JP2605035B2 - Accelerator for solubilization of CFCs in aromatic polyester polyols - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a CFC solubilization accelerator for aromatic polyester polyols. More specifically, the present invention relates to an accelerator for solubilizing CFCs in an aromatic polyester polyol for a urethane resin raw material.

(Prior art)

Polyurethane resins are mainly composed of polyisocyanates and polyol compounds. There are various types of the polyisocyanate compound and the polyol compound, and a polyurethane resin having various characteristics can be obtained depending on a combination thereof. At present, it is used in various fields by making use of its various characteristics and functions. For example, when classified according to the form of use, there are fibers, synthetic leathers, films, foams, molding materials, elastomers, adhesives and paints. In addition, when categorized according to the use, subdivided individual uses such as clothing, miscellaneous goods, space development equipment, surgery, sealant, caulking, resin concrete, soil improvement agent, seamless floor, paint film waterproofing agent, etc. are found. Are increasingly proliferating. Especially in polyurethane foam, vehicles,
It is used in the fields of building materials, furniture, ships, plants, packaging, cold insulation materials, and cold insulation materials for cryogenic freezers with a temperature of -30 ° C.

Reaction injection molding (Reaction Injection Molding), a process for producing polymer products from highly reactive chemical raw materials
The term RIM is being used for short. This reaction injection molding has been experimentally attempted on various polymers. However, it is well known that polyurethane resins are the only polymers produced by this process industrially to date. this is,
That is, even if it is industrially produced, there is no other chemical raw material that is more reactive than the raw material of the polyurethane resin. In addition, since almost all of the raw materials are in a liquid state at a normal outside temperature, they also have an advantage in handling that they are very easy to handle.

In reaction injection molding, injection molding is performed using a high-pressure collision mixer. However, polyurethane resin has attracted public attention because it can be easily molded without using a large-scale RIM molding apparatus. For example, by selecting the type of the isocyanate and the polyol to be combined or the type of the catalyst, there is a characteristic that the reaction molding can be performed at room temperature or a low temperature condition such as 0 ° C. or lower. The use of a foaming agent also has the characteristic that the apparent density can be reduced to about 0.020 g / cm ³ and can be made very light. The expansion of applications of polyurethane resins having various properties and functions is inevitable, but this is due to technological advances in raw materials such as polyisocyanate, additives such as catalysts and foam stabilizers, and molding machines. This is largely due to advances in molding techniques. However, even more than that, the progress of the raw material technology for polyol compounds has been a major factor, and the technology for making the best use of them has been greatly advanced.

Most of the raw material polyols for polyurethane resins produced as polyol compounds are polyether polyols having an ether bond in the main chain. Examples of general-purpose polyether polyols include polyoxyalkylene glycol (PPG and the like) and polytetramethylene ether glycol (PTMG). Various polyols can be obtained by selecting starting materials for polyoxyalkylene glycol. When the starting material is water, propylene glycol or ethylene glycol, etc.
It becomes a diol type polyol having two groups. When the starting material is glycerin, trimethylolpropane, triethanolamine, or the like, a triol-type polyol having three OH groups is obtained. In the same manner, a tetraol type polyol from pentaerythritol and the like, a hexaol type polyol from sorbitol and the like, and an octitol type polyol from sucrose can be obtained, respectively. These polyols can be obtained relatively inexpensively because they are produced in large quantities.

Polyester polyols are roughly classified into two types. That is, they are non-aromatic and aromatic polyols. Non-aromatics have been conventionally produced and used industrially, but are not quantitatively higher than polyether-based polyols. For example, there are condensed polyester polyols produced by dehydration condensation of a dibasic acid such as adipic acid and glycol or triol, and lactone polyester polyols obtained by ring-opening polymerization of ε-caprolactone.

On the other hand, aromatic polyether polyols are hardly produced and used industrially in Japan, but are used in foreign countries, especially in Europe and the United States, in the same amount as polyether type polyols. . In recent years, the aromatic polyester polyol has been imported at a low cost, and in response to this trend, some manufacturers have tried to produce it in Japan.

However, at the current technical level, the amount in which the aromatic polyester polyol can be blended without deteriorating the physical properties of the polyurethane resin is up to 30 to 40% by weight in the total polyol. With such a composition, there is no cost advantage, and the amount used does not increase. Although the price is very low, it has a fatal drawback. The disadvantage is that it is hardly compatible with Freon gas used as a foaming agent. Even if the aromatic polyester all and the fluorocarbon are stirred and mixed, they do not dissolve each other, and immediately cause separation. Therefore, as long as freon gas is used as a foaming agent, all polyols such as polyethers currently used as polyols for polyurethane resin raw materials are replaced with this aromatic polyester polyol, and, of course, only a part thereof is replaced. Very difficult to use. Even if molding such as foaming is performed by mechanically forcibly stirring and mixing, the physical properties of the molded article are deteriorated. Therefore, in order to improve this disadvantage as much as possible, a solubilization accelerator for improving the solubility of CFCs in the aromatic polyester polyol has been required.

