JP7380020B2 - polyol composition - Google Patents

Description

The present disclosure relates to a polyol composition that is a raw material for polyurethane and has excellent handling properties and heat resistance.

Polyurethane is manufactured by mixing a polyol and an isocyanate compound.

Conventionally, flame retardants have been added to make polyurethane foam flame retardant. As flame retardants, flame retardants that are liquid at room temperature, such as phosphate ester monomers, have been mainly used.

Generally, when a phosphoric acid ester monomer, which is liquid at room temperature, is used as a flame retardant for polyurethane foam, it has a plasticizing effect, so as the amount of flame retardant used increases, the moldability of polyurethane tends to deteriorate. Ta.

In order to solve the above problem, a method using a chlorinated polyether polyol obtained by ring-opening polymerization of 3,4-dichloro-1,2-epoxybutane has been proposed (Patent Document 1).

Patent No. 5655281

However, such chlorinated polyether polyols have extremely high viscosity and have problems in handling. In addition, it contains many byproducts such as unsaturated components generated by side reactions during production, and there are problems with compatibility with other polyols and heat resistance.

Therefore, one aspect of the present invention is directed to providing a polyol composition that is excellent in handleability, compatibility with other polyols, and heat resistance, and is used as a raw material for producing polyurethane with excellent flame retardancy. .

Each aspect of the present invention is [1] to [2] shown below.
[1]
The number average molecular weight is 2,000 or more and 10,000 or less, and the total unsaturation degree is 0.07 meq. /g or less, has a molecular weight distribution (Mw/Mn) of 1.1 or less, and has an average number of functional groups of 2 to 4. contains a halogen-containing polyether polyol (B) with a number average molecular weight of 500 or more and 5,000 or less and a total degree of unsaturation of 0.020 meq/g or less in a range of 5% by weight or more and 90% by weight or less. polyol composition.

(In the above formula (1), m is an integer of 2 to 4, n is an integer, R ¹ is an active hydrogen-containing compound residue, and X represents a halogen atom.)
[2]
The polyol composition according to [1], which has a viscosity of 20,000 mPa·s or less at a temperature of 25°C.
<Polyol composition>
The polyol composition according to one aspect of the present invention is
Contains high purity polypropylene glycol and halogen-containing polyether polyol.
<<Polypropylene glycol (A)>>
The total unsaturation degree of the polypropylene glycol (A) is 0.07 meq. /g or less, preferably 0.04meq/g or less. If the total unsaturation degree is greater than 0.07 meq/g, it is not preferable because the compatibility with the halogen-containing polyether polyol and the heat resistance of the resulting composition deteriorate.

In this embodiment, the degree of unsaturation of polypropylene glycol was measured in accordance with the NMR method described in Kobunshi Ronsen 1993, 50, 2, 121-126. In this embodiment, since polypropylene glycol containing less unsaturated monool is to be measured, the number of scans in the NMR measurement was set to 500 or more in order to improve measurement accuracy.

Mw/Mn of the polypropylene glycol of the invention is 1.10 or less, preferably 1.08 or less. If Mw/Mn is larger than 1.10, the compatibility with the halogen-containing polyether polyol and the heat resistance of the resulting composition will deteriorate, which is not preferable.

Polypropylene glycol (A) may be a homopolymer of propylene oxide or a copolymer with ethylene oxide.
Here, polypropylene glycol (A) is obtained, for example, by ring-opening polymerization of propylene oxide using an active hydrogen-containing compound as an initiator in the presence of a polypropylene glycol polymerization catalyst containing a phosphazene compound.

Examples of the phosphazene compound include a phosphazenium salt represented by formula (2).

In formula (2),
R ² and R ³ are each independently,
hydrogen atom,
a hydrocarbon group having 1 to 20 carbon atoms,
A ring structure in which R ² and R ³ are bonded to each other, or
Represents a ring structure in which R ² or R ³ are bonded to each other;
Z ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion;
Y represents a carbon atom or a phosphorus atom;
a is
2 when Y is a carbon atom,
When Y is a phosphorus atom, it is 3. )
Examples of hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, and t-butyl group. , cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, Examples include cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group.

