JP2002212273A - Polyesterpolyol and polyurethane, and their manufacturing methods - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polyesterpolyol having excellent hydrophobicity, a polyurethane which exhibits excellent waterproofness and flexibility, and their manufacturing methods. SOLUTION: The polyesterpolyol has a glycol constituting component having a polyhydric alcohol having a side chain of a hydrocarbon group in the main chain as the essential component and a carboxylic acid constituting component having a dimer acid as the essential component, and a number average molecular weight of 700-4,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester polyol having excellent hydrophobicity, a polyurethane using the same, and a method for producing the same, and exhibits excellent waterproofness while maintaining the conventional flexibility. It can be applied to polyurethane applied products.

[0002]

2. Description of the Related Art Polyurethane compositions have high elasticity, flexibility,
It has excellent wear resistance and is widely used in many fields such as foams, elastomers, films, synthetic leathers, adhesives, and paints.

[0003] Polyurethane compositions are mainly produced from polyhydroxy compounds such as polyester polyols and polyether polyols, polyisocyanates and, if necessary, chain extenders, foaming agents, foam stabilizers and the like. However, among them, those using polyether polyol as a raw material are superior to those using polyether polyol in mechanical properties, abrasion resistance, oil resistance, solvent resistance, but water resistance, waterproof. In many cases, there is a problem that the properties are poor, and the use is restricted.

In order to solve these problems, it is considered effective to reduce the ester group concentration in the polyester polyol. For example, a carboxylic acid having 13 or more carbon atoms, such as dimer acid or hydrogenated dimer acid, and diethylene glycol or ethylene are preferred. Polyester polyols obtained from glycol components such as glycols have been proposed. However,
At present, these polyester polyols do not have sufficient water resistance and waterproofness.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyester polyol having excellent hydrophobicity, a polyurethane exhibiting excellent waterproofness while having flexibility, and a process for producing the same. And

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides a glycol component having a polyhydric alcohol having a side chain of a hydrocarbon group as a main component and a carboxylic acid component having a dimer acid as an essential component, and a number average molecular weight of 700 to 4000. An object of the present invention is to provide a certain polyester polyol and a method for producing the same, and also provide a polyurethane having excellent waterproofness and flexibility obtained by using the same, and a method for producing the same.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester polyol of the present invention comprises, as an essential component, a polyhydric alcohol having a side chain of an alkyl group in the main chain as an essential component, and dimer acid as an essential component, as a carboxylic acid component. And a number average molecular weight of 700 to 4000.

The above-mentioned polyhydric alcohol is a compound having a hydrocarbon group as a side chain in the main chain of the hydrocarbon, and the compound preferably has 3 to 34 carbon atoms, more preferably 3 to 17 carbon atoms. For example, 1,2-propylene glycol, 2-methyl-1,3-propanediol, di-1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3,5-pentanetriol, 2,2,4-trimethyl-1,3-pentane Diol, 2-
Ethyl-1,3-hexanediol, 2,2-dimethyl-3-
Hydroxypropyl-2,2-dimethyl-3-hydroxypropanate, neopentyl glycol, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl- 1,5-pentanediol, 2,2-diethyl-1,3-propanediol,
3-octyl-1,5-pentanediol, 2-ethyl-1,3
-Hexanediol, 3-myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol, 3-
Phenyl-1,5-pentanediol, 3- (4-nonylphenyl) -1,5-pentanediol, 3,3-bis (4-nonylphenyl) -1,5-pentanediol, 1,2-bis (hydroxy Methyl) cyclopropane, 1,3-bis (hydroxyethyl) cyclobutane, 1,3-bis (hydroxymethyl) cyclopentane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane, 1,4-bis (hydroxyethyl)
Cycloheptane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4′-hydroxymethoxycyclohexyl) propane, 2,2-bis (4′-hydroxyed (Xycyclohexyl) propane, trimethylolpropane, etc., and these can be used alone or in combination of two or more.

The above-mentioned polyhydric alcohol having a side chain in the main chain preferably accounts for at least 50% by weight of the alcohol component. If the amount is less than 50% by weight, excellent hydrophobicity may not be obtained. As the alcohol component, other glycols can be used together as long as the effect is not impaired.

Other glycols which can be used in combination may be those generally used in polyester polyols, such as ethylene glycol, 1,3-propylene glycol, diethylene glycol, 1,4-butylene glycol, and 1,5-pentane. Examples include glycols such as methyl glycol, 1,6-hexamethylene glycol, bishydroxyethoxybenzene or p-xylene glycol, and polyfunctional polyhydroxy compounds such as glycerin, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine. .