By the way, when a polyurethane resin is usually produced on an industrial scale, the reaction is performed in the same manner on a laboratory scale, but the raw material is divided into two liquids in advance, and the two liquids are mixed and reacted. It produces and manufactures polyurethane resin products. These two liquids are each liquid A,
It is called B liquid. The liquid A is mainly composed of a polyisocyanate compound. Usually, the liquid B contains 2 to 4 kinds of polyol compounds, a catalyst such as a tertiary amine, an additive such as a silicone-based foam stabilizer, and CFC11.
And the like. A small amount of water may be added to the solution B.

Therefore, even if an aromatic polyester polyol is blended and stored as one of the polyols in the liquid B composition, if the compatibility with Freon is low, separation occurs at this storage stage and the product is introduced into the production process. You can't.

[Object of the invention]

An object of the present invention is to provide a solubilizing accelerator polyol that promotes solubilization of CFCs in an aromatic polyester polyol.

[Configuration of the invention]

According to the present invention, the following general formulas (I), (II) and / or
Alternatively, there is provided an accelerator for solubilizing CFCs in an aromatic polyester polyol, comprising at least one compound selected from the compounds represented by (III) as an essential component.

Or / and (Where R, R ¹ , R ² , x ₁ , x ₂ , y ₁ , y ₂ , y ₃ , z ₁ , z ₂ ,
n represents the following.

R: linear or branched alkyl group, hydroxyalkyl group, alkenyl group or hydroxyalkenyl group having an average of 19 to 40 carbon atoms R ¹ : hydrogen or methyl group (however, a hydrogen or methyl group is randomly or blockwise combined) R ² : linear or branched alkyl group, hydroxyalkyl group, alkenyl group or hydroxyalkenyl group having an average of 18 to 39 carbon atoms x ₁ , x ₂ , y ₁ , y ₂ , y ₃ , z ₁ , z ₂ : each an integer of 1 to 20 n: an integer of 2 or 3) Hereinafter, the present invention will be described in more detail.

The higher aliphatic amine-based polyol, which is a solubilizing accelerator for CFCs of the present invention, is characterized by having a long-chain hydrocarbon group, and is represented by the general formulas (I) and (II). R is a linear or branched alkyl group, hydroxyalkyl group, querenyl group or hydroxyalkenyl group having 19 to 40, preferably 20 to 26 carbon atoms.

R ² represented by the general formula (III) has an average carbon number of 18 to 39,
It is preferably a linear or branched alkyl group, hydroxyalkyl group, alkenyl group or hydroxyalkenyl group of 19 to 25.

R groups of the general formulas (I) to (III) and Examples of the fatty acid residue include eicosanoic acid (C ₂₀ : the symbol represents the number of carbon atoms, in this case, a fatty acid having 20 carbon atoms. The same applies hereinafter), docosanoic acid (C ₂₂ ), tetracosanoic acid (C ₂₄ ), hexacosanoic acid (C
₂₆ ), residues of linear saturated fatty acids such as octacosanoic acid (C ₂₈ ) and triacontanic acid (C ₃₀ ). cis-9-eicosenoic acid (C ₂₀ F1: Numerical attached to the symbol F represents the number of unsaturated bonds that is, this case represents a fatty acid 20 carbon atoms and having one double bond subsequent similar...) , cis-11- eicosenoic acid _{(C 20 F1), cis-} 13- docosenoic acid (C ₂₂ F1), c
IS-15-tetracosenoic acid _{(C 24 F1), cis-} 17- hexacosenoic acid _{(C 26 F1), cis-} 19- octacosenoic acid (C ₂₈ F
1), residue of cis-21- triacontene acid (C ₃₀ F1) monoene unsaturated fatty acids such as. 8,11,14- eicosatrienoic acid (C ₂₀ F3), 7,10,13- docosatriene acid (C ₂₂ F3)
Residues of triene unsaturated fatty acids such as 5,8,11,14-eicosatetraenoic acid (C ₂₀ F4), 8,12,16,19- docosatetraenoic acid (C ₂₂ F4) residues of tetraene unsaturated fatty acids such as. 4,8,12,15,18- eicosapentaenoic acid (C ₂₀ F5), 4,8,12,15,19- docosapentaenoic acid (C ₂₂ F5) residues of pentane unsaturated fatty acids such as. Alternatively, 4,8,12,15,18,21- tetra co hex enoic acid (C ₂₂ F6) residues such hexaene unsaturated fatty acids, and the like. The R groups of the general formulas (I) and (II) And an R group obtained by a method such as reduction of an aliphatic residue.

These fatty acid residues may be natural fatty acid residues derived from plants or animals, or may be synthetic fatty acid residues such as chemically synthesized. In the case of synthetic fatty acid residues, not only those having an even number of carbon atoms as described above but also those having an odd number of carbon atoms are included. Further, 22-hydroxy docosanoic acid (C _22), may be the residue of a fatty acid such as oxygenated such as 2-hydroxy-tetra-co San acid (C _24).

Examples of natural fatty acid residues of vegetable or animal origin include, for example, peanut oil, crambe oil, carnauba wax, montan wax, shark liver oil, horn shark liver oil, herring oil, whale oil, jojoba oil, sardine oil It can be obtained from squid oil, sardine whale oil, rapeseed oil, oily family seed oil, shabby seed oil, and the like. The oxygen-containing fatty acid residue can be obtained from bark oil of cork, cereproside of brain and the like.

