JP2021054923A - Polyol composition - Google Patents

Abstract

To provide a polyol composition which is used as a raw material for producing a polyurethane excellent in flame retardancy and is excellent in handleability, compatibility with other polyols, and heat resistance.SOLUTION: The polyol composition contains 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 in the range of 5 wt.% or more and 90 wt.% or less in a polypropylene glycol (A) having a number average molecular weight of 2,000 or more and 10,000 or less, a total degree of unsaturation of 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 2-4.SELECTED DRAWING: None

Description

The present disclosure relates to a polyol composition which is a raw material of polyurethane and has excellent handleability and heat resistance.

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

Conventionally, in order to make polyurethane foam flame-retardant, a flame retardant has been added and used. As the flame retardant, a flame retardant that is liquid at room temperature, such as a phosphoric acid ester monomer, has been mainly used.

Generally, when a phosphoric acid ester monomer that is liquid at room temperature is used as a flame retardant for polyurethane foam, it has a plasticizing effect, so that there is a problem that the moldability of polyurethane tends to decrease as the amount of the flame retardant used increases. It was.

In order to solve the above problems, 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).

Japanese Patent No. 5655281

However, such a chlorinated polyether polyol has a very high viscosity and has a problem in handleability. In addition, many by-products such as unsaturated components produced by side reactions during production are contained, and there are problems in compatibility with other polyols and heat resistance.

Therefore, one aspect of the present invention is directed to providing a polyol composition having excellent handleability, compatibility with other polyols, and heat resistance, which is a raw material for producing polyurethane having 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 degree of unsaturation is 0.07 meq. It is represented by the formula (1) in polypropylene glycol (A) characterized by having a molecular weight distribution (Mw / Mn) of 1.1 or less and an average number of functional groups of 2 to 4. The 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 is contained in the range of 5% by weight or more and 90% by weight or less. Polypropylene 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 is a halogen atom.)
[2]
The polyol composition according to [1], wherein the viscosity is 20,000 mPa · s or less at a temperature of 25 ° C.
<Polyform 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 degree of unsaturation of the polypropylene glycol (A) is 0.07 meq. It is / g or less, preferably 0.04 meq / g or less. If the total degree of unsaturation is larger than 0.07 meq / g, the compatibility with the halogen-containing polyether polyol and the heat resistance of the obtained composition are deteriorated, which is not preferable.

In this embodiment, the degree of unsaturation of polypropylene glycol was measured according to the NMR method described in Polymer Papers 1993, 50, 2, 121-126. In this embodiment, since polypropylene glycol having a small amount of unsaturated monool is targeted for measurement, the number of scans in NMR measurement is set to 500 or more in order to improve the measurement accuracy.

The Mw / Mn of the polypropylene glycol of the present 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 obtained composition are deteriorated, which is not preferable.

Polypropylene glycol (A) may be a homopolymer of propylene oxide or a copolymer with ethylene oxide.
Here, polypropylene glycol (A) can be 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 the formula (2).

In equation (2),
R ² and R ³ are independent of each other.
Hydrogen atom,
Hydrocarbon groups with 1 to 20 carbon atoms,
A ring structure in which R ² and R ³ are bonded to each other, or
R ² together or R ³ together represent a bond and the ring structure;
Z ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a bicarbonate anion;
Y represents a carbon atom or a phosphorus atom;
a is
When Y is a carbon atom, it is 2,
It is 3 when Y is a phosphorus atom. )
Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group and a 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, Cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group and the like can be mentioned.

The R ² and R ^3, becomes alkylene oxide polymerization catalysts having excellent catalytic activity, from the viewpoint of easy availability of raw materials, a methyl group, an ethyl group, an isopropyl group is preferable.

^{Further, Z −} in the phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, 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, t-butoxy anion and the like.

Examples of the alkylcarboxy 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 because it is an alkylene oxide polymerization catalyst having excellent catalytic activity.

Examples of the phosphazene compound include tetrakis (1,1,3,3-tetramethylguanidino) phospasenium hydroxide, tetrakis (1,1,3,3-tetramethylguanidino) phosphasenium hydrogen carbonate, and tetrakis. [Tris (dimethylamino) phosphoranilideneamino] Phosphonium hydroxide can be mentioned.