The dimer acid used in the present invention is a carboxylic acid obtained by polymerization of tall oil fatty acid obtained from sap or cereals. The tall oil fatty acid is a mixture of an unsaturated acid such as oleic acid and linoleic acid and palmitic acid and stearic acid. The carboxylic acid obtained by polymerization is mainly composed of a dibasic acid having 36 carbon atoms, and a small amount of a monobasic acid having 18 carbon atoms (monomer acid) and an acid-base acid having 54 carbon atoms (trimer acid). It is preferable to include them, but they are not particularly limited as long as the effects of the present invention are achieved.

Industrially, a mixture of monomeric acid and trimeric acid is generally used, and depending on the type of purified vegetable fatty acid, a compound having an aromatic ring, a compound having an aliphatic ring, or a linear compound not containing a cyclic substance is used. It becomes a mixture of various structures such as compounds. Either a purified dimer acid alone or a mixture may be used. It is also possible to use a hydrogenated dimer acid obtained by further hydrogenating the dimer acid.

The above-mentioned dimer acid is preferably present in an amount of 50% by weight or more in the carboxylic acid component. 50% by weight
When used as described above, more excellent hydrophobicity can be obtained. As the carboxylic acid component, other carboxylic acids used in general polyester polyols can be used together to the extent that their effects are not impaired.

As the aliphatic dicarboxylic acid which can be used in combination,
For example, malonic acid, succinic acid, maleic acid, fumaric acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, 1,11-undecamethylenedicarboxylic acid, 1,12- Dodecamethylene dicarboxylic acid and the like. Examples of the aromatic dicarboxylic acid include, for example, orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracenedicarboxylic acid and phenanthenedicarboxylic acid, and of course, anhydrides or various derivatives thereof can also be used. These may be used as a mixture of two or more.

In order to prepare the polyester polyol using the above-mentioned various raw materials, a conventionally known esterification technique carried out using a vacuum and / or a catalyst can be employed. Examples of the method include a method of reacting glycols and dicarboxylic acids under normal pressure, a method of esterification under vacuum, and a method of performing esterification in the presence of an inert solvent such as toluene, and then condensing water and a solvent. And azeotropic removal of the compound from the reaction system.

Although it is of course possible to carry out the reaction in a system in the absence of a catalyst, usually, an inorganic or organic acid; Li, Na, K, Rb, C
a, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fc, Co, Ni, Cu, Zr, Pd, Sn, Sb or Pb metal chloride, oxide, hydroxide or acetic acid Fatty acid salts such as oxalic acid, octylic acid, lauric acid or naphthenic acid; alcohols such as sodium methylate, sodium ethylate, aluminum triisopropoxide, isopropyl titanate or n-butyl titanate; sodium phenolate and the like Phenols; or Al, Ti, Zn, Sn, Zr
Alternatively, it is desirable to use all the catalysts used for ordinary esterification and transesterification, such as other organometallic compounds of metals such as Pb.
At this time, the amount of the catalyst used is suitably in the range of 0.00001 to about 5% by weight, preferably 0.001 to 2% by weight, based on the total amount of the raw materials for preparing the polyester diol. The reaction temperature at this time is usually 10
The range is 0 to 250 ° C.

The number average molecular weight of the polyester polyol of the present invention is preferably in the range of 700 to 4000, particularly preferably in the range of 1000 to 2500. Number average molecular weight of polyester polyol is 700 to
If it is 4000, the synthesis itself of the polyester polyol is easy, it has an appropriate viscosity, it is excellent in workability, and its hydrophobicity is appropriately maintained, so that it has good compatibility with other raw materials and is uniform. There is a merit of bringing urethane.

The polyurethane composition of the present invention includes the above-mentioned polyester polyol and polyisocyanate and, if necessary, a chain extender, a foaming agent, a foam stabilizer, a catalyst, a surfactant, a pigment, a dye, a flame retardant, and a stabilizer. , Fillers and plasticizers.

The polyisocyanate which can be used in the present invention is 2,4-tolylene diisocyanate.
2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p
-Xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, (diphenylmethane-4,4'-diisocyanate) 3,3'-dimethyl-diphenylmethane-4,4-biphenylene diisocyanate 3,3-dichloro-4,4-biphenylene diisocyanate, 4,4-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, trizine cyocyanate, ifosalone diisocyanate, cyclohexane diisocyanate, toluidine diisocyanate, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate, There are triphenylmethane triisocyanate and various derivatives thereof.

These polyisocyanates may be used in combination and are not limited thereto. These polyisocyanates are selected according to the desired resin properties.