Currently, industrial methods for the synthesis of fatty acids from petroleum are as follows: liquid-phase air oxidation of paraffin, hydroformylation of olefins (oxo method) or carbonylation (Koch method).
Etc., and are manufactured on a large scale. If it is a fatty acid residue derived from animal and vegetable oils, those having an average carbon number of about 30 are considered to have the maximum carbon number.However, under conditions of high temperature and high pressure, the higher alcohol is dehydrogenated, and aldol condensation is performed. By performing dimerization or the like by a Guerbet reaction or the like for performing hydrogenation or the like, a higher fatty acid having twice the number of carbon atoms can be obtained. By using this method and the like, one having about 40 carbon atoms can be synthesized, and is actually used industrially. In the oxo method, etc., olefin is brought into contact with carbon monoxide and hydrogen,
An aldehyde having one more carbon atom than the olefin of the raw material is obtained, and the aldehyde is further induced to a resin acid. By using this method, a fatty acid having an odd carbon number can be synthesized, and is industrially used. . Fatty acid residues derived from synthetic fatty acids obtained by these methods and the like can also be used in the present invention. An R group similarly derived from an aliphatic residue represented by the formula (1) can be used in the present invention.

Fatty acids derived from these animal and vegetable oils or synthetic fatty acids Alternatively, the R groups derived therefrom may be used alone or as a mixture of two or more.

R ¹ bonded to the oxyethylene group in the general formulas (I), (II) and (III) is selected from hydrogen and a methyl group, and hydrogen and a methyl group are independently introduced while bonded to the oxyethylene group. And may be introduced in a random or block-like combination.

X ₁ , x ₂ , y ₁ , y of the general formulas (I), (II) and (III)
₂ , y ₃ , z ₁ and z ₂ represent the average number of moles of oxyethylene group added, and are each in the range of 1 to 20, preferably 3 to 15.

N in the general formula (II) represents an average number of methylene groups, and 2
３3.

As the aromatic polyester polyol, a monomer or a condensate obtained by condensation-polymerizing 1 to 50 monomers with the monomer (here, simply referred to as “aromatic polyester polyol”) is usually used. Examples of inexpensive aromatic polyester polyols that are currently commercially available include, for example, resin polyols of Herates' Terate ™ (Re
sin Polyol), Dixie Chemical's D400 Polyol ™ resin polyol, Jim Walter Reserch Coporation
Famol 250 ™ resin polyol, UCC NIAX A
There are those such as PP315 ™ resin polyol. Also,
It has begun to be manufactured by domestic polyurethane resin raw material manufacturers. For example, there is HIT-15 of Harima Kasei Kogyo Co., Ltd.

Although the details of the production method and structure of these commercially available aromatic polyester polyols are unknown, for example, by-products generated in the oxidation step of p-xylene during the production of terephthalic acid or dimethyl terephthalate, or It is presumed that they are produced by the reaction of these bottom products with diethylene glycol or propylene glycol. It is presumed that the structure of these aromatic polyester polyols is as shown below.

Here, n ₁ is 0 to 50, preferably 1 to 40, more preferably 1 to 20, R ₁₁ is hydrogen or a methyl group, and the average value of p and q is 1 to 10, respectively. Or Here, n ₂ is 1 to 20, R ₁₁ is hydrogen or a methyl group, p 1
And q1 have an average value of 1 to 5, respectively.

Alternatively, a mixture of these may be considered, and one having a structure other than this may be sufficiently considered, but the details are unknown.

Fluorocarbon is a blowing agent used for urethane resin foam, and is inert to the reaction between the polyisocyanate compound and the polyol compound. A typical Freon gas used as a blowing agent is trichlorofluoromethane (CCl ₃ F,
Boiling point 23.8 ° C, abbreviated as Freon 11. ). Boiling point is 2
Since the temperature is 3.8 ° C., it is highly volatile at the time of blending the raw materials, but can be handled in liquid form, and at the time of foaming, it is vaporized by the reaction heat generated by the reaction between the raw material polyisocyanate compound and polyol to form foam.

If it is desired to foam the foam at a temperature higher than the bubble formation temperature of Freon 11, trichlorotrifluoroethane having a slightly higher boiling point (CCl ₂ F-CClF ₂ , boiling point of 47.6 ° C.
Abbreviated as 113. ) Is used alone or mixed with Freon 11. Also, dichlorodifluoromethane (CCl ₂ F ₂ ,
Boiling point-29.8 ° C, abbreviated as Freon 12. ) Is also used as a foaming agent, but since the boiling point is as low as −29.8 ° C.,
7 kg / cm ² ). Using this Freon 12,
Pressurized foaming equipment is required, but when the foaming raw material is mixed and discharged from the nozzle of the foaming machine, when returning from the pressurized state to normal pressure, this Freon 12 immediately vaporizes and becomes foamy, and Freon 11 was used. In this case, the raw material mixture of the liquid A and the liquid B at the time of foaming behaves differently from foaming in liquid form, and the foam properties also show different physical properties. Usually, it is used in combination with Freon 11 and is often blended at a ratio of about three times the weight of Freon 11. In this case, Freon gas is vaporized firstly, Freon 12 having a low boiling point is vaporized and then reacted. This occurs twice because the CFC 11 is vaporized by the generation of heat, and undergoes a two-stage foaming process.