As R ² and R ³ , methyl, ethyl, and isopropyl groups are preferable because they provide an alkylene oxide polymerization catalyst with excellent catalytic activity and raw materials are easily available.

Further, Z ⁻ in the above phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

Examples of the alkoxy anion having 1 to 4 carbon atoms include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion, and t-butoxy anion.

Examples of the alkyl carboxy anion having 2 to 5 carbon atoms include acetoxy anion, ethyl carboxy anion, n-propyl carboxy anion, isopropyl carboxy anion, n-butyl carboxy anion, isobutyl carboxy anion, t-butyl carboxy anion, and the like. .

Among these, Z ^- is preferably a hydroxy anion or a hydrogen carbonate anion, since they provide an alkylene oxide polymerization catalyst with excellent catalytic activity.

Examples of the phosphazene compound include tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydroxide, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydrogen carbonate, and tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydrogen carbonate. Mention may be made of [tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide.

Examples of the active hydrogen-containing compound include, but are not limited to, water, hydroxy compounds, amine compounds, carboxylic acid compounds, thiol compounds, polyether polyols having hydroxyl groups, and the like.

Examples of the polyether polyol having a hydroxyl group include polyether polyols having a molecular weight of 200 or more and 1000 or less.

These active hydrogen-containing compounds may be used alone or in combination of several types.
<<Halogen-containing polyether polyol>>
The halogen-containing polyether polyol is
It is shown by formula (1),
The average molecular weight is 500 or more and 5,000 or less,
The degree of unsaturation is 0.020 meq/g or less.

In formula (1), R ¹ represents an active hydrogen-containing compound residue,
X represents a halogen atom.

In formula (1), the halogen atom represented by X is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom, and bromine atom are preferred from the viewpoint of ease of handling, and fluorine atom or chlorine atom is more preferred.

In formula (1), the active hydrogen-containing compound residue represented by R ¹ is not particularly limited, and examples thereof include hydroxy compound residues, carboxylic acid compound residues, thiol compound residues, etc. .

Examples of the hydroxy compound residue include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5 - Residues such as hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, bisphenol, and polyether polyols having hydroxyl groups.

Examples of carboxylic acid compound residues include phthalic acid and adipic acid residues.

Examples of thiol compound residues include ethanedithiol, butanedithiol, and other residues.

Among these active hydrogen-containing compound residues, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and 1,9-nonane can be used to efficiently produce halogen-containing polyether polyols. Diol, 2,5-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, residues of polyether polyols having a molecular weight of 200 or more and 1,000 or less, tripropylene glycol, 2, Particularly preferred are 5-hexanediol, 1,9-nonanediol, and residues of polyether polyols having a molecular weight of 200 or more and 1,000 or less.

The number average molecular weight of the halogen-containing polyether polyol is 500 or more and 5,000 or less, and it has excellent handling properties and compatibility with polypropylene glycol. It is preferably 500 or more and 3,000 or less. When used as a polyol composition, if the number average molecular weight is less than 500, the heat resistance will deteriorate, and if it is larger than 5,000, the viscosity will be high and the handling properties will be poor, which is not preferable.

The total unsaturation degree of the halogen-containing polyether polyol is 0.02 meq/g or less, and is particularly preferably 0.01 meq/g or less since it has excellent heat resistance when used as a polyol composition. If the total unsaturation degree is greater than 0.02 meq/g, it is not preferable because the compatibility with polypropylene glycol and the heat resistance of the resulting composition deteriorate.

The ratio (Mw/Mn) of the mass average molecular weight Mw to the number average molecular weight Mn of the halogen-containing polyether polyol is preferably 2.00 or less, particularly preferably 1.50 or less, since it has excellent heat resistance. However, the number average molecular weight determined by gel permeation chromatography measurement using polystyrene as a standard substance is Mn, and the mass average molecular weight is Mw.
<<Production method of halogen-containing polyether polyol>>
There are no particular restrictions on the method for producing the halogen-containing polyether polyol, and it can be produced by conventionally known production methods.

For example, a method of ring-opening polymerization of a halogen-containing alkylene oxide in the presence of a bifunctional or more active hydrogen-containing compound, the above-mentioned phosphazene compound or an onium salt catalyst such as an ammonium salt or a phosphonium salt, and a Lewis acid catalyst. ; can be mentioned.

