JP2018123308A - Polyol composition and method for producing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition having excellent reaction activity and good compatibility with hydrofluoroolefin and to provide a method for producing a polyurethane foam using the polyol composition.SOLUTION: There is provided a polyol composition for producing a polyurethane foam (H), which comprises a polyether polyol (A) which is an adduct obtained by adding an alkylene oxide (C) to a compound having two or more active hydrogens (C), hydrofluoroolefin (D) and water, wherein the polyether polyol (A) satisfies all of the following (1) to (3): (1) the alkylene oxide (C) includes a 1,2-alkylene oxide (C1) having 3 or more carbon atoms, (2) a content of ethylene oxide in the alkylene oxide (C) is 0 to 35 mol% and (3) a primary hydroxyl group percentage among terminal hydroxyl groups of the polyether polyol (A) is 40% or more.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition suitable for producing a polyurethane foam and a method for producing a polyurethane foam using the same.

  Rigid polyurethane foam is used in a wide range of heat insulating materials such as building materials, refrigerators, freezers, structural materials, and on-site building construction sprays because of its heat insulating performance, dimensional stability at low temperatures, and workability. .

  In the past, chlorofluorocarbons have been used for foaming urethane foam. However, HFC-245fa and HFC-365mfc are used as alternative chlorofluorocarbons as hydrofluorocarbons (HFCs) instead of chlorofluorocarbons with high greenhouse effect. However, all of them have a high global warming potential (GWP), and in 2020, a regulation prohibiting the use of alternative chlorofluorocarbons for building materials will be implemented.

  Hydrofluoroolefins HFO-1233zd and HFO-1336mzz-Z, which have less environmental impact (smaller GWP), have been developed as alternatives to alternative chlorofluorocarbons, and are being replaced toward 2020.

  However, hydrofluoroolefins have the drawback of decomposing and reacting with amines with high nucleophilic power, so the types of amine catalysts and amine polyols that can be used are limited, and polyols using conventional blowing agents It is difficult to increase the reaction activity during urethane foaming compared to the composition.

The polyol composition containing hydrofluoroolefin as a foaming agent includes a technique (Patent Document 1) containing a imidazole catalyst and an organic acid in the polyol composition, a salt such as an amine and an organic acid, and a pH of 7 By the technique (patent document 2) containing the catalyst composition which becomes 0.0 or less, it is possible to impart reaction activity and maintain storage stability.
However, in these methods, the amount of the catalyst used is increased in order to obtain the same level of activity as in the prior art, and the cost increase as a polyol composition is a problem.
In rigid polyurethane foam applications, it is common to use polyols with a high ethylene oxide content as a method for improving the reaction activity with isocyanates, but the polyol composition has poor compatibility with hydrofluoroolefins, and foam However, there is a problem that the swelling and strength at the time of demolding are small. Moreover, if the compatibility is poor, separation of the premix solution containing hydrofluoroolefin and polyol and poor foaming may occur.

International Publication 2015/012267 JP2016-29180A

  The present invention relates to a polyol composition which is excellent in reaction activity with isocyanate even when hydrofluoroolefin is used instead of hydrofluorocarbon, and has good compatibility between polyol and hydrofluoroolefin; and polyurethane foam using the same It aims at providing the manufacturing method of.

As a result of intensive studies, the present inventors have found that the use of a polyol composition having the following contents can solve the problem, and have reached the present invention.

That is, the present invention contains a polyether polyol (A), which is an adduct obtained by adding an alkylene oxide (C) to a compound (B) having two or more active hydrogens, a hydrofluoroolefin (D), and water. A polyol composition for producing a polyurethane foam (H) in which the polyether polyol (A) satisfies all of the following (1) to (3): This polyol composition for producing a polyurethane foam (H) It is a manufacturing method of the polyurethane foam which makes an organic polyisocyanate (Z) react.
(1) The alkylene oxide (C) contains 1,2-alkylene oxide (C1) having 3 or more carbon atoms.
To do.
(2) The content of ethylene oxide in the alkylene oxide (C) is 0 to 35 mol%.
(3) The primary hydroxyl group ratio of the terminal hydroxyl group of the polyether polyol (A) is 40% or more.

  The polyol composition of the present invention is excellent in reaction activity as compared with the conventional polyol composition and has high compatibility with the hydrofluoroolefin.

The polyol composition (H) for producing the polyurethane foam of the present invention comprises a polyether polyol (A), water, hydrofluoroolefin (D) and, if necessary, a flame retardant (E), a foam stabilizer (F), and a catalyst (G). In addition to the polyether polyol (A), a polyester polyol may be further used.