Other blowing agents include water and the like, but in terms of the amount used, Freon gas is more often used. Water reacts with the urethane resin raw material polyisocyanate compound to generate carbon dioxide gas,
This carbon dioxide serves as a blowing agent. However, when water is used as a blowing agent, the isocyanate compound is consumed, and a urea bond is formed in the urethane foam structure, and the foam becomes hard. It is often used in small quantities as an agent.

As a blowing agent, this CFC 113 and 12, or
Further, it is generally considered that the case using water or the like is often a special case.

Freon in, the addition to monochloro difluoromethane (CHClF _2, boiling point -40.8 ° C., Freon 22) dichlorotetrafluoroethane (CClF ₂ -CClF _2, boiling point 3.6 ° C., Freon 1
14) and the like, but of course, these Freon gases may be used alone or in combination with Freon 11 or the like as a foaming agent for the urethane resin foam.

The amount of CFC varies depending on the type of urethane resin foam, for example, the type of rigid urethane foam in which cells of the foam are independent. That is, the ratio differs depending on the ratio between the NCO group of the raw material polyisocyanate compound and the OH group of the polyol compound (NCO / OH ratio, this ratio is abbreviated as INDEX ratio). What is generally called urethane foam has an INDEX ratio of about 1.05 to 1.2, and usually 30 to 50 parts by weight based on 100 parts by weight of the polyol compound as the raw material. Those with an INDEX of 3.5 or more are generally called isocyanurate foams or nullate foams,
Freon is blended in an amount of about 130 parts by weight or more.

What is generally called urethane foam has elasticity, the foam is not brittle, and has high physical properties.
However, what is generally referred to as isocyanurate foam or nullate foam has a brittle foam, and when rubbed with a hand, the surface of the foam collapses and the powder sticks to the finger. When the INDEX ratio is further increased, the foam becomes so brittle that a character can be written on the foam surface with a finger, or the entire surface collapses.

However, in view of the physical properties of inevitability, NCO / OH IN
The higher the DEX ratio, the more difficult it is to burn, and what is generally called this isocyanurate foam or nullate foam is relatively incombustible. However, what is generally called urethane foam having a low INDEX ratio has a disadvantage that it is very flammable.

Urethane foam produced using aromatic polyester polyol as a raw material has excellent physical properties that urethane foam usually has, and because it has an aromatic ring in its chemical structure, it is easily carbonized and hardly burns. There is also a great demand from users for blending a large amount of this aromatic polyester polyol with a urethane resin foam to make it more difficult to burn.

〔The invention's effect〕

The higher aliphatic amine-based polyol which is a solubilizing accelerator for chlorofluorocarbon of the present invention can blend an aromatic polyester polyol having almost no compatibility with chlorofluorocarbon in a larger amount than ever before, and furthermore, a mixture of the liquid B composition can be mixed with chlorofluorocarbon. Long-term stable storage without separation. Further, this B solution is so-called A
A urethane resin molded product obtained by reaction molding with a liquid has excellent physical properties and good flame retardancy.

〔Example〕

Next, the present invention will be described in detail with reference to examples. In addition, the evaluation of the performance of accelerating the solubilization of CFCs of the present invention,
The test was performed according to the following “Solubilizing ability evaluation test method”. Test methods for evaluating the physical properties of the foam are also shown below.

(Solubilization ability evaluation test method)

An aromatic polyester polyol and a solubilizing agent are weighed at a predetermined ratio, heated to 60 to 70 ° C., and sufficiently stirred and mixed. After mixing uniformly, allow to cool at room temperature, about 100 ml in internal volume
The mixed polyol test solution and Freon 11 are weighed so as to have a predetermined mixing ratio in a pressure-resistant glass container. During this measurement, measure the amount of volatile Freon 11 slightly and volatilize it so that the air in the container is replaced with this Freon gas, shake vigorously to mix the test solution and Freon, and use it as a valve for a pressure-resistant glass container. Seal with.

After sealing with a valve, bring this mixture to about 60 ° C,
Heat for 2 hours, shake and mix evenly.

Judgment is made occasionally with the pressure-resistant glass container containing this test solution.
The solution is allowed to cool slowly while being shaken, and is allowed to stand still after one day.

(Judgment criteria)

 ：: The test solution had no separation of CFCs, and was a clear transparent liquid. ：: The test solution had no separation of CFCs, but was translucent.

[Apparent Density] Conforms to JIS A9514 "Rigid Urethane Foam Insulation Material" Specimens are taken from those that have passed for at least 24 hours after foaming, and their dimensions are 50 x 50 x 50 mm.

[Closed cell rate] ASTM D2856 "OPEN CELL CONTENT OF RIGI
D CELLULAR PLASTICS BY THE AIR PYCNOMETER "A test piece is taken from a sample that has passed 24 hours or more after foaming, its dimensions are 25 × 25 × 25 mm, and it is obtained from the following equation using a Beckman air-comparison hydrometer.

V _a : volume of sample piece V _b : volume blank value of hydrometer V _c : reading of closed cell volume However, this reading of closed cell volume V _c also includes the cell volume of foam.

(Compressive strength)

JIS A9514 "Rigid urethane foam heat insulating material" Test pieces were collected from those that had passed 24 hours or more after foaming, the dimensions were 50 x 50 x 50 mm, and the compression rate was set using Tensilon UTM5000 manufactured by Toyo Baldwin Co., Ltd. 10mm /
Perform the test in min and determine from the following formula.