Examples of Lewis acid catalysts include aluminum compounds, zinc compounds, and boron compounds.

The structure of ammonium salt or phosphonium salt is represented by formula (3):

In formula (3),
D represents a nitrogen atom or a phosphorus atom;
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently,
an alkyl group, aryl group, alkoxy group, or dialkylamino group having 1 to 20 carbon atoms;
a halogen atom, or
Represents a hydrogen atom;
E ^- represents a counter ion consisting of an inorganic or organic group;
Two to four of R ⁴ to R ⁷ may be combined to form a cyclic structure, and the cyclic structure may contain a heteroatom.

The polymerization temperature when producing a halogen-containing polyether polyol is not particularly limited, but is in the range of 70 to 150°C because the polyalkylene oxide decomposes and the molecular weight distribution is difficult to widen, making it easy to develop catalytic activity. The temperature is preferably in the range of 90 to 110°C, and more preferably in the range of 90 to 110°C.

In the method for producing a halogen-containing polyether polyol, the polymerization reaction is preferably carried out without a solvent, but it can also be carried out in a solvent. Examples of the solvent used include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1,2-dimethoxyethane.
<<Polyol composition>>
In the polyol composition according to one embodiment of the present invention, the above-mentioned halogen-containing polyether polyol (B) is contained in the above-mentioned polypropylene glycol (A) in a range of 5% by weight or more and 90% by weight or less. In order to exhibit good flame retardancy with good handling properties when used as a raw material for polyurethane, the content is preferably 8% by weight or more and 80% by weight or less, and particularly preferably 10% by weight or more and 80% by weight. . If the halogen-containing polyether polyol (B) is less than 5% by weight, sufficient flame retardancy will not be exhibited when made into polyurethane, and if it is more than 90% by weight, the polyol composition will have poor handling properties, which is not preferable.

Since the polyol composition according to one aspect of the present invention has good handling properties when used as a raw material for polyurethane, it is preferable that the viscosity is 20,000 mPa·s or less at a temperature of 25°C, and 15,000 mPa·s. The following is particularly preferable.

The polyol composition according to one embodiment of the present invention can be used for various purposes, and the uses are not particularly limited, but for example, it can be used as a raw material for polyurethane.

The polyurethane described above is produced by reacting a polyol composition according to one embodiment of the present invention with an isocyanate compound. The isocyanate compound is not particularly limited, and any compound having at least two isocyanate groups can be used. Examples include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

The above-mentioned polyurethane can be used for urethane foam applications such as rigid foam or flexible foam. Also, the name is taken from the English initials of these four uses, such as coatings, adhesives, sealants, thermoplastic or thermosetting elastomers, etc. It can be used for what is called CASE in this technical field.

Due to the characteristics of the polyurethane produced using the polyol composition according to one embodiment of the present invention, polyurethane foams can be used, for example, in seats and interior materials for automobiles and vehicles, pillows, furniture and interior decoration, bedding, shoe soles, It can be used in applications where soft polyurethane foam is applied, such as sponges, various cushions, tennis balls, and landing mats. Furthermore, the polyurethane foam made of the reaction product of the composition of the present invention can be used in applications where rigid polyurethane foam is applied, such as heat insulating/cold insulating materials, vibration isolating/sound absorbing materials, cushioning materials, buoyancy materials, etc. . For example, it can be used as insulation material for fishing boats, large ships, refrigerated cargo ships, LNG ships, LPG ships, liquefied gas ships, containers, core materials for FRP boats, and buoyancy materials for large ships, lifeboats, buoys, and floating objects. Insulation for refrigerated cars, refrigerated cars, railway containers, tank trucks, ceiling insulation for cars and trucks, insulation for chemical industry equipment tanks and piping, heat insulation for heavy oil tanks and piping, LPG, etc. Insulating materials for LNG low-temperature liquefied gas and piping, insulating covers, tank lids for plants, insulating materials for refrigerators and freezers, insulating materials for air conditioners, showcases, stockers, vending machines, water heaters, hot water storage tanks, etc. Insulation materials for various types of insulation equipment, as well as insulation materials for homes and office buildings (walls, under floors, ceilings, under roofs, etc.), insulation building materials (laminate boards, composite panels, siding materials, etc.), and bathtubs (stainless steel and FRP).・Enamel) insulation material, insulation material for frozen warehouses, refrigerated warehouses, agricultural warehouses, livestock barns, etc., void filling (insulation sash), construction and construction materials as insulation material for constant temperature rooms and regional central heating and cooling, insulation for road floors. For civil engineering as timber and anti-vibration material, as well as chair core materials, door panels, decorative crafts, recreational equipment (cooler boxes, water bottles), teaching materials (3D maps, etc.), mold materials and jigs, and surfing cores. Materials, RIM products (ski core materials, racket core materials, housings), packaging materials, etc.