The active hydrogen-containing compound is not particularly limited, and examples thereof include water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group.

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

Then, these active hydrogen-containing compounds may be used alone or in combination of several kinds.
<< Halogen-containing polyether polyol >>
The halogen-containing polyether polyol is
Expressed by equation (1)
With an average molecular weight of 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 the 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. Of these, a fluorine atom, a chlorine atom, and a bromine atom are preferable from the viewpoint of ease of handling, and a fluorine atom or a chlorine atom is more preferable.

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

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, and 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 Includes residues such as hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoe cloth, glucose, 2-naphthol, bisphenol, polyether polyols with hydroxyl groups.

Examples of the carboxylic acid compound residue include residues such as phthalic acid and adipic acid.

Examples of the thiol compound residue include residues such as ethanedithiol and butanedithiol.

Among these active hydrogen-containing compound residues, halogen-containing polyether polyol can be efficiently produced. Therefore, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonane. Residues of diols, 2,5-hexanediols, 1,6-hexanediols, 2-methylpentane-2,4-diols, polyether polyols having a molecular weight of 200 or more and 1,000 or less are preferable, and tripropylene glycol, 2, Residues of 5-hexanediol, 1,9-nonanediol, and polyether polyols having a molecular weight of 200 or more and 1,000 or less are particularly preferable.

The halogen-containing polyether polyol has a number average molecular weight of 500 or more and 5,000 or less, and is excellent in handleability and compatibility with polypropylene glycol. Therefore, the number average molecular weight is 500 or more and 5,000 or less. It is preferable, and it is particularly preferable that it is 500 or more and 3,000 or less. When the polyol composition is prepared, if the number average molecular weight is less than 500, the heat resistance deteriorates, and if it is more than 5,000, the viscosity is high and the handleability is poor, which is not preferable.

The total degree of unsaturation of the halogen-containing polyether polyol is 0.02 meq / g or less, and 0.01 meq / g or less is particularly preferable because it is excellent in heat resistance when made into a polyol composition. If the total degree of unsaturation is larger than 0.02 meq / g, the compatibility with polypropylene glycol and the heat resistance of the obtained composition deteriorate, which is not preferable.

The ratio (Mw / Mn) of the mass average molecular weight Mw of the halogen-containing polyether polyol to the number average molecular weight Mn is preferably 2.00 or less, and particularly preferably 1.50 or less because of its excellent heat resistance. However, using polystyrene as a standard substance, the number average molecular weight determined by gel permeation chromatography measurement is Mn, and the mass average molecular weight is Mw.
<< Manufacturing method of halogen-containing polyether polyol >>
The method for producing the halogen-containing polyether polyol is not particularly limited, and the halogen-containing polyether polyol can be produced by a conventionally known production method.

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

Examples of the Lewis acid catalyst include an aluminum compound, a zinc compound, a boron compound and the like.

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

In equation (3),
D represents a nitrogen atom or a phosphorus atom;
R ⁴ , R ⁵ , R ⁶ and R ⁷ are independent of each other.
An alkyl group, an aryl group, an alkoxy group, or a dialkylamino group having 1 to 20 carbon atoms.
Halogen atom or
Represents a hydrogen atom;
E ⁻ represents a counterion consisting of an inorganic or organic group;
Two to four of R ^{4 to} R ⁷ may be bonded to form a cyclic structure, or a hetero atom may be contained in the cyclic structure.

The polymerization temperature at the time of producing the halogen-containing polyether polyol is not particularly limited, but is in the range of 70 to 150 ° C. because the polyalkylene oxide is decomposed and the molecular weight distribution is difficult to spread and the catalytic activity is easily exhibited. It is 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, 1,2-dimethoxyethane and the like.
<< polyol composition >>
In the polyol composition according to one aspect of the present invention, the halogen-containing polyether polyol (B) is contained in the polypropylene glycol (A) in the range of 5% by weight or more and 90% by weight or less. When used as a raw material for polyurethane, it has good handleability and exhibits good flame retardancy. Therefore, it 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 or less. .. If the amount of the halogen-containing polyether polyol (B) is less than 5% by weight, sufficient flame retardancy is not exhibited when the polyurethane is used, and if it is more than 90% by weight, the handling property of the polyol composition is poor, which is not preferable.