The polyether polyol (A) can be obtained by adding the alkylene oxide (C) to the compound (B) having two or more active hydrogens by the method described later.

Examples of the compound (B) having two or more active hydrogens include polyhydric alcohols, amines, polyhydric phenols, and polycarboxylic acids. Specific examples are given below.

Examples of polyhydric alcohols include dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol. And alicyclic diols such as cyclohexane diol and cycloalkylene glycol such as cyclohexane dimethanol, trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylol propane and trimethylol) Alkanetriols such as ethane and hexanetriol); 4 to 8 or more polyhydric alcohols having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, alkane polyols and their intramolecular or intermolecular dehydration products, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.

Examples of amines include alkanolamines, polyamines and monoamines.

Examples of the alkanolamines include alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine).

Examples of polyamines include aliphatic amines such as alkylene diamines having 2 to 6 carbon atoms (for example, ethylene diamine, propylene diamine, and hexamethylene diamine), and polyalkylene polyamines having 4 to 20 carbon atoms (the alkylene group having 2 carbon atoms). To 6 dialkylenetriamine to hexaalkyleneheptamine, such as diethylenetriamine and triethylenetetramine).

Also, aromatic polyamines having 6 to 20 carbon atoms (for example, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); alicyclic polyamines having 4 to 20 carbon atoms ( Examples thereof include isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine); heterocyclic polyamines having 4 to 20 carbon atoms (for example, piperazine and aminoethylpiperazine) and the like.

As monoamines, ammonia; as aliphatic amines, alkylamines having 1 to 20 carbon atoms (for example, n-butylamine and octylamine); aromatic monoamines having 6 to 20 carbon atoms (for example, aniline and toluidine) An alicyclic monoamine having 4 to 20 carbon atoms (for example, cyclohexylamine); a heterocyclic monoamine having 4 to 20 carbon atoms (for example, piperidine), and the like.

Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; condensates of phenol and formaldehyde (novolaks); for example, US Pat. No. 3,265,641 And polyphenols described in the book.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid and the like), and a mixture of two or more thereof.

Of these, polyhydric alcohols are preferred, and preferably have an average of 2 to 8, more preferably an average of 2.5 to 8 hydroxyl groups from the viewpoint of reactivity and viscosity.

The alkylene oxide (C) (hereinafter, alkylene oxide may be abbreviated as AO) contains 1,2-alkylene oxide (C1) having 3 or more carbon atoms, and 1,2-alkylene having 3 or more carbon atoms. The oxide preferably has 3 to 20 carbon atoms, more preferably 3 to 8 carbon atoms, such as 1,2-propylene oxide (hereinafter sometimes referred to as PO), 1,2-butylene. Examples thereof include oxide, 1,2-pentene oxide, styrene oxide and combinations of two or more of these (block and / or random addition). Preferably, it is PO.

As part of the alkylene oxide (C), as specified in the requirement (2), ethylene oxide (hereinafter sometimes referred to as EO) is added in an amount of 0 to 35 mol as the alkylene oxide (C). You may contain within the range used as%.
When the content of ethylene oxide exceeds 35 mol%, there is a concern that the compatibility with the hydrofluoroolefin deteriorates and the storage stability of the polyol composition deteriorates.
The mol% of EO with respect to the alkylene oxide (C) is preferably 20 mol% or less, more preferably 10 mol% or less, and most preferably from the viewpoints of compatibility with the hydrofluoroolefin and the physical properties of the urethane foam. Is 0%.

A method for obtaining this polyol is the method described in Japanese Patent No. 4355307, and in the presence of a specific catalyst, the compound (B) having two or more active hydrogens is added to 1,2- Examples include a method of adding alkylene oxide and further adding ethylene oxide.

The primary hydroxyl group ratio of the terminal hydroxyl group of the polyether polyol (A) is 40% or more, and preferably 45% or more, more preferably 50% or more from the viewpoint of reactivity at the time of urethane foam formation.
When the primary hydroxyl group ratio of the terminal hydroxyl group of (A) is less than 40%, there is a problem that good reaction activity cannot be obtained.
Specific examples of the polyether polyol (A) include a polyether polyol having a hydroxyl value of 428 and a primary OH conversion rate of 63% obtained by adding 5.2 mol of propylene oxide to 1 mol of glycerin having 3 functional groups, A polyether polyol having a hydroxyl value of 474, a primary OH conversion rate of 54%, and a sorbitol having a functional group number of 3.9, obtained by adding 5.9 moles of propylene oxide to 1 mole of a sorbitol / glycerin mixture having a base number of 3.9 A polyether polyol having a hydroxyl value of 474 and a primary OH conversion rate of 60%, which is obtained by adding 5.15 mol of propylene oxide to 1 mol of glycerin mixture and then adding 1 mol of ethylene oxide.