Here, P is the load (k
g) If no yield point occurs, load at 10% strain (kg). A is the pressure receiving area (cm ² ) of the test piece.

The physical properties of urethane foam usually have directionality. For example, in the case of this compressive strength, the compression direction is parallel to the foaming direction of the foam (indicated by the symbol and called vertical direction) or at right angles. (Represented by the symbol of 、 and called the horizontal direction). Generally,
When the compression strength is compressed at right angles to the foaming direction (⊥, horizontal direction), the compression strength becomes about 1 / of that when compressed in parallel (, vertical direction).

[Dimensional stability] In accordance with ASTM D2126 Test specimens were collected from those that had passed 24 hours or more after foaming, their dimensions were 50 × 50 × 50 mm, and the temperature was -20 ° C.
Tested at either 70 ° C, 70 ° C and 95% relative humidity or 100 ° C for 24 hours,
Examine dimensional changes and appearance changes. For the dimensional change, in the case of urethane foam, the dimensional change rate (%) in the direction parallel to the foaming direction (longitudinal direction) and in the direction perpendicular to the foaming direction (⊥, horizontal direction) is determined. judge.

(Judgment criteria)

 ：: No change in strain or the like was observed in the test piece.

Δ: Deformation such as slight distortion is observed in the test piece.

X: The test piece is remarkably deformed.

[Combustion test] JIS A9514 "Rigid urethane foam heat insulating material" Test specimens were collected from those that had passed for 24 hours or more after foaming, the dimensions were 150 x 50 x 13 mm, and they were placed horizontally in a test specimen stationary frame. The test piece is set on a 48 mm wide Bunsen burner with a fish tail light, using propane gas as the ignition source.

In the test, the inner flame of a propane gas fire was about 6.5 mm and the outer flame was about 38 mm, and this flame was applied to the end of a test piece placed horizontally for 60 seconds. After the flame has been applied for 60 seconds, the flame of the Bunsen burner is kept away and the test piece is burned until the flame disappears spontaneously. The measurement is performed by measuring the time (sec) from the time when the flame is applied to the test piece to the time when the flame of the test piece disappears and the longest burning distance of the burned portion of the test piece. Those with a burning time of less than 120 seconds and a burning distance of 60 mm or less are acceptable. When comparing the flame retardancy, the comparison is made based on the magnitude of the measured value.

[Oxygen index] JIS K7201 "Test method for combustion of polymer materials by the oxygen index method" Minimum oxygen concentration (volume%) in the mixed gas necessary for the material to sustain combustion in a mixed gas stream of oxygen and nitrogen Is referred to as the oxygen index of this test material, a test piece is taken from a sample that has passed 24 hours or more after foaming, and its dimensions are 150 × 6.5 ×
3.0 mm, and test with a candle burning tester manufactured by Toyo Seiki Seisaku-sho.

The oxygen concentration in the air is 21% by volume, and the flame retardancy is determined based on the oxygen index based on this. In other words, a higher oxygen index indicates higher flame retardancy, and the higher the oxygen concentration required for the material to continue burning, and the lower the oxygen concentration, the easier it is to extinguish a fire. If the value is small, the flame retardancy is low, indicating that once the fire starts, it is not easily extinguished.

(Reference example)

Three commercially available aromatic polyester polyols were obtained, and their solubility in CFCs was examined. The solubility test method was performed in accordance with the “solubilization ability evaluation test method”, which is an evaluation test method for the performance of accelerating the solubilization of CFCs of the present invention. That is, a test was conducted by blending 5 to 50 parts by weight of CFC 11 with respect to 100 parts by weight of the aromatic polyester polyol, and the results are shown in Table 1.

 Judgment was performed after standing at room temperature for 2 months.

Usually, the compounding amount of Freon 11 is a so-called urethane foam, the INDEX range of the NCO / OH ratio generally called 1.0
In the case of 5 to 1.2, it is usually in the range of 30 to 50 parts by weight with respect to 100 parts by weight of the raw material polyol compound or the B solution containing the polyol compound, and NCO / OH called a nurate foam. If the ratio INDEX range is 3.5 or more,
It is in the range of 70 to 130 parts by weight or more.

Therefore, the solubility of CFC 11 in the polyol is required to be at least 30 parts by weight or more based on 100 parts by weight of the polyol. Considering that it is used as a raw material polyol for a nurate foam, it is necessary that the solubility of this CFC 11 be higher.

Here, although the solubility of the aromatic polyester polyol with respect to Freon was examined as few as three, it can be seen that all of the aromatic polyester polyols have low solubility in Freon.

In the following examples, among the three aromatic polyester polyols described above, NIAX APP315 of UCC, which has the lowest solubility for chlorofluorocarbon, is used as the target aromatic polyester polyol in the examples. Abbreviated.

Further, "... oil amine", "... oil diamine" and "... fatty amine" are obtained by using "... oil amine" and "... fatty amine" as natural raw materials. Represents a higher aliphatic amine represented by the general formula (I) or (II) having an R group, and "... oil amide" is also obtained by using "... oil" as a natural raw material. Represents a higher aliphatic amide represented by the general formula (III) synthesized from the fatty acid represented by the obtained R ² COOH.