Furthermore, due to the characteristics of the polyurethane produced using the polyol composition according to one embodiment of the present invention, it can be used as a coating material in many applications such as interior coating for buildings and public structures, woodworking, ships, and automobiles. I can do it.

Furthermore, due to the characteristics of the polyurethane produced using the polyol composition according to one embodiment of the present invention, adhesives can be used, for example, for laminating flexible packaging materials, that is, for snacks, boiled foods, and retort foods. For adhesion of laminated bags and laminated bags for non-food items such as detergents, etc. In the construction field, for adhesion for wrapping, underfloor heating, flooring, etc. In the electronics field, for adhesion of solar cell back sheets, LCD TVs, and other battery areas, etc. It can be used for.

In addition, due to the characteristics of polyurethane produced using the polyol composition according to one embodiment of the present invention, it can be used as a sealant for building exteriors, such as sealing ALC panels and sashes, joining RC walls, and under tiles. Sealing for building frames and window frames, sealing for water areas and plasterboard in architectural interiors, sealing for architectural materials such as waterproof bases and roofs, and special vehicles such as refrigerated cars and automobile window frames. Furthermore, it can be used for gaskets in electrical/electronic equipment, communication equipment, especially hard disk devices, etc.

Further, due to the characteristics of the polyurethane produced using the polyol composition according to one embodiment of the present invention, it is suitable for use as a thermoplastic elastomer in hoses such as high-pressure hoses, fire hoses, agricultural hoses, and painting hoses. , pneumatic tubes, hydraulic tubes, fuel tubes, dialysis tubes, tubes for arteries, veins, heart tubes, etc., scratch-prevention films and sheets for automobiles, scratch-prevention films for instrument panel skins, sofas, air mats, nursing bed sheets , diaphragms, keyboard sheets, rubber screens, conveyor belts, gaskets, synthetic leather, elastic sheets, flexible films, tarpaulins, clothing, life jackets, wet suits, hot melts, diaper supplies, packaging buffer films, medical surgical films, etc. Films and sheets, various gears, various grips, solid tires, casters, rollers, vibration/soundproof parts, pickers, bushes, bearings, anti-slips, building materials, packing, caps, watch straps, connectors, rubber screens, printing Industrial parts such as drums, grease covers, hammers, dust covers, flue parts, ball joints, instrument panel skins, gear knob skins, console box skins, leather seats, bumpers and side moldings, tail lamp seals, snow chains, bushes, dust covers, Automotive parts such as gears, bearings, caps, ball joints, pedal stoppers, door lock strikers, spring covers, anti-vibration parts, belts such as conveyor belts, timing belts, round belts, V-belts, flat belts, power and communications Can be used for electric wires such as cables, automotive ABS sensor cables, robot cables, industrial cables, and computer wiring.Other uses include sports shoes, mountain climbing shoes, ski shoes, ski boards, snowboards, motocross boots, safety shoes, high heels, Snorkels, flippers, golf ball covers, anti-slip stairs, road pole cones, roller skate wheels, various tags, sailboard supplies, ski parts, various ropes, binders, medical dressings, catheters, medical ropes, bandages, etc. , and as a thermosetting elastomer, it is used in paper manufacturing, iron plate rolling rolls, printing, small rolls for office equipment, platen rolls, rolls such as skate rollers, solid tires, casters, battery forklifts, and work transportation. For cars (pallet lifts, etc.), wheels such as industrial truck wheels, idlers for conveyor belts, guide rolls and prairie springs for cables and belts, belts such as belt cushioning materials, oil seals, electronic equipment parts and copying machines. Can be used for secondary processing materials such as cleaning grade OA equipment, round bars, pipes, square columns, plates, sheets, etc. Other items include various gears, connection rings and liners, pump linings, impeller cyclone cones, and cyclone liners. It can be used in a wide range of applications such as , polishing pads, etc.