Since the polyol composition according to one aspect of the present invention has good handleability when used as a raw material for polyurethane, the viscosity is preferably 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 aspect of the present invention can be used for various purposes, and the use is not particularly limited, but it can be used as a raw material for polyurethane, for example.

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

As the polyurethane, it can be used for urethane foam applications such as hard foam or soft foam. In addition, the English acronyms for these four uses are taken, such as coatings / coatings, adhesives / adhesives, sealants, and thermoplastic or thermosetting elastomers. It can be used for an application called CASE in the present technology.

From the characteristics of polyurethane produced by using the polyol composition according to one aspect of the present invention, polyurethane foam includes, for example, seats and interior materials for automobiles / vehicles, pillows, furniture / interiors, bedding, shoe soles, and the like. It can be used in applications where soft polyurethane foam is applied, such as sponges, various cushions, tennis balls, and landing mats. Further, the polyurethane foam composed of the reaction product of the composition of the present invention can be used in applications to which a hard polyurethane foam such as a heat insulating / cold insulating material, a vibration isolating / sound absorbing material, a cushioning material and a buoyancy material is applied. .. For example, for ships such as fishing boats, large boats, frozen freight boats, LNG boats, LPG boats, liquefied gas boats, container insulation materials, FRP boat core materials, and large boats, lifeboats, buoys, and floats. For vehicles such as refrigeration vehicles, cold storage vehicles, railway containers, tank lorry insulation materials, and vehicle / truck ceiling insulation materials, chemical industry equipment tank / piping insulation materials, heavy oil tank / piping insulation materials, LPG / LNG low temperature liquefied gas cold insulation / piping insulation, insulation cover, for plants for tank lids, refrigerator / refrigerator insulation, air conditioner insulation, showcases / stockers / vending machines / water heaters / hot water tanks, etc. Insulation materials for various types of insulation equipment, as well as insulation materials for houses and office buildings (walls, underfloors, ceilings, under roofs, etc.), insulation building materials (laminated boards, composite panels, siding materials, etc.), bathtubs (stainless steel / FRP)・ Insulation of road floors for insulation of horo), insulation of frozen warehouses, refrigerated warehouses, agricultural warehouses, livestock barns, void filling (insulation sashes), insulation of constant temperature greenhouses and regional centralized heating and cooling For civil engineering as materials and anti-vibration materials, as well as chair core materials, door panels, decorative crafts, entertainment equipment (cooler boxes / water cylinders), teaching materials (three-dimensional maps, etc.), mold materials / jigs, surfing cores Examples include materials, RIM type products (ski core materials, racket core materials, housings), packing materials, and the like.

Further, due to the characteristics of polyurethane produced by using the polyol composition according to one aspect of the present invention, it is used as a coating material for many applications such as intermediate coating of buildings / public structures, woodworking, ships, and automobiles. Can be done.

Further, from the characteristics of polyurethane produced by using the polyol composition according to one aspect of the present invention, the adhesive may be, for example, a laminate for flexible packaging materials, that is, for foods for snacks, boil, and retort. For bonding non-food laminated bags such as laminated bags and detergents, for wrapping, floor warming floors, and flooring in the construction field, and for bonding solar cell backsheets, LCD TVs, and other batteries in the electronics field. Can be used for.

Further, due to the characteristics of polyurethane produced by using the polyol composition according to one aspect of the present invention, in the use of a sealing material, for building exteriors, for example, sealing of ALC panels and sashes, jointing of RC walls, and under tiles. For sealing for skeletons and window outer frames, for sealing water and gypsum boards in building interiors, for sealing for building materials such as waterproof bases and roofs, and for special vehicles such as cold storage cars and automobile window frames. It can be used for sealing, and also for gaskets in electrical / electronic equipment, communication equipment, especially hardwall equipment.