[Example 1] Behenylamine E15 of higher aliphatic amine-based polyol
[Raw fatty acid: behenyl fatty acid using rapeseed oil as a raw material, alkyl distribution: carbon number 22 or more, about 80%, ethylene oxide addition mole number: 15], to promote the solubilization of CFCs to APP with almost no CFC solubility The results were evaluated, and the results were shown as Example 1 and shown in Table 2.

 Judgment was performed after standing at room temperature for 3 months.

As a comparative example, tallow amine E15 mol adduct [raw fatty acid: tallow fatty acid using tallow as a raw material, alkyl distribution: 24% having 18 carbon atoms, 37% of 18 carbon atoms having one unsaturated bond and 30% of 30 carbon atoms %, Number of moles of ethylene oxide added: 15], and the results are shown in Table 2 as Comparative Example 1.

The performance required as a solubilizer for CFCs with respect to the aromatic polyester polyol is that the amount of the solubilizers to be added is as small as possible, and that as much as possible CFCs can be solubilized. Further, a mixed liquid containing Freon, which is referred to as a so-called Liquid B, can be stored in this liquid B state for as long as possible without causing separation of Freon. Of course, it is required that even if the urethane resin molding is performed using the liquid B stored for a long period of time, there is no decrease in physical properties and the like.

The criterion for determining the solubilization accelerator in the present invention is based on the fact that CFC 11 can be solubilized by 30 parts by weight or more with respect to 100 parts by weight of a mixed polyol obtained by mixing a solubilization accelerator and APP of an aromatic polyester polyol. Then, it was evaluated whether a small amount of the solubilization accelerator could be solubilized over a wide range.

From Table 2, even if the addition amount of the solubilizing accelerator is reduced to 10 parts by weight and the aromatic polyester polyol APP is blended at a high ratio of 90 parts by weight, the solubilizing accelerator of the present invention, behenylamine E15, And 30 parts by weight of CFC11, and was stable without causing separation of CFC for a long period of three months. When 30 parts by weight of Freon 11 was added to the adduct of tallowamine E15 mol of the comparative example, separation of Freon occurred after one day of blending, not to mention three months later, of course.

In addition, 35 parts by weight of SU464, a sucrose polyether polyol manufactured by Mitsui Toatsu Chemicals, Inc., was mixed with 65 parts by weight of the mixed polyol obtained by mixing behenylamine E15 and APP at a ratio of 1: 9, and further, a foam modifier Water, 1.5 parts by weight of SH193, a silicone surfactant, a foam stabilizer from Toray Co., Ltd., and TMHD, a lower tertiary amine urethanization catalyst, from Mitsui Toatsu Chemicals Co., Ltd. Liquid B is prepared by mixing Freon 11 manufactured by Daikin Industries, Ltd.

The mixing amount of Freon 11 is different from this B solution and this B solution.
Mitsui Toatsu Chemical Co., Ltd. so that the NCO / OH INDEX ratio is 1.1
CR200, which is crude MDI of isocyanate produced, is blended so as to be 13% of the total amount with the liquid A to be measured and prepared. Therefore, although the amount of the chlorofluorocarbon varies depending on the difference in the OH value of each polyol, approximately 33 parts by weight is added to 100 parts by weight of the mixed polyol.

The separately prepared solution B and solution A were mixed with high-speed stirring at room temperature for 7 to 8 seconds and immediately heated to 45 ° C.
Transfer to a closed aluminum foam container of 00 x 50 mm, cover with lid, and foam the panel. When foaming the panel, seal the lid so that it will not lift due to the foaming pressure of the foam,
Insulate for 20 minutes in a thermostat with air circulation at 45 ° C. 45 minutes for 20 minutes
After holding the foam, demold the foam.

Here, in order to see the effect of the present invention, the closed cell rate, which is a typical physical property of urethane foam, was measured. The measurement is
Two days after foaming of the panel foam. This is because the evaluation of the physical properties is usually performed on a foam that has passed 24 hours or more after foaming, and the physical properties of the foam are almost stable after 24 hours.

From Table 2, it can be seen that the closed cell rate of the panel foamed foam of the example in which behenylamine E15, which is the higher aliphatic amine-based polyol of the solubilization accelerator of the present invention, is as high as 96.2%. There was no decrease in the porosity.

If the closed cell rate is high, this fluorocarbon gas, which has a very low thermal conductivity and is also a nonflammable gas, can be efficiently trapped in the foam cells. For example, when used as a heat insulating material for building materials, the efficiency of heat insulation increases by that much, the thickness of the heat insulating material can be reduced, and even if it burns due to fire, it will be difficult to burn The effect is expected.

On the other hand, beef tallow amine foam-molded in the same manner as in the above example
It can be seen that the value of the closed cell ratio is low in the comparative example in which the E15 mole adduct is blended. That is, when used as a heat insulating material for building materials, the closed cell rate is low, so the heat insulating efficiency is correspondingly low. It is necessary to increase the thickness of the material. It is also understood that the flame retardancy is inferior to those of the examples.