Using the above raw materials, a polyurethane composition may be produced by various known methods such as a one-shot method and a prepolymer method. In the prepolymer method, a polyol component and a polyisocyanate are preliminarily reacted to obtain a kind of prepolymer, which is then reacted with urethane foam in the presence of a foaming agent, a catalyst, a foam stabilizer and other additives. In producing an elastomer, a chain extender and a polyol component are added to the prepolymer to cause a crosslinking reaction. Alternatively, the one-shot method involves reacting a polyol component with a polyisocyanate in the presence of other additives such as a catalyst, a foaming agent, and a screening agent.

In addition to the bulk polymerization method in which the various components are reacted in a molten state, the urethane reaction is carried out using dimethylformamide, diethylformamide, dimethylsulfoxide,
A solution polymerization method performed in a solvent composed of one or more of dimethylacetamide, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, isopropanol, toluene, xylene, ethyl cellosolve, trichlene and the like can also be used.

In obtaining the polyurethane of the present invention, a polyester polyol obtained from a glycol component having a polyhydric alcohol having a side chain in the main chain as an essential component and a carboxylic acid component having a dimer acid as an essential component is combined with another polyester polyol. Polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol and the like may be used in combination. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like.

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by a methanol removal condensation reaction of a polyhydric alcohol and diethyl carbonate, a phenol condensation reaction of a polyhydric alcohol and diphenyl carbonate, or a ethylene glycol reaction of a polyhydric alcohol and ethylene carbonate. Is mentioned.

The polyurethane of the present invention may contain a catalyst, a foaming agent, a foam stabilizer, a filler, an antistatic agent, a coloring agent, a flame retardant, etc., depending on the required performance. It can be added unless otherwise.

In the present invention, the polyester polyol has excellent hydrophobicity, and the polyurethane using the polyester polyol has the conventional flexibility and the excellent waterproofness. In addition, it can be used in fields requiring mechanical properties.

[0027]

Next, embodiments of the present invention will be described, but the present invention is not limited to these embodiments. In the description, “parts” and “%” are based on weight.

Example 1 337 parts of 1,2-butanediol, 1463 parts of dimer acid and 0.018 part of tetrabutyl titanate as a catalyst were charged, and nitrogen gas was passed therethrough at normal pressure while flowing out condensed water at about 200 ° C. A dehydration esterification reaction was performed to obtain a polyester polyol having an acid value of 0.39 mgKOH / g and a hydroxyl value of 80.2 mgKOH / g. The obtained polyester polyol was analyzed. Infrared absorption spectrum: CO absorption of ester bond 1
Absorption of 730 cm ^-1 terminal OH group 3500 cm ^-1 C-nmr (ppm): 9.673, 9.749
(Methyl group of branched alcohol) 23.631, 23.891, 26.432 (Methylene group of branched alcohol) 72.135, 76.433 (Secondary carbon of branched alcohol) 173.313, 173.971 (Dimer acid) Derived carbon) Number average molecular weight: 1347 and identified. The infrared absorption spectrum was measured using a Fourier-transform infrared spectrophotometer (FT-FT, manufactured by JASCO Corporation).
IR5300) using a KBr plate. The C-nmr (spectrum) was measured with a deuterated chloroform solvent using an NMR measuring device manufactured by JEOL Ltd. (using JNM-EX-270). In addition, the number average molecular weight was determined by fitting the results of GPC (using HLC-8220 manufactured by Tosoh Corporation) to a calibration curve of polystyrene having a standard molecular weight. Next, the hydrophobicity of the polyester polyol was evaluated by the method described below. Table 1 shows the results.

Example 2 337 parts of 2-methyl-1,3-propanediol, 1463 parts of dimer acid and 0.018 part of tetrabutyl titanate as a catalyst were charged, and a polyester polyol was synthesized in the same manner as in Example 1. . The obtained polyester polyol was identified in the same manner as in Example 1. As a result, infrared absorption spectrum: CO absorption of ester bond 1
Absorption of OH groups of 730 cm ^-1 terminal ^{3500cm -1 C-nmr (ppm)} : 13.591,13.86
1 (methyl group of branched alcohol) 32.477, 35.523 (tertiary carbon of branched alcohol) 173.711, 174.247 (carbon derived from dimer acid) Number average molecular weight: 1763, and identified. In addition, its hydrophobicity was evaluated. Table 1 shows the results.

Example 3 234 parts of 1,2-butanediol, 118 parts of diethylene glycol, 1448 parts of dimer acid and 0.018 part of tetrabutyl titanate as a catalyst were prepared.
A polyester polyol was identified in the same manner as in Example 1 in the same manner as in Example 1. As a result, the infrared absorption spectrum and C
-The NMR spectrum had the same absorption as in Example 1, and the number average molecular weight was 1,877. In addition, its hydrophobicity was evaluated. Table 1 shows the results.