Furthermore, in addition to the uses referred to as CASE, due to the characteristics of the polyurethane produced using the polyol composition according to one embodiment of the present invention, it can be used for leather, spandex, various inks, and the like.

EXAMPLES The present invention will be explained below with reference to Examples, but these Examples do not limit the present invention in any way. The raw materials and evaluation methods used in the following Examples and Comparative Examples are as shown below.
(Raw material 1-1) Polypropylene glycol (A) used in the examples
Polyalkylene oxides (A1) and (A3) are trifunctional polyoxypropylene glycol with a molecular weight of 400, which is obtained by sufficiently dehydrating and removing solvent using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst). It was obtained by adding sufficiently dehydrated propylene oxide to . (A1) and (A3) are polyoxypropylene glycols (triols) having three hydroxyl groups in one molecule. The properties of (A1) and (A3) are shown in Table 1. (A1) and (A3) have a small amount of unsaturated monool (low degree of unsaturation) and a narrow molecular weight distribution.

Polyalkylene oxide (A2) is sufficiently dehydrated and desolvented using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst), and is sufficiently converted into trifunctional polyoxypropylene glycol with a molecular weight of 400. It was obtained by adding dehydrated propylene oxide and then adding ethylene oxide. (A2) is polyoxypropylene glycol (triol) having three hydroxyl groups in one molecule. The properties of (A2) are shown in Table 1. (A2) has a small amount of unsaturated monool (low degree of unsaturation) and a narrow molecular weight distribution.
(Raw material 1-2) Polypropylene glycol (AC) used in comparative example
Polypropylene glycol (AC1) was obtained by adding propylene oxide to glycerin in a conventional manner using a potassium hydroxide catalyst. (AC1) is a polyoxypropylene glycol (triol) having only a propylene oxide group as an alkylene oxide group and two hydroxyl groups in one molecule. The properties of (AC1) are shown in Table 1. (AC1) has a high degree of unsaturation and does not satisfy the range of 0.070 meq/g or less.

(Raw material 2-1) Halogen-containing polyether polyol (B) used in Examples
Halogen-containing polyether polyols (B1) and (B3) are fully dehydrated and desolventized using a combination of an IPZ catalyst and triisopropoxyaluminum, and are sufficiently converted into trifunctional polyoxypropylene glycol with a molecular weight of 400. Obtained by adding dehydrated epichlorohydrin. (B1) and (B3) are polyepichlorohydrin glycols (triols) having three hydroxyl groups in one molecule. The properties of (B1) and (B3) are shown in Table 2. (B1) and (B3) have a small amount of unsaturated monool (low degree of unsaturation) and a narrow molecular weight distribution.

The halogen-containing polyether polyol (B2) is made by using a combination of an imino group-containing phosphazenium salt (hereinafter referred to as an IPZ catalyst) and triisopropoxyaluminum, thoroughly dehydrating and removing the solvent, and producing a trifunctional polyether polyol with a molecular weight of 600. It was obtained by adding sufficiently dehydrated epichlorohydrin to oxypropylene glycol. (B2) is polyepichlorohydrin glycol (triol) having three hydroxyl groups in one molecule. The properties of (B2) are shown in Table 2. (B2) has a small amount of unsaturated monool (low degree of unsaturation) and a narrow molecular weight distribution.
(Raw material 2-2) Halogen-containing polyether polyol (BC) used in comparative example
By adding epichlorohydrin to a trifunctional polyoxypropylene glycol with a molecular weight of 400 using Lewis acid catalyst BF ₃ -Et ₂ O, a trifunctional polyether polyol with a molecular weight of 2,000 ( BC1) was produced. The properties of (BC1) are shown in Table 2. (BC1) has a high degree of unsaturation and does not satisfy the range of 0.020 meq/g or less.