Example 2 Sardine oil amine as higher aliphatic amine-based polyol
E15 [raw fatty acid: fish oil fatty acid using sardine as a raw material, alkyl distribution: about 90% having 20 to 22 carbon atoms, ethylene oxide addition mole number: 15], behenylamine E15 of Example 1, and Behenylamine E7 obtained by adding 7, 10, 20, and 25 moles of ethylene oxide to behenylamine, respectively.
Behenylamine E10, behenylamine E20 and behenylamine E25, sardine and squid oil amine E15 [raw fatty acid: sardine and squid as raw materials for fish oil fatty acids, respectively:
1 mixed fatty acid, alkyl distribution: about 8 with 20 or more carbon atoms
0%, ethylene oxide added mole number: 15], synthetic fatty acid amine E15 [raw material fatty acid: synthetic fatty acid, alkyl distribution: about 73% having 20 to 30 carbon atoms, ethylene oxide added mole number: 15], behenyl of Example 1 After addition of 2 moles of propylene oxide to the amine, besenylamine P2 / E13 obtained by adding 13 mole blocks of ethylene oxide, and sardine oil diamine E15 and 11 sardine oil amide E15 synthesized using the same raw material fatty acid as aromatic compounds. The ability of the polyester polyol to promote solubilization of CFCs with respect to APP was evaluated. The results are shown in Table 3.

The evaluation was 30 parts by weight of the solubilizing accelerator, 70 parts by weight of the aromatic polyester polyol APP, and 100 parts of the mixed polyol.
50 parts by weight of Freon 11 was blended with respect to parts by weight, and the judgment was carried out after allowing to stand at room temperature for 3 months.

One of the required performances as a solubilizing accelerator for chlorofluorocarbon with respect to the aromatic polyester polyol is that the amount of the solubilizing accelerator to be added is as small as possible and that a large amount of chlorofluorocarbon can be solubilized.

From Table 3, it can be seen that even when the amount of the solubilizing accelerator added is 30 parts by weight and the aromatic polyester polyol APP is blended at a ratio of 70 parts by weight, the higher aliphatic amine-based polyol which is the solubilizing accelerator of the present invention is obtained. All were able to solubilize 50 parts by weight of Freon 11, and were stable without flon separation for three times.

However, the comparative examples described in Table 3 were obtained by selecting typical surfactants, or representative monools, diols, triols and tetraols from general-purpose polyether polyols and the like, and In this comparative example, most of the flon was separated immediately after blending 50 parts by weight of flon 11, and after 3 months, all of the flon was separated. Was.

In addition, except that the mixing ratio in the mixed polyol of the solubilizing accelerator and APP mentioned as the present invention and Comparative Example was 3: 7,
Under the same conditions as in Example 1, panel foaming was performed in an aluminum closed foam container, and closed cells were measured in the same manner as in Example 1.
Table 3 shows the results.

From Table 3, the solubilizing accelerator of the present invention shows a good value of the closed cell rate, and from this, the solubilizing accelerator of the present invention shows that the foam has heat insulating properties or physical properties such as flame retardancy. It will be determined that there will be no effect of lowering the value.

However, the solubilization accelerators listed in the comparative examples do not have such a high closed cell rate.

That is, it can be seen that the solubilizer of the comparative example adversely affects physical properties such as heat insulation and flame retardancy.

[Example 3] The blending amount of Freon 11 was 50 parts by weight in Example 2, but here, 65 parts by weight was used to evaluate the solubilization accelerator of the present invention. That is, 30 parts by weight of the solubilization accelerator of the present invention and a mixed polyol of 70 parts by weight of the aromatic polyester polyol APP were prepared, and the mixed polyol 10 was prepared.
By mixing 70 parts by weight of Freon 11 with respect to 0 parts by weight, the ability of the aromatic polyester polyol to promote solubilization of Freon with respect to APP was evaluated. The results are shown in Table 4.

The higher aliphatic amine-based polyols evaluated as the solubilizing accelerator of the present invention were sardine oil amine E15 of Example 2, behenylamine E15 of Example 1, bebenylamine E20 of Example 2, sardine / squid oil amine E15, and synthesized. Fatty acid amines
E15, behenylamine P2 / E13, sardine oil diamine E15 and sardine oil amine E15 were used.

 In addition, the judgment was performed after standing at room temperature for 3 months.

From Table 4, as in Example 2, the amount of the
30 parts by weight, the APP of the aromatic polyester polyol is 70 parts by weight, and even if the blending amount of Freon 11 is 65 parts by weight, all the higher aliphatic amine-based polyols that are the solubilizing accelerators of the present invention can solubilize Freon. Was. In addition, the fluorocarbon was stable for 3 months without separation of CFCs.

However, in the case of using the solubilizing accelerator of the comparative example shown in Table 4, separation of the fluorocarbon started immediately after mixing 65 parts by weight of fluorocarbon 11, and was completely separated after three months.

In addition, except that the compounding ratio of the solubilizing accelerator and APP in the mixed polyol described in the present invention and the comparative example in the mixed polyol was set to 3: 7, the panel was formed in a closed aluminum foam container under the same conditions as in Example 1. After foaming, the closed cell ratio was measured in the same manner as in Example 1, and the results are shown in Table 4.

The measured value of the closed cell rate of the foam containing the solubilization accelerator of the present invention is the same as the measured value of the foam of Example 2. This is because the amount of Freon 11 as a foaming agent is
It is blended so as to be a constant amount of 13% of the total weight of the raw materials used for foaming (this is approximately 33% for 100 parts by weight of the raw material mixed polyol). This is because the foaming and molding conditions are set to be the same as those of a general urethane foam.