Further, due to the characteristics of the polyurethane produced by using the polyol composition according to one aspect of the present invention, in the use of elastomers, hoses such as high-pressure hoses, fire hoses, pesticide hoses, and coating hoses are used as thermoplastic elastomers. , Pneumatic tube, hydraulic tube, fuel tube, dialysis tube, arterial / vein / heart tube, etc., scratch prevention film / sheet for automobiles, instrument panel skin material, scratch prevention film for sofa, air mat, bed sheet for nursing , Diaphragm, keyboard sheet, rubber screen, conveyor belt, gasket, synthetic leather, elastic sheet, flexible film, tarpaulin, clothing, life jacket, wet suit, hot melt, diaper supplies, packing cushioning film, medical surgical film, etc. Films / sheets, various gears, various grips, solid tires, casters, rollers, anti-vibration / soundproof parts, pickers, bushes, bearings, anti-slip, building materials, packings, caps, watch belts, connectors, rubber screens, printing Industrial parts such as drums, grease covers, hammers, dust covers, hose parts, ball joints, instrument panel skins, gear knob skins, console box skins, leather seats, bumper side moldings, tail lamp seals, snow chains, bushes, dust covers, Auto parts such as gears, bearings, caps, ball joints, pedal stoppers, door lock strikers, spring covers, anti-vibration parts, conveyor belts, timing belts, round belts, V-belts, flat belts and other belts, power / communication It can be used for electric wires such as cables, ABS sensor cables for automobiles, robot cables, industrial cables, computer wiring, etc. Others include sports shoes, mountain climbing shoes, ski shoes, ski boards, snowboards, motocross boots, safety shoes, high heels, etc. Snorkels, fins, golf ball covers, non-slip stairs, road pole cones, roller skate wheels, various tags, sailboard supplies, ski parts, various ropes, binders, medical dressing materials, catheters, medical ropes, adhesive plasters, etc. For a wide range of applications, and as thermosetting elastomers, papermaking, iron plate rolling rolls, printing, small rolls for office equipment, platen rolls, rolls such as skate rollers, solid tires, casters, battery forklifts, work transportation For cars (pared lift) Etc.), Wheels such as industrial truck wheels, idlers for conveyor belts, guide rolls and prairie springs for cables and belts, belts such as belt shock absorbers and oil seals, OA for electronic equipment parts and cleaning grades for copiers, etc. It can be used for secondary processing materials such as equipment, round bars, pipes, square pillars, plates, sheets, etc. In addition, various gears, connection ring liners, pump linings, impeller cyclone cones, cyclone liners, polishing pads, etc. It can be used for a wide range of purposes.

Furthermore, in addition to these uses called CASE, it can be used for leather, spandex, various inks, etc. due to the characteristics of polyurethane produced by using the polyol composition according to one aspect of the present invention.

Hereinafter, the present invention will be described with reference to Examples, but the present Examples do not limit the present invention in any way. The raw materials used in the following Examples and Comparative Examples and the evaluation method are as shown below.
(Raw Material 1-1) Polypropylene Glycol (A) Used in Examples
Polyalkylene oxides (A1) and (A3) are trifunctional and have a molecular weight of 400 polyoxypropylene glycol after sufficient dehydration and desolvation using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst). Was obtained by adding fully dehydrated propylene oxide. (A1) and (A3) are polyoxypropylene glycol (triol) having three hydroxyl groups in one molecule. The properties of (A1) and (A3) are shown in Table 1, and (A1) and (A3) have a small amount of unsaturated monool (low degree of unsaturation) and a narrow molecular weight distribution.

The polyalkylene oxide (A2) is sufficiently dehydrated and desolvated using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst) to be sufficiently trifunctional and having a molecular weight of 400 to polyoxypropylene glycol. It was obtained by adding dehydrated propylene oxide and then further adding ethylene oxide. (A2) is a polyoxypropylene glycol (triol) having three hydroxyl groups in one molecule. The properties of (A2) are shown in Table 1. In (A2), the amount of unsaturated monool is small (the degree of unsaturation is low), and the molecular weight distribution is narrow.
(Raw Material 1-2) Polypropylene Glycol (AC) Used in Comparative Examples
Polypropylene glycol (AC1) was obtained by adding propylene oxide to glycerin by a conventional method using a potassium hydroxide catalyst. (AC1) is a polyoxypropylene glycol (triol) having only a propylene oxide group as an alkylene oxide group and having two hydroxyl groups in one molecule. The properties of (AC1) are shown in Table 1. In (AC1), the degree of unsaturation is high and the degree of unsaturation does not satisfy the range of 0.070 meq / g or less.