The hydrofluoroolefin (D), which is an essential component of the present invention, is a next-generation blowing agent characterized by a very low global warming potential GWP that replaces the conventional hydrofluorocarbon (HFC). For example, HFO-1233zd (trans-1-chloro-3,3,3-trifluoropropene) has a global warming potential GWP generally lower than 1 compared with the conventionally used blowing agent hydrofluorocarbon HFC, and is nonflammable. It is a non-fluorocarbon material.

In the polyol composition (H) for producing polyurethane foam, water is preferably 0.1 to 10% by weight, more preferably 0.5 to 5.0% from the viewpoint of foam physical properties of the foam, based on the weight of (H). Contains by weight. The hydrofluoroolefin (D) is preferably contained in an amount of 1 to 40% by weight, more preferably 10 to 30% by weight, based on the weight of (H), from the viewpoint of foam physical properties of the foam.

The characteristics of the polyol composition for producing polyurethane foam are that it is excellent in reaction activity as compared with the conventional polyol composition, is highly compatible with hydrofluoroolefin, and has good storage stability.

The polyol composition (H) for producing a polyurethane foam of the present invention can be reacted with an organic polyisocyanate (Z) to produce a polyurethane foam.
The isocyanate index of the organic polyisocyanate (Z) is preferably 100 to 350, and more preferably 120 to 300.

As organic polyisocyanate (Z) used by this invention, what is necessary is just a compound which has two or more isocyanate groups in a molecule | numerator, and what is normally used for manufacture of a polyurethane foam can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

Moreover, when the hydroxyl value of polyether polyol (A) is 200-650 mgKOH / g, the polyol composition (H) for polyurethane foam production of the present invention is preferred for the production of rigid polyurethane foam. For production of rigid polyurethane foam, the hydroxyl value of (A) is more preferably from 250 to 600 mgKOH / g, still more preferably from 300 to 550 mgKOH / g.

Examples of the flame retardant (E) include phosphate esters, halogenated phosphate esters, aluminum hydroxide, antimony oxide, boron compounds, bromine compounds, chlorinated paraffins, and cyclic fatty acids. Of these, preferred are phosphoric acid esters and halogenated phosphoric acid esters.

Examples of the foam stabilizer (F) include dimethylsiloxane-based and polyether-modified dimethylsiloxane-based.

Examples of the catalyst (G) include primary to tertiary amine catalysts such as bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, 3,3′-iminobis (N, N-dimethylaminopropyl). Amine), N-methyl- (dimethylaminopropyl) aminoethanolamine, dimorpholinodiethyl ether, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, dimethylethanolamine, diethylethanolamine , Dimethylaminopropylamine, tetramethylethylenediamine, tetramethylpropylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, dimethylcyclohexylamine, methyldicycle Hexylamine, triethylenediamine, tris (3-dimethylaminopropyl) amine, tris (3-dimethylaminopropyl) hexahydro-s-triazine, tris (dimethylaminomethyl) phenol, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, N-methylmorpholine, N-ethylmorpholine, dimethylaminoethylmorpholine, diaminobicyclooctane, and 1,8-diazabicyclo- [5,4,0] -undecene-7,1,5 -Diazabicyclo [4,3,0] -nonene-5 and the like, and salts of these primary to tertiary amines and carboxylate anions. Metal catalysts such as stannous octylate, dibutylstannic dilaurate, lead octylate, etc.). Examples of the trimerization catalyst include potassium octylate and quaternary ammonium salts.

In the production method of the present invention, other additives can be used as necessary.
Other additives include colorants (dyes, content, etc.), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resins, etc.) ), Antioxidants (hindered phenols, hindered amines, etc.), anti-aging agents (triazoles, benzophenones, etc.), mold release agents (wax, metal soaps, or a mixture thereof), etc. The reaction can be carried out in the presence of an agent.