(Analysis of polyol properties)
<Unsaturation degree>
It was measured according to the method of JIS-K1557-6.
<Molecular weight distribution (Mw/Mn)>
10 mg of polyol and 10 ml of THF were added to a sample bottle, dissolved by standing overnight, and a sample was obtained by filtering with a PTFE cartridge filter (0.5 μm).

RI detector RI8020 was used as a detector, and TSKgel GMR-HHRL x 2 in series and HLC-8020GPC were used as measurement columns (both manufactured by Tosoh Corporation).

The measurement conditions were a column temperature of 40°C, a flow rate of 1.0 ml/min, and a solvent of THF.The molecular weight distribution (Mw/Mn) was calculated using a cubic approximated curve using standard polystyrene manufactured by Tosoh Corporation as a calibration curve. An analysis was performed.
(Evaluation method of polyol composition)
<Adjustment of polyol composition>
A mixed solution was prepared by stirring at 1500 rpm using a Primix Disper until a predetermined amount of polyol became uniform.
<Handling>
The viscosity of the prepared polyol composition was measured using a cone-plate rotational viscometer (MCR-300 manufactured by Anton-Paar) at a temperature of 25° C. and a shear rate of 0.1 (1/s).
〇 (handling performance passed): less than 20,000 mPa・s × (handling performance failure): 20,000 mPa・s or more <compatibility>
Measure the time it takes for the polyol composition to become uniform when adjusting it.
〇 (compatibility passed): less than 10 seconds
× (Compatibility failure): 10 seconds or more <Initial heat resistance>
The prepared polyol composition was subjected to TGA measurement using a DSC/TGA thermal analyzer (manufactured by TA Instruments Japan, SDT Q600), and the 1% weight loss temperature was measured. The measurement was performed under a nitrogen atmosphere with a scanning temperature of 500° C. from room temperature, a temperature increase rate of 10° C./min, and a flow rate of 100 mL/min.
〇 (Heat resistance passed): 1% weight loss temperature was 170°C or higher × (Heat resistance failed): 1% weight loss temperature was less than 170°C Examples 1 to 6.
According to the method for evaluating polyol compositions, polypropylene glycol (A) and halogen-containing polyether polyol (B) were mixed in the proportions shown in Table 3, and evaluated. All polyol compositions were excellent in handleability, compatibility, and initial heat resistance.

Comparative example 1.
According to the method for evaluating polyol compositions, 1 part by weight of polypropylene glycol (A3) and 99 parts by weight of halogen-containing polyether polyol (B1) were mixed and evaluated. The polyol composition had excellent compatibility and initial heat resistance, but poor handling properties.

Comparative example 2.
According to the method for evaluating polyol compositions, 70 parts by weight of polypropylene glycol (AC1) and 30 parts by weight of halogen-containing polyether polyol (B1) were mixed and evaluated. The polyol composition had excellent handling properties, but was inferior in compatibility and heat resistance.

Comparative example 3.
According to the method for evaluating polyol compositions, 60 parts by weight of polypropylene glycol (A2) and 40 parts by weight of halogen-containing polyether polyol (BC1) were mixed and evaluated. The polyol composition had excellent handling properties, but was inferior in compatibility and heat resistance.

The results of Examples 1 to 6 and Comparative Examples 1 to 3 are also shown in Table 3.

Claims (2)

The number average molecular weight is 2,000 or more and 10,000 or less, and the total unsaturation degree is 0.07 meq. /g or less, a molecular weight distribution (Mw/Mn) of 1.1 or less, and an average number of functional groups of 2 to 4 , and a polypropylene glycol (A) represented by formula (1). , a polyol composition comprising a halogen-containing polyether polyol (B) having a number average molecular weight of 500 or more and 5,000 or less and a total degree of unsaturation of 0.020 meq/g or less, wherein 100 weight of the polyol composition %, the halogen-containing polyether polyol (B) is contained in a range of 5% by weight or more and 30 % by weight or less.
(In the above formula (1), m is an integer of 2 to 4, n is an integer, R ¹ is an active hydrogen-containing compound residue, and X represents a halogen atom.) The polyol composition according to claim 1, having a viscosity of 20,000 mPa·s or less at a temperature of 25°C.