Comparative Example 1 388 parts of diethylene glycol, 1412 parts of dimer acid and 0.018 of tetrabutyl titanate as a catalyst
The polyester polyol was synthesized in the same manner as in Example 1, and the hydrophobicity was evaluated. Table 1 shows the results.

Comparative Example 2 242 parts of ethylene glycol, 1558 parts of dimer acid, and 0.018 part of tetrabutyl titanate as a catalyst were charged, and a polyester polyol was synthesized in the same manner as in Example 1 and evaluated for hydrophobicity. Table 1 shows the results.

Comparative Example 3 1,748 parts of 1,2-butanediol, 1052 of adipic acid
Parts and tetrabutyl titanate as a catalyst
Eight parts were charged, a polyester polyol was synthesized in the same manner as in Example 1, and the hydrophobicity was evaluated. Table 1 shows the results.
Shown in

[Evaluation of Hydrophobicity] 10 g of a polyester polyol was weighed and placed in a metallic petri dish and allowed to stand at 80 ° C. and 95% RH in an open state. After 24 hours and 48 hours, the sample is taken out, the water on the metal petri dish is wiped off, and cooled to room temperature, and then the weight is measured. The initial weight was defined as 100%, and the weight increase was calculated.

[0035]

[Table 1]

Example 4 A solution prepared by dissolving 0.15 part of triethylenediamine and 2.0 parts of water in 100 parts of the polyester polyol obtained in Example 1, 1.0 part of a silicone-based surfactant, and stannase octoate In an amount of 0.15 to 0.35 parts, and 33 parts of TDI-80 (NCO index 1)
05), and the mixture was vigorously stirred and poured into an appropriate mold to obtain a polyurethane foam.

Example 5 A polyurethane foam was obtained in the same manner as in Example 4 except that 100 parts of the polyester polyol obtained in Example 2 was used as the polyol.

Comparative Example 4 A polyurethane foam was obtained in the same manner as in Example 4 except that 100 parts of the polyester polyol obtained in Comparative Example 1 was used as the polyol.

Comparative Example 5 A polyurethane foam was obtained in the same manner as in Example 4 except that 100 parts of the polyester polyol obtained in Comparative Example 2 was used as the polyol.

Comparative Example 6 A polyurethane foam was obtained by foaming in the same manner as in Example 4 except that 100 parts of the polyester polyol obtained in Comparative Example 3 was used as the polyol.

<Evaluation of Water Resistance> Each of the obtained urethane foams is cut into a size of 15 × 15 × 30 (thickness) mm. The test piece was formed into a U-shape, sandwiched between two acrylic plates from both sides in the thickness direction in a state of being compressed by 50%, and water was poured into the U-shape so as to have a height of 50 mm. Measure the time until water seeps out. Table 2 shows the results.
Shown in

<Evaluation of Flexibility> JIS K-6401
(25% compression hardness (kg / 314 cm2)). Table 1 shows the results.

[0043]

[Table 2]

[0044]

According to the present invention, there is provided a polyester polyol having excellent hydrophobicity, and a polyurethane obtained by using the same can exhibit excellent waterproofness while maintaining flexibility as before.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J029 AA03 AB01 AB04 AC01 AC02 AD01 AE18 BA07 BA08 BA09 BA10 CA02 FC02 GA11 GA12 HA01 HB01 KE03 4J034 AA01 AA06 BA03 DA01 DB03 DC50 DF16 DF20 HA01 HA06 HA07 HA08 HC02 HC03 HC46 HC13 HC HC52 HC61 HC64 HC66 HC67 HC71

Claims (5)

[Claims] 1. A glycol component having a polyhydric alcohol having a side chain of a hydrocarbon group in the main chain as an essential component and a carboxylic acid component having a dimer acid as an essential component, and having a number average molecular weight of 700 to 4,000. Polyester polyol. 2. A polyhydric alcohol having 3 to 3 carbon atoms in the molecule.
The polyester polyol according to claim 1, which is 17. 3. A polyester polyol, comprising a polycondensation reaction between a glycol component having a polyhydric alcohol having an alkyl group side chain in the main chain as an essential component and a carboxylic acid component having a dimer acid as an essential component. Production method. 4. A polyurethane obtained by reacting any of the polyester polyols of claims 1 and 2 and the polyester polyol obtained in claim 3 with a polyisocyanate as essential components. 5. A process for producing a polyurethane, comprising reacting a polyester polyol selected from the polyester polyols of claim 1 and 2 and the polyester polyol obtained in claim 3 with a polyisocyanate as essential components.