reaction of unreacted propylene oxide, the temperature of the reactor is increased to 135 ° C for 1 hour. After completion of the reaction, the reactor was kept in vacuum at 125 ^° C. for 30 minutes to remove unreacted PO. In order to remove the residual catalyst, 50g and 5g of magnesol and a filter agent were added to the reactor, stirred for 1 hour, passed through a pressure filter to remove the catalyst, and 1 kg of a polyether polyol having two amine groups in the molecule was obtained.

Example 4

3 kg of di (1-dimethylamine-2-propanol) -ethanolamine and 800.2 g of PO and 164.9 g of EO were used as starting materials in Example 3 to obtain 1 kg of a polyether polyol having two amine groups in a molecule.

Comparative Example 1

Polyglycerol polyol was synthesized in the same manner as in Example 1 using glycerin as a starting material.

Comparative Example 2

Polyether polyol was synthesized in the same manner as in Example 3 using glycerin as a starting material.
Physical property values of the polyether polyols obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are as shown in Table 1 below.
TABLE 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 OHV 56.3 55.8 28.4 28.3 56.1 27.9 Mw 2973 2016 5926 5946 3000 6032 EO,% 8.6% 8.5% 16.4% 16.5% 8.5% 16.6% Amine value, (MgKOH / g) 36.5 37.7 18.1 18.5 0 0

※ OHV: OH Value

Mw: weight average molecular weight
<Polyurethane foam manufacturing example>

Examples 5-8

Polyurethane foams were prepared using the polyols of Examples 1 to 4 according to the formulation shown in the table below. In Examples 5 and 6, polyurethane foams can be produced without using an amine catalyst (A-1).

Comparative Examples 3 to 4

As shown in the table below, the polyol and the chain extender, the surfactant, and the water of Comparative Examples 1 and 2 were added and mixed at a temperature of 25 ° C., and then mixed with the polyisocyanate for 7 seconds at a high speed of 7000 rpm or more. Polyurethane foams were synthesized by pouring foam into a square frame of cm and free foaming.
TABLE 2

Example 5 Example 6 Comparative Example 3 Raw materials Polyol,, H ₂ O T-9 (catalyst) A-1 (foaming aid) BF-2730 methylene chloride TDI Example 1 / Comparative Example 1 20/80 3.7 0.26-1.2 5 115 Example 2 / Comparative Example 1 10/90 3.7 0.26-1.2 5 115 Comparative Example 1 100 3.7 0.26 0.1 1.2 5 115 Foam Reactivity Crime time, (sec) Rise Time, (sec) 13 80 12 83 12 81 Foam property Density, (kg / m ³ ) ILD 25%, (kg / 314cm ²⁾ 65%, (kg / 314cm ²⁾ Tear, (kg / cm) Tensile, (kg / cm ²⁾ Elongation, (%) Breathable, ( Ft ³ / min) resilience, (%) Amine content (ppm) 26.3 22.3 45.3 0.69 0.99 117 1.48 31- 27.2 21.9 45.2 0.68 0.94 112 1.42 32- 27 21.7 44.9 0.64 0.94 105 1.85 41 2
T-9: Octyl acid tin
A-1: amine catalyst (bis (dimethylaminoethyl) ether)
BF-2730: Silicone Oil
TDI: toluene diisocyanate
TABLE 3

Example 7 Example 8 Comparative Example 4 Raw materials Polyol, Y-7325N H ₂ O triethylenediamine EF-600 T-12 DEOA silicone oil (defoamer) MDI Example 5 / Comparative Example 2 50/30 20 3.5-0.03 0.1 MC50 Example 6 / Comparative Example 2 30/50 20 3.5-0.03 0.1 MC50 Comparative Example 2 80 20 3.5 0.3 / 0.14 / 0.2--0.7 0.8 MC50 Foam property Density, (kg / m ³ ) ILD 25%, (kg / 314cm ² ) ILD 65%, (kg / 314cm ² ) Tear, (kg / cm) Tension, (kg / cm ² ) Elongation, (%) Resilience , (%) Compression set, (%, Dry) cyclic compressive strain, (%) 25% Loss 50% Loss 65% Loss Thickness Loss Amine Content (ppm) 34.5 19.3 61.5 0.93 1.18 131 53 68.0 33.6 27.4 18.8 8.6- 35.0 19.5 62.3 0.96 1.29 128 53 65.8 33.7 27.2 17.5 9.8- 34.6 19.6 61.4 0.96 1.22 129 52 67.2 33.7 27.4 18.2 9.3 7
T-12: dibutyl tindilaurate
Y-7325N: Polyol (trade name of SKC Corporation)
EF-600: Silicone Oil
DEOA: diethanolamine

The polyether polyol prepared by the method of the present invention does not use an amine catalyst in the manufacture of polyurethane foam or the amount of amine catalyst used can be reduced by 50 to 100%, which can greatly reduce the off-flavor or fogging of polyurethane foam. It has an effect.

Claims (3)

In the method for producing a polyether polyol for producing polyurethane foam, a secondary amine is reacted with a halogenated epoxy compound to obtain an amino alcohol having 2 to 3 amino groups, which are obtained by epoxide polymerization of an epoxy compound under a catalyst using a polymerization initiator. A method for producing a polyether polyol for producing polyurethane foam having 2 to 3 amine groups in a molecule. The method of claim 1, The secondary amine is selected from dimethylamine, diethylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, diphenylamine, dicyclohexylamine, 3-methyldiphenylamine The halogenated epoxy compound is selected from epichlorohydrin, epibromohydrin, epifluorohydrin, and aminoalcohol is methanol, ethanolamine, propanolamine, isopropanolamine, butanolamine, isobutanolamine, sec- Butanolamine, t-butanolamine, pentanolamine, 2-amino-1-phenylethanol, dimethanolamine, diethanolamine, diisopropanolamine, diisobutanolamine, di-sec-butanolamine, dibutanolamine, di Pentanolamine, N-methylethanolamine, and the catalyst is KOH, and the epoxy compound is selected from ethylene oxide or propylene oxide. Manufacturing method. delete