A specific example of the method for producing the rigid polyurethane foam of the present invention is as follows.
First, a predetermined amount of polyether polyol (A), water, hydrofluoroolefin (D) and, if necessary, flame retardant (E), foam stabilizer (F), and catalyst (G) are mixed. At this time, conventionally used polyether polyols and polyester polyols may be used. Next, using a polyurethane foaming machine or a stirrer, a mixed solution (foaming stock solution) obtained by rapidly mixing the mixture and the organic polyisocyanate (E) is poured into a mold, cured for a predetermined time, and demolded to obtain a rigid polyurethane foam. The mold may be either an open mold (free foaming) or a closed mold (mold foaming), and may be at room temperature or under heating (for example, 30 to 80 ° C.). Moreover, either spray foaming or continuous foaming may be used. The urethanization reaction is preferably a one-shot method in the prepolymer method because the viscosity of the stock solution in which each component is mixed increases.
The method of the present invention can be applied to slab foam and molding by RIM (reaction injection molding) method, and can also be used to obtain rigid polyurethane foam by mechanical flossing method.

The rigid polyurethane foam obtained by the production method of the present invention is excellent in compressive strength and dimensional stability. This is because the reaction activity is improved by using the polyether polyol (A) having a low EO content and a high primary OH conversion rate.

As for the density (kg / m ³ ) of the rigid polyurethane foam obtained by the production method of the present invention, the core density with skin is preferably 80 or less, more preferably 15 to 78, particularly preferably 20 to 75, in mold foaming. Most preferably, it is 25-70. In free foaming, the core density is preferably 50 or less, more preferably 10 to 65, particularly preferably 15 to 63, and most preferably 20 to 61.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.

Examples 1 to 5 in Table 1 show the polyol composition of the present invention.
In addition, comparative polyol compositions were shown in Comparative Examples 1 to 9 in Table 1. The raw materials used in Table 1 are as follows.
(1) Polyether polyol (A)
(A-1) 5.2 mol of PO was added to 1 mol of glycerol using tris (pentafluorophenyl) boron as a catalyst [amount of catalyst: 50 ppm (based on reaction product), reaction temperature: 75 ° C.]. Mn (number average molecular weight) = 394, hydroxyl value = 428, EO / AO = 0 mol%, primary hydroxyl group ratio of terminal hydroxyl groups = 63%.
(A-2) 1 mol of glycerol was added with 3.9 mol of PO using tris (pentafluorophenyl) boron as a catalyst, 1.7 mol of EO was further added using potassium hydroxide as a catalyst, and then the catalyst component was removed. is there.
Mn = 393, hydroxyl value = 428, EO / AO = 30 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 75%.
(A-3) 1 mol of a sorbitol / glycerin mixture having a functional group number of 3.9 is added with 5.9 mol of PO using tris (pentafluorophenyl) boron as a catalyst. Mn = 461, hydroxyl value = 474, EO / AO = 0 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 54%.
(A-4) Add 5.2 mol of PO using tris (pentafluorophenyl) boron as a catalyst to 1 mol of a sorbitol / glycerin mixture having 3.9 functional groups, and add 1.0 mol of EO using potassium hydroxide as a catalyst. Then, the catalyst component is removed. Mn = 462, hydroxyl value = 474, EO / AO = 16 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 60%.

(2) Polyether polyol (X)
(X-1) 1 mol of m-toluenediamine is added with 2.5 mol of EO in the absence of a catalyst, 5.6 mol of PO is further added with potassium hydroxide as a catalyst, and the catalyst is neutralized with acetic acid. .
Mn = 557, hydroxyl value = 403, EO / AO = 31 mol%, primary hydroxyl group ratio of terminal hydroxyl groups = 2%.
(X-2) PO4 mol is added to 1 mol of ethylenediamine under no catalyst. Mn = 292, hydroxyl value = 768, EO / AO = 0 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 2%.