Generally speaking, the so-called blowing agent Freon 11 blended in urethane foam is a mixed polyol 100 of the raw material.
Although it is 30 to 50 parts by weight with respect to parts by weight, in this example, even if 65 parts by weight of the normal compounding range or more is mixed, the aromatic polyester polyol having almost no solubility of CFC is used.
Because it can contain 70 parts by weight of APP and is stable for a long period of 3 months, for example, the flexibility of urethane foam formulation is greatly expanded, and so-called NURATE, which requires high flame retardancy, is required. It can be said that the possibility of application to the foam formulation is sufficiently revealed.

Also, from Table 4, it can be seen that the solubilizing accelerator of the present invention was obtained in Example 2
, But showed a good value of the closed cell ratio, which indicates that the solubilizing accelerator of the present invention did not exert an effect of deteriorating the physical properties of the foam.

However, the solubilization accelerator mentioned in the comparative example cannot be said to have such a high closed cell rate. That is, it can be seen that the solubilizer of the comparative example has a bad influence on the physical properties of the foam.

[Example 4] One of the performances required as a solubilizing accelerator for chlorofluorocarbon with respect to an aromatic polyester polyol is to form a urethane resin using a so-called liquid B that has been stored for a long period of time without causing chlorofluorocarbon separation. No decrease in physical properties and the like.

Further, it is considered that a urethane foam containing a large amount of an aromatic polyester polyol has high flame retardancy.

Therefore, here, as the solubilizing accelerator of the present invention, behenylamine E15 of Example 1 and sardine oil amine E of Example 2 were used.
15 and the stability of Solution B and B after this stability evaluation.
Using the liquid, urethane foam was subjected to panel foaming in the same manner as in Example 1, and the physical properties and flame retardancy of this foam were evaluated. The results are shown in Table 5.

From Table 5, it can be seen that behenylamine E15 and sardine oil amine E15 of the present invention are aromatic polyester polyol APP, sucrose polyether polyol SU464, foam modifier water, silicone surfactant SH193, and lower tertiary. Solution B was prepared by mixing predetermined amounts with the amine catalysts TMHD and Freon 11, respectively, and stored at room temperature of 20-23 ° C for 2 months. When the stability was checked, no separation of Freon was observed and it was stable. Met.

Further, using the solution B after evaluating the stability, the NCO /
A of CR200 of Crude MD1 so that INDEX ratio of OH is 1/1
Panel foaming was performed using an aluminum closed foam container together with the liquid, and one week after the panel molding, foam properties were evaluated.

In this panel foam, the aromatic polyester polyol APP was blended in a considerably large amount of 50 parts by weight in the mixed polyol, and the foam properties showed good values despite the foaming molding two months after the preparation of the solution B. No decrease in physical properties due to the addition of APP was observed. In other words, the closed cell ratio, which is a measure of heat insulation properties, the compressive strength that indicates the strength of the foam, and the high-temperature, high-humidity dimensional stability measurement that evaluates the possibility of use under severe conditions of high temperature and high humidity The values were high as shown in Table 5.

Further, as shown in Table 5, when the flame retardancy of this panel foam was evaluated, the combustion test of JIS A9514 was naturally clear, and the aromatic polyester polyol was blended in a high proportion without causing separation from Freon. It can be seen that flame retardancy is achieved at a high level, and the measured value of the oxygen index of JIS K7201 also shows a high value.

However, in the comparative example in which tallowamine E15 was blended, the solubilizing ability of CFCs was not so good, so that the physical properties of this foam formed into a panel as in the example were not so good, and the flame retardancy was low. Is also clear in JIS A9514, but from the results of the oxygen index, it can be seen from Table 5 that the flame retardancy is not so high.

From this, it can be seen that the use of the higher aliphatic amine-based polyol which is a solubilizing accelerator for chlorofluorocarbons of the present invention makes it possible to compound a large amount of an aromatic polyester polyol having almost no compatibility with chlorofluorocarbons. Can be stored stably for a long period of time without causing separation of CFCs.
It can be seen that the use of the B liquid can suppress the deterioration of the physical properties of the urethane resin molded product obtained by reaction molding to an extremely small value, and further enhance the flame retardancy of the foam.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 71/02 LQE C08L 71/02 LQE

Claims (1)

(57) [Claims] An aromatic polyester polyol comprising at least one compound selected from the compounds represented by the following general formulas (I), (II) and / or (III) as an essential component: Fluorocarbon solubilizer. Or / and (Where R, R ¹ , R ² , x ₁ , x ₂ , y ₁ , y ₂ , y ₃ , z ₁ , z ₂ , n
Represents the following, respectively. R: linear or branched alkyl group having an average carbon number of 19 to 40,
Hydroxyalkyl group, alkenyl group or hydroxyalkenyl group R ¹ : hydrogen or methyl group (however, hydrogen and methyl group may be introduced in a random or block form) R ² : having an average carbon number of 18 to 39 Linear or branched alkyl group, hydroxyalkyl group, alkenyl group or hydroxyalkenyl group x ₁ , x ₂ , y ₁ , y ₂ , y ₃ , z ₁ , z ₂ : an integer of 1 to 20 n: 2 or An integer of 3)