(Raw Material 2-1) Halogen-Containing Polyether Polyester (B) Used in Examples
The halogen-containing polyether polyols (B1) and (B3) are sufficiently dehydrated and desolvated by using an IPZ catalyst and triisopropoxyaluminum in combination, and sufficiently to be trifunctional and have a molecular weight of 400 polyoxypropylene glycol. It was 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, and (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 a trifunctional poly with a molecular weight of 600 after sufficient dehydration and desolvation by using an imino group-containing phosphazenium salt (hereinafter referred to as IPZ catalyst) and triisopropoxyaluminum in combination. It was obtained by adding fully dehydrated epichlorohydrin to oxypropylene glycol. (B2) is a polyepichlorohydrin glycol (triol) having three hydroxyl groups in one molecule. The properties of (B2) are shown in Table 2. In (B2), the amount of unsaturated monool is small (the degree of unsaturation is low), and the molecular weight distribution is narrow.
(Raw Material 2-2) Halogen-Containing Polyether Polyester (BC) Used in Comparative Examples
By adding epichlorohydrin to a trifunctional, 400 molecular weight polyoxypropylene glycol using a Lewis acid-catalyzed BF _3- Et _{2 O, a 2,000 molecular weight, trifunctional polyether polyol (} BC1) was prepared. The properties of (BC1) are shown in Table 2. In (BC1), the degree of unsaturation is high and the degree of unsaturation does not satisfy the range of 0.020 meq / g or less.

(Analysis of polyol properties)
<Degree of unsaturation>
The measurement was performed 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 allowing to stand overnight, and filtered through a PTFE cartridge filter (0.5 μm) to obtain a sample.

An RI detector RI8020 was used as a detector, and a TSKgelGMR-HHRL × 2 series, HLC-8020GPC was used as a measurement column (both manufactured by Tosoh Corporation).

The measurement conditions were a column temperature of 40 ° C., a flow velocity of 1.0 ml / min, and a solvent THF, and the molecular weight distribution (Mw / Mn) was measured using a cubic approximation curve using standard polystyrene manufactured by Tosoh Corporation as a calibration curve. The 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 prepared polyol composition was viscous measured at a temperature of 25 ° C. and a shear rate of 0.1 (1 / s) using a cone-plate rotational viscometer (MCR-300 manufactured by Antonio-Par).
〇 (Handling passability): Less than 20,000 mPa · s × (Handleability failure): 20,000 mPa · s or more <Compatibility>
When the polyol composition was prepared, the time required for homogenization was measured.
〇 (passing compatibility): 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 (SDT Q600, manufactured by TA Instruments Japan), and the 1% weight loss temperature was measured. The measurement was performed under a nitrogen atmosphere in which the scanning temperature was room temperature to 500 ° C., the rate of temperature rise was 10 ° C./min, and the flow rate was 100 mL / min.
〇 (passed heat resistance): 1% weight loss temperature is 170 ° C or higher × (failed heat resistance): 1% weight loss temperature is less than 170 ° C Examples 1 to 6.
According to the evaluation method of the polyol composition, polypropylene glycol (A) and halogen-containing polyether polyol (B) were mixed at the ratios shown in Table 3 and evaluated. All of the polyol compositions were excellent in handleability, compatibility, and initial heat resistance.

Comparative example 1.
According to the evaluation method of the polyol composition, 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 was excellent in compatibility and initial heat resistance, but inferior in handleability.

Comparative example 2.
According to the evaluation method of the polyol composition, 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 was excellent in handleability, but inferior in compatibility and heat resistance.

Comparative example 3.
According to the evaluation method of the polyol composition, 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 was excellent in handleability, but 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 degree of unsaturation is 0.07 meq. It is represented by the formula (1) in polypropylene glycol (A) characterized by having a molecular weight distribution (Mw / Mn) of 1.1 or less and an average number of functional groups of 2 to 4. The 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 is contained in the range of 5% by weight or more and 90% by weight or less. Polypropylene 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 is a halogen atom.) The polyol composition according to claim 1, wherein the viscosity is 20,000 mPa · s or less at a temperature of 25 ° C.