(3) Polyether polyol (Y)
(Y-1) PO 5.2 mol is added to 1 mol of glycerol using potassium hydroxide as a catalyst, and then the catalyst component is removed. Mn = 394, hydroxyl value = 428, EO / AO = 0 mol%, primary hydroxyl group ratio of terminal hydroxyl groups = 2%.
(Y-2) After adding 3.4 mol of PO with 1 mol of glycerin as a catalyst, 2.3 mol of EO was subsequently added, and then the catalyst components were removed.
Mn = 390, hydroxyl value = 431, EO / AO = 40 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 40%.
(Y-3) One mole of glycerin is added with 1.6 moles of PO as potassium hydroxide as a catalyst, followed by 4.7 moles of EO, and then the catalyst components are removed.
Mn = 392, hydroxyl value = 430, EO / AO = 75 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 75%.
(Y-4) PO5.9 mol was added to 1 mol of a sorbitol / glycerin mixture having a functional group number of 3.9 using potassium hydroxide as a catalyst, and then the catalyst component was removed. Mn = 461, hydroxyl value = 474, EO / AO = 0 mol%, primary hydroxyl group ratio of terminal hydroxyl groups = 2%.
(Y-5) After adding 3.9 mol of PO using potassium hydroxide as a catalyst to 1 mol of a sorbitol / glycerin mixture having a functional group number of 3.9, subsequently adding 2.6 mol of EO, and then removing the catalyst components It is. Mn = 460, hydroxyl value = 476, EO / AO = 40 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 40%
(Y-6) After adding 2.7 mol of PO using potassium hydroxide as a catalyst to 1 mol of a sorbitol / glycerin mixture having a functional group number of 3.9, subsequently adding 4.2 mol of EO, and then removing the catalyst components It is. Mn = 460, hydroxyl value = 475, EO / AO = 61 mol%, primary hydroxyl group ratio of terminal hydroxyl group = 60%.

(4) Foaming agent (D-1) Hydrofluoroolefin HFO-1233zd (Honeywell “Solstice® LBA”)

(5) Flame retardant (E)
(E-1) Trichloropropyl phosphate (manufactured by Daihachi Chemical Co., Ltd.)

(6) Foam stabilizer (F)
(F-1) Polyether siloxane polymer (“SH-193” manufactured by Toray Dow Corning Co., Ltd.)

(7) Catalyst (G)
(G-1) Catalyst (“POLYCAT201” manufactured by AIR PRODUCTS)
(G-2) Catalyst (salt consisting of 1,2-dimethylimidazole and formic acid)

(8) Organic polyisocyanate (Z)
(Z-1) Crude MDI (“MR-200” manufactured by Tosoh Corporation), NCO% = 31.5

[Examples 1-5, Comparative Examples 1-9] (Method for producing polyurethane foam)
The manufacturing method of the rigid polyurethane foam of Examples 1-5 and Comparative Examples 1-9 is as follows.
In the number of parts shown in Table 1, the temperature of the polyol composition (H) for producing polyurethane foam was adjusted to 20 ± 5 ° C., and the predetermined amount of the organic polyisocyanate (Z) adjusted to 20 ± 5 ° C. was predetermined. The mixture was rapidly mixed at 8000 rpm for 7 seconds with a stirrer [Homodisper: manufactured by Primex]. Thereafter, free foaming was performed using a 250 × 250 × 400 mm box to confirm the reactivity. The physical properties of the foam were measured.

The primary hydroxyl group ratio of the terminal hydroxyl group of the polyether polyol (A) used in each Example and Comparative Example, the EO content in (A), and the compatibility of the hydrofluoroolefin (D) and the polyether polyol (A), Table 1 shows the measurement results of the reaction activity (cream time, gel time, rise time) of the polyol composition (H) for producing polyurethane foam, the density of the molded polyurethane foam, the compressive strength, and the dimensional stability.
The measurement method is described below.

<Measurement of primary hydroxyl group ratio of terminal hydroxyl groups>
In the present invention, the primary hydroxyl group ratio of the terminal hydroxyl group is calculated by ¹ H-NMR method after pre-treatment of the sample in advance. Details of the ¹ H-NMR method will be specifically described below.
Sample Preparation Method About 30 mg of a measurement sample is weighed into a ¹ H-NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added, and the mixture is allowed to stand at 25 ° C. for about 5 minutes.
Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

NMR measurement ¹ H-NMR measurement is performed under normal conditions.
Calculation Method of Primary Hydroxyl Ratio of Terminal Hydroxyl Group A signal derived from a methylene group bonded with a primary hydroxyl group is observed around 4.3 ppm, and a signal derived from a methine group bonded to a secondary hydroxyl group is observed around 5.2 ppm. Therefore, the primary hydroxyl group ratio of the terminal hydroxyl group is calculated by the following formula.
Primary hydroxyl group ratio (%) = [r / (r + 2s)] × 100
However,
r: integrated value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm s: an integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm.

<Method for evaluating compatibility of hydrofluoroolefin (D) and polyether polyol (A)>
In a 250 mL pressure bottle, 100 g of polyether polyol (A) is weighed. Hydrofluoroolefin (D) is added thereto, and the maximum dissolution amount (g) is confirmed. If no separation occurs even when 100 g or more of (D) is added, the test ends. (A) and (D) are temperature-controlled at 25 ° C., and the measurement is performed at 25 ° C.
The compatibility is indicated by the maximum dissolution amount (g) of (D).

<Measurement of molded product density>
It was calculated by the following formula. Unit is kg / m ³
Molded product density (kg / m ³ ) = (Molded product weight (g)) / Molded product volume (cm ³ ) × 1000
<Measurement of compressive strength>
Conforms to JISA9511 (2009).
<Measurement of dimensional stability>
Conforms to JISK7249 (2006).

When Example 1 and Comparative Example 1 are compared with each other, a polyether polyol composed only of PO starting from glycerin and having a hydroxyl value of 428 is used, but Example 1 has a primary OH conversion rate of 63%. Therefore, the reaction activity is 38 (s) in gel time. In contrast, Comparative Example 1 shows that the primary OH conversion rate is as low as 2%, the gel time is as low as 90 (s), and the activity of the polyether polyol is low.
Further, when Example 1 and Comparative Examples 3 and 4 are compared, all are polyether polyols having a glycerol start and a hydroxyl value of 428. In order to obtain the same reaction activity as Example 1, the polyether of Comparative Example 4 is used. Like polyol (Y-3), it is necessary to make EO / AO in (C) 75 mol% or more. When the reaction activity is increased by increasing the EO content as in (Y-3), the compatibility with the hydrofluoroolefin (D-1) is decreased, which may cause separation.
Therefore, it turns out that the polyether polyol (A-1) used in Example 1 has high reaction activity and high compatibility with the hydrofluoroolefin.

  Regarding the reaction activity, the same can be said for Example 2 and Comparative Example 2, and Example 4 and Comparative Example 7. The same can be said for Example 4 and Comparative Examples 8 and 9 in terms of compatibility.

Comparing Example 3 and Comparative Example 3, Example 3 uses a polyether polyol (A-2) having a glycerin starting value, a hydroxyl value of 428, EO / AO = 30 mol%, and a primary conversion rate of 75%. Comparative Example 3 uses a polyether polyol (Y-2) having a glycerin starting value, a hydroxyl value of 431, EO / AO = 40 mol%, and a primary conversion rate of 40%.
Although (A-2) of Example 3 has a high primary conversion rate of 75% despite having EO / AO = 30 mol%, it has good compatibility and high reaction activity. On the other hand, although (Y-2) of the comparative example 3 is EO / AO = 40 mol%, since the primary rate is as low as 40%, compatibility falls and reaction activity is also low.
The same can be said for Example 5 and Comparative Example 8.

  When Example 1 is compared with Comparative Examples 5 and 6, in Comparative Examples 5 and 6, amine-based polyether polyols (X-1) and (X-2) are used to increase the reaction activity. It can be seen that the activity as high as the polyether polyol (A-1) of Example 1 cannot be obtained.

The polyurethane foam obtained by reacting the polyol composition (H) for producing the polyurethane foam of the present invention with the organic polyisocyanate (Z) can be applied to a heat insulating material or a structural material such as a building material, a household appliance, and a transportation machine.

Claims (5)

A polyol composition comprising a polyether polyol (A), which is an adduct obtained by adding an alkylene oxide (C) to a compound (B) having two or more active hydrogens, a hydrofluoroolefin (D), and water. The polyol composition (H) for producing a polyurethane foam, in which the polyether polyol (A) satisfies all of the following (1) to (3).
(1) The alkylene oxide (C) contains 1,2-alkylene oxide (C1) having 3 or more carbon atoms.
(2) The content of ethylene oxide in the alkylene oxide (C) is 0 to 35 mol%.
(3) The primary hydroxyl group ratio of the terminal hydroxyl group of the polyether polyol (A) is 40% or more. The polyol composition according to claim 1, wherein the 1,2-alkylene oxide (C1) having 3 or more carbon atoms is 1,2-propylene oxide. The polyol composition according to claim 1 or 2, comprising 0.1 to 10% by weight of water and 1 to 40% by weight of hydrofluoroolefin (D) based on the weight of the polyol composition (H). The polyol composition according to any one of claims 1 to 3, wherein the polyether polyol (A) has a hydroxyl value of 200 to 650 mgKOH / g. The manufacturing method of the polyurethane foam which makes the polyol composition for polyurethane foam manufacture of any one of Claims 1-4 react with organic polyisocyanate